Microparticles comprising a polymer

Abstract

The invention relates to solid polymeric microparticles, the volume median size of which is between 1 µm and 100 µm. The solid microparticles comprise at least one polymer comprising units corresponding to at least one monomer comprising at least one ester group.

Description

[0001] Description

[0002] Title: Microparticles comprising a polymer

[0003] Microparticles comprising a polymer, whether they are bulk microparticles based on a polymer or microcapsules comprising a core and a shell based on a polymer, are widely used in various industrial sectors.

[0004] The properties and uses of microparticles are primarily linked to the polymers that can constitute the bulk microparticles or the shell of microcapsules. Bulk microparticles are used, for example, in coating compositions.

[0005] Microcapsules are used to protect, deliver, and / or control the release of active compounds within a core composition surrounded by a polymer shell. For example, interfacial polymerization processes that form polyurethane-based polymer shells are widely used to encapsulate active ingredients. However, polyurethanes have limited properties and uses, and very low biodegradability.

[0006] The industry still needs alternative microparticles.

[0007] Document EP0230329 describes a monomer comprising a (meth)acrylate group and a caprolactone-type group, and its use as a comonomer in emulsion or suspension polymerization processes.

[0008] Document W00220683 describes, in examples 3, 8, 9, 10, and 12, the formation of microcapsules comprising a core and a shell. The core is an adhesive formed by polymerization of a composition that may contain up to 10% by weight of carpolactone acrylate. The shell is formed from colloidal aqueous compositions. There is a need for alternative particles that may not exhibit adhesive properties.

[0009] US patent 5510169 describes coating formulations for magnetic tapes. These coating formulations include, among other things, as fillers, particles ranging in size from 0.5 to 5 µm, of polymers derived from (meth)acrylic monomers. The monomers comprise at least 50% by weight of a di-(meth)acrylate and at most 50% by weight of a monomer that may be a caprolactone acrylate monomer. There is a need for alternative particles suitable for uses other than fillers.

[0010] Document W02015059024 describes hydrolyzable microparticles and their use in underground hydrocarbon extraction. The particles have a diameter of 0.05 to 10 µm and consist of a copolymer based on acrylamide-type units crosslinked with a 0.01 to 5 mol% multifunctional monomer containing several ester units. The multifunctional monomer can be, for example, monomer F, which has two acrylate groups and several caprolactone units. When a fluid containing the particles is injected into an underground formation, the crosslinking units degrade, allowing the particles to increase viscosity. There is a need for different particles suitable for other applications.

[0011] There is a need for microparticles comprising a polymer that allows for other uses and / or exhibits improved biodegradability.

[0012] The invention addresses at least one of the needs or problems described above, by proposing bulk polymeric microparticles, whose median volume size is between 1 µm and 100 µm, preferably between 1 and 50 µm, characterized in that: - the microparticles comprise at least one polymer comprising at least 50% by weight relative to the total weight of the polymer of units corresponding to at least one monomer A of formula (I):

[0013] CH2=CR 1 (COO-R 2 O-[-CO-CH2-CH2-CH2-CH2-CH2-O-] x -H) (I)

[0014] in which

[0015] - R 1 is a hydrogen atom or a methyl group,

[0016] - R 2 is a linear or branched C1-C6 alkylene group, preferably an ethylene group, and -x is a real number between 1 and 10, preferably between 1 and 3,

[0017] or (II)

[0018] C

[0019]

[0020] H2=CR 1 (CO-[O-CH2-CH2-CH2-CH2-CH2-CO-] x -OH) (II)

[0021] in which

[0022] - R 1 is a hydrogen atom or a methyl group,

[0023] And

[0024] - x is a real number between 1 and 10, preferably between 1 and 3.

[0025] The microparticles can, in particular, be included in a concentrated composition, typically suitable for use in a downstream formulation, for example as an ingredient. The invention also relates to such concentrated compositions.

[0026] The use of the microparticles according to the invention, or concentrated compositions comprising them, as an ingredient in a swallow formulation is also described.

[0027] In particular, it has been found that microparticles can effectively deliver so-called active compounds, for example impregnated in the microparticles or coating the microparticles.

[0028] The invention also relates to the use of microparticles in formulations of lubricants, fuels, raw material mining, purification, materials, coatings, household care, plant protection compositions, optical compositions, compositions for electronic use, textile fiber compositions, textile coatings, adhesives, thermal or acoustic insulation, inks for substrates, or electronic inks.

[0029] In particular, it has been found that the polymer exhibits improved biodegradability. For the purposes of the present invention, the term "concentrated composition" means a set of microparticles that may be substantially pure or mixed with at least one additional compound.

[0030] For the purposes of this invention, the term "microparticles" refers to a set or plurality of unit particles, which may individually exhibit different shapes or morphologies and / or dimensions. The dimensions are therefore typically expressed as distributions or averages. Microparticles have a median volumetric size ranging from 1 µm to 100 µm.

[0031] The median volumetric size of the particles or droplets from which they are formed, also known as D50, corresponds to the particle size defined such that 50% by volume of the particles have a size smaller than D50. The median volumetric size can be determined by light diffraction, with the particles or droplets dispersed in a liquid medium. It can be determined by light diffraction using a laser particle size analyzer. For example, it can be determined by light diffraction using a Malvern MasterSizer® laser particle size analyzer, in particular the MasterSizer® 3000, with the particles or droplets dispersed in a liquid medium.

[0032] For the purposes of the present invention, the term "bulky microparticles" refers to microparticles that are not microcapsules. Bulky microparticles may thus have a homogeneous composition, in particular a homogeneous polymer composition. They are typically free of closed cavities distributed within them and filled with a gaseous or non-gaseous composition. It is specified that massive microparticles may exhibit porosities, i.e., open cavities, which may be homogeneously distributed within them and / or around their periphery. It is noted that the massive microparticles of the invention are distinct from microcapsules having at least one core with a first non-gaseous chemical composition and a polymer shell with a second chemical composition, different from the first, the shell forming an envelope around the at least one core.

[0033] For the purposes of the present invention, the term "between", used with a range of values, includes the bounds of the range of values.

[0034] An important aspect of the microparticles according to the invention is the polymer described above which is contained within the microparticles. This polymer comprises at least 50% by weight relative to the total weight of the polymer of units corresponding to at least one monomer A of formula (I):

[0035] CH2=CR 1 (COO-R 2 O-[-CO-CH2-CH2-CH2-CH2-CH2-O-] x -H) (I)

[0036] in which

[0037] - R 1 is a hydrogen atom or a methyl group,

[0038] - R 2 is a linear or branched C1-C6 alkylene group, and -x is a real number between 1 and 10, preferably between 1 and 3

[0039] or formula (II)

[0040] CH2=CR 1 (CO-[O-CH2-CH2-CH2-CH2-CH2-CO-] x -OH) (II)

[0041] in which

[0042] - R 1 is a hydrogen atom or a methyl group, and

[0043] - x is a real number between 1 and 10, preferably between 1 and 3.

[0044] Monomer A

[0045] In a first aspect of the polymer, monomer A has the formula (III):

[0046] CH2=CH(COO-R 2 O-[-CO-CH2-CH2-CH2-CH2-CH2-O-] X -H) (III)

[0047] in which

[0048] - R 2 is a linear or C1-C6 branched alkylene group, and

[0049] - x is a real number between 1 and 10, preferably between 1 and 3.

[0050] In a second aspect of the polymer, monomer A has the formula (IV):

[0051] CH2=CCH3(COO-R 2 -O-[-CO-CH2-CH2-CH2-CH2-CH2-O-]XH) (IV)

[0052] in which

[0053] - R 2is a linear or C1-C6 branched alkylene group, and

[0054] - x is a real number between 1 and 10, preferably between 1 and 3.

[0055] In a third aspect of the polymer, monomer A has the formula (V):

[0056] CH2=CH(CO-[O-CH2-CH2-CH2-CH2-CH2-CO-] X -OH) (V)

[0057] in which

[0058] - x is a real number between 1 and 10, preferably between 1 and 3.

[0059] In a fourth aspect of the polymer, monomer A has the formula (VI):

[0060] CH2=CCH3(CO-[O-CH2-CH2-CH2-CH2-CH2-CO-] X -OH) (VI)

[0061] in which

[0062] - x is a real number between 1 and 10, preferably between 1 and 3.

[0063] In monomers A with formulas (I), (II), (III), (IV), (V), or (VI), x is often an average number. In this case, x reflects the presence and proportions of at least two monomers Al and A2 with the same formula, except that x is a natural number with different values ​​for Al and A2, respectively. In other words, monomer A can be a mixture of molecules having the same R groups. 1 and R 2 so that x is a real number reflecting the average number of repeating units in all the molecules that make up monomer A used to synthesize the polymer. For example, for a given monomer A, some molecules have a single repeating unit -CO-CH2-CH2-CH2-CH2-CH2-O-, while others have two repeating units -CO-CH2-CH2-CH2-CH2-CH2-O-, so the value of x is a decimal number between 1 and 2 corresponding to the average molar number of molecules in monomer A. In monomers A with formulas (I), (III), or (IV), R 2is often a linear C1-C6 alkylene group. R 2 In this case, R is chosen from methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene. 2 is preferably an ethylene (ethandiyl) group. R 2 can also be a C1-C6 branched alkylene group.

[0064] A particularly preferred monomer A, in which R 1 is a hydrogen atom, R 2 is an ethanediyl group, and x is equal to 2, has formula (VII):

[0065] CH2=CH(COO-CH2-CH2-O-[-CO-CH2-CH2-CH2-CH2-CH2-O-]2-H) (VII)

[0066] In one aspect, monomer A is a mixture of monomers with different formulas. Monomer A may, for example, comprise a mixture of monomers with formula (I) such as R 1 is a hydrogen and monomer of formula (I) such that R 1 is a methyl, or be made up of a mixture of these two monomers.

[0067] Commercially available monomers that can be used as A monomers include, in particular, Sartomer® SR495B, Placcel® FAI, FA2, FA3, FA4, FA5, or FA10L, Placcel® FMI, FM2, FM3, FM4 or FM5, Photomer 4034, Miramer® M100 and SC1010 and SC1033S, Hydroxyethylcaprolactone Acrylate (HECLA), and Hydroxyethylcaprolactone Acrylate (HECLA), marketed by BASF.

[0068] Monomer A may include a mixture of monomers of formula (I) and (II) or be made up of a mixture of monomers of formula (I) and (II).

[0069] Monomer A may also comprise a mixture of monomers of formula (III) and (IV) or be made up of a mixture of monomers of formula (III) and (IV).

[0070] Monomer A may also comprise a mixture of monomers of formula (V) and (VI) or be made up of a mixture of monomers of formula (V) and (VI).

[0071] Monomer A may also comprise a mixture of monomers of formula (III) and (V) or be made up of a mixture of monomers of formula (III) and (V).

[0072] Monomer A may also comprise a mixture of monomers of formula (IV) and (VI) or be made up of a mixture of monomers of formula (IV) and (VI).

[0073] Monomer A may also comprise a mixture of monomers of formula (III) and (VI) or be made up of a mixture of monomers of formula (III) and (VI).

[0074] Monomer A may also comprise a mixture of monomers of formula (IV) and (V) or be made up of a mixture of monomers of formula (IV) and (V).

[0075] When monomer A comprises a binary mixture of monomers with different formulas (I) to (VI), or is itself composed of a binary mixture of monomers with different formulas (I) to (VI), the weight ratio between the two constituents of the mixture can vary. It is generally from 0.1:99.9 to 99.9:0.1, often from 1:99 to 99:1, for example from 10:90 to 90:10.

[0076] In another aspect, monomer A comprises a ternary or quaternary mixture of monomers of different formulas (I) to (VI) or is made up of a ternary or quaternary mixture of monomers of different formulas (I) to (VI). In the microparticles according to the invention, the polymer often comprises more than 50% by weight relative to the total weight of the polymer, preferably at least 60%, preferably at least 75%, preferably at least 90%, preferably at least 95% by weight, for example, 90% to 95% or 95% to 96% or 96% to 97% or 98% to 99% of units corresponding to monomer A. In a particularly preferred aspect, the polymer comprises at least 99% by weight relative to the total weight of the polymer, preferably at least 99.5%, of units corresponding to monomer A relative to the total weight of the polymer.

[0077] In one embodiment of the microparticles according to the invention, the polymer comprises at least 85% by weight relative to the total weight of the polymer, preferably at least 90%, for example from 90% to 97% or from 92% to 96% of units corresponding to monomer A. This embodiment applies in particular when monomer A is of formula (I) or formula (VII).

[0078] In one embodiment the polymer does not comprise, or substantially does not comprise, units corresponding to a multifunctional monomer B.

[0079] Monomer B

[0080] In a first particular embodiment, the polymer further comprises units corresponding to a multifunctional monomer B. The multifunctional character allows these units to crosslink, by linking them, typically linear macromolecular chains, possibly having a comb-like structure, formed of units corresponding to monomer A and possibly other units corresponding to other monofunctional or multifunctional monomers.

[0081] The multifunctional monomer B can be selected, for example, from molecules bearing at least two polymerizable functions with groups included in monomer A, particularly with -OH, -COOH, and / or (meth)acrylic groups. These functions may be selected from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate, and peroxide. In a particular embodiment, the at least two polymerizable functions of monomer B are identical. In a particular embodiment, monomer B has two polymerizable functions. In a particular embodiment, monomer B has two identical polymerizable functions.

[0082] Advantageously, the multifunctional monomer B is a multi(meth)acrylate monomer, such as a multiacrylate or a multimethacrylate, comprising at least two (meth)acrylate groups, such as the acrylate or methacrylate group.

[0083] In a first embodiment, monomer B is a difunctional monomer, having exactly two reactive functions, also referred to as "difunctional monomer B1" or simply "monomer B1". It is preferably a di(meth)acrylate, that is, having exactly two (meth)acrylate groups. The multi(meth)acrylate monomer typically comprises a multivalent group bearing from 2 to 8 methacrylate groups. In the case of a di(meth)acrylate monomer B1, the two methacrylate groups are preferably located at opposite ends of the divalent group.

[0084] The multivalent group can be saturated or unsaturated, linear, branched, alicyclic or cyclic, aliphatic or aromatic.

[0085] The multivalent group comprises carbon and hydrogen atoms and may include one or more heteroatoms selected from oxygen and nitrogen. The multivalent group may therefore include at least one functional group selected from ether, carbonyl, ester, urethane, or amine.

[0086] The multivalent group is, for example, a group derived from a linear, branched or cyclic alkane or from an aromatic compound.

[0087] A multivalent group may include one or more aromatic rings, such as a phenyl group.

[0088] Monomer B may be a monomer designated as a polyol-multi(meth)acrylate, the polyol comprising at least two alcohol functional groups, and preferably the polyol comprising the same number of alcohol functional groups as the number of (meth)acrylate groups. Polyol-multi(meth)acrylates comprise a multivalent group preferably derived from a polyol comprising 2 to 8 alcohol functional groups.

[0089] The polyol, comprising 2 to 8 alcohol groups, can be selected from among the alpha, omega-diols that include a linear or cyclic carbon chain and correspond to a multivalent group derived from a linear alkane. Examples of alpha, omega-diols include C2-C12 alpha, omega-diols, particularly C4-C10 alpha, omega-diols, such as ethylene glycol, propylene glycol, or polyethylene glycol containing at least two ethylene units. Examples of polyethylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, and tricyclodecane dimethanol.

[0090] A polyol can be branched or cyclic. An example of a branched polyol is a branched diol such as 1,3-butanediol, or a branched polyol comprising six alcohol groups such as dipentaerytritol.

[0091] In the case of a B1 di(meth)acrylate monomer, the divalent group can be designated by the term "alkylene" or "alkanediyl." In this case, the B1 di(meth)acrylate monomer is, for example, an alkylene-di(meth)acrylate, which can also be designated as a diol-di(meth)acrylate. Linear alkylene-diacrylates, particularly in the C12-Cl range, and linear alkylene-dimethacrylates, particularly in the C12-Cl range, are well-suited as B1 di(meth)acrylate monomers. The B1 alkylene-di(meth)acrylate monomer can also be referred to as diol-di(meth)acrylate, the diol being, for example, an alpha, omega-diol in the C2-C12 position, and more particularly an alpha, omega-diol in the C6-C10 position. In a particular embodiment, the multivalent group consists of carbon, hydrogen, and oxygen, or of carbon, hydrogen, and nitrogen. For example, the multivalent group is saturated and includes alcohol, ether, and / or amine functional groups.

[0092] Monomer B may, in particular, be free of more than one urethane group. It may, in particular, be free of any urethane group.

[0093] Monomer B1

[0094] Monomer B1 comprises a divalent group bearing a reactive function, preferably a (meth)acrylate group, at each of its ends. The divalent group may be saturated or unsaturated, linear, branched, alicyclic or cyclic, aliphatic or aromatic.

[0095] The divalent group of monomer B1 can comprise carbon and hydrogen atoms and may include one or more heteroatoms selected from oxygen and nitrogen. The divalent group can therefore include at least one functional group selected from ether, carbonyl, ester, urethane, or amine.

[0096] In the first case, the divalent group is a linear, branched, or cyclic alkane derivative designated by the term "alkylene" or "alkanediyl." In this case, the B1 di(meth)acrylate monomer is, for example, an alkylene-di(meth)acrylate, which can also be referred to as a diol-di(meth)acrylate. Linear alkylene-diacrylates, particularly those with a C12-C12 dicarbonate, and linear alkylene-dimethacrylates, particularly those with a C12-C12 dicarbonate, are well-suited as B1 di(meth)acrylate monomers. The B1 alkylene-di(meth)acrylate monomer can also be designated as a diol-di(meth)acrylate, the diol being, for example, an alpha, omega-diol with a C2-C12 dicarbonate, and more specifically, an alpha, omega-diol with a C6-C10 dicarbonate.

[0097] In a second case, the divalent group may include one or more aromatic rings, such as a phenyl.

[0098] In a third case, the divalent group consists of carbon, hydrogen, and oxygen. It is preferably saturated and includes alcohol and / or ether functional groups.

[0099] Monomer B1 may, in particular, be free of more than one urethane group. It may, in particular, be free of any urethane group.

[0100] Examples of difunctional B1 monomers include:

[0101] - 1,6-hexanediol diacrylate (HDDA),

[0102] - 1,6-hexanediol dimethacrylate,

[0103] - 1,10-decanediol diacrylate,

[0104] - 1,10-decanediol di methacrylate (DDDMA),

[0105] - polyethylene glycol dimethacrylate,

[0106] - 1,9-nonanediol dimethacrylate,

[0107] - 1,4-butanediol dimethacrylate,

[0108] - 2,2-bis(4-methacryloxyphenyl)propane, - 1,3-butanediol dimethacrylate,

[0109] - 1,4-butanediol diacrylate,

[0110] - ethylene glycol diacrylate,

[0111] - 1,5-pentanediol dimethacrylate,

[0112] - 1,4-phenylene diacrylate,

[0113] - tetraethylene glycol diacrylate,

[0114] - ethylene glycol dimethacrylate,

[0115] - diethylene glycol diacrylate,

[0116] - triethylene glycol diacrylate,

[0117] - triethylene glycol dimethacrylate,

[0118] - difunctional (meth)acrylated amines,

[0119] - tricyclodecane dimethanol diacrylate.

[0120] In this first particular embodiment and its particular aspects, the polymer may comprise at most 30%, preferably at most 25% by weight, for example from 1% to 20%, of units corresponding to monomer B. The polymer may, for example, comprise at most 30%, preferably at most 25% by weight, for example from 1% to 20%, of units corresponding to the multifunctional di(meth)acrylate monomer B1 relative to the total weight of the polymer.

[0121] Depending on the specific option, monomer B represents 1% to 15% by weight, for example, 1% to 10% by weight, and preferably 3% to 7% by weight, relative to the total weight of the monomers, and possibly the photoinitiator, used to prepare the microparticles. Monomer B1 can, for example, represent 1% to 15% by weight, for example, 1% to 10% by weight, and preferably 3% to 7% by weight, relative to the total weight of the monomers, and possibly the photoinitiator, used to prepare the microparticles.

[0122] Monomer B2

[0123] In a second embodiment, monomer B is a multifunctional multi(meth)acrylate monomer B2, different from a di(meth)acrylate monomer B1, comprising at least two urethane groups and at least two (meth)acrylate groups.

[0124] In particular, it can be a di(meth)acrylate monomer with urethane groups, which can also be referred to as urethane di(meth)acrylate. The chemical structure of urethane dimethacrylate includes, for example, a carbon chain comprising at least two urethane functions and a (meth)acrylate group at each end of the chain.

[0125] In the first case, the monomer B2 is represented by the formula (VIII):

[0126] CH2=CR 3 -CO-OR 4 -O-CO-NH-R 5 -NH-CO-OR 4 -O-CO-CR 3 =CH2(VIII)

[0127] in which- R 3 is a hydrogen atom or a methyl group,

[0128] - R 4 is a linear or branched aliphatic group at C1-C6, preferably an ethyl group, -R 5 is a linear or branched aliphatic group in C6-C12 or an alicyclic group or an aromatic group.

[0129] In this first case, the monomer B2 can be a dimethacrylate diurethane in which the R group 3 is a methyl group, R 4 is an ethanediyl, and the R group 5 is a C6-C10 branched al-kylene, preferably at C8-C10. For example, monomer B2 may correspond to formula (IX) and / or have CAS number 72869-86-4:

[0130] CH2=C(CH3)-COO-(CH2)2-O-CO-NH-CH2-CH(CH3)-CH2-C(CH3)2-(CH2)2-NH-CO-O-(CH2)2-OCO-C(CH3)=CH2(IX)

[0131] In a second case, the monomer B2 can correspond to the formula (X):

[0132] CH2=CR 3 -CO-OR 4 -O-[CO-NH-R 5 -NH-CO-OR 6 -O] y -R 4 -O-CO-CR 3 =CH2(X)

[0133] in which

[0134] - R 3 is a hydrogen atom or a methyl group,

[0135] - R 4is a linear or branched aliphatic group at C1-C6, preferably an ethyl group, -R 5 and R 6 are groups, called chain extenders, linear or branched aliphatic groups in the C6-C12 range, or alicyclic groups, or aromatic groups,

[0136] - y is a real number between 1 and 10, preferably between 1 and 3.

[0137] In a third case, the monomer B2 can be represented by the formula (XI):

[0138] R 8 (R 7 -O-CO-NH-R 5 -NH-CO-OR 4 -O-CO-CR 3 =CH2) n (XI)

[0139] in which

[0140] - R 3 , R 4 , R 5 are defined as before,

[0141] - R 7 is a linear or branched divalent aliphatic group in Cl-ClO that may contain ether, carbonyl, ester or amine functions,

[0142] - R 8 is an n-valent group,

[0143] - n is a real number between 3 and 10.

[0144] In a fourth case, monomer B2 can correspond to formula (XII):

[0145] R 8 (R 7 - O[CO-NH-R 5 -NH-CO-OR 6 -O] y -R 4 -O-CO-CR 3 =CH2) n2 (XII)

[0146] in which

[0147] - R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , n and y are defined as before.

[0148] Monomer B2 according to formula (IX) can be obtained by reacting a diisocyanate compound with an aliphatic monoalcohol bearing a (meth)acrylate group. One isocyanate group reacts with the -OH group of a C1-C6 hydroxyalkyl methacrylate. The second isocyanate group can react with a chain extender R 6bearing a functional group capable of reacting with the isocyanate as an alcohol and another functional group capable of reacting with the aliphatic monoalcohol bearing the (meth)acrylate group as a carboxylic acid -COOH, forming a di(meth)acrylate diurethane. The monomer B2 according to formula (X) can be obtained by reacting three or more diisocyanate compounds with aliphatic monoalcohols bearing a (meth)acrylate group. One isocyanate functional group reacts with the -OH group of a C1-C6 hydroxyalkyl methacrylate. The second isocyanate functional group of the isocyanate compounds reacts with a polyfunctional compound bearing the R groups 7 and R 8 such as a polyol to form a multifunctional poly(meth)acrylate and polyurethane monomer.

[0149] Monomer B2 according to formula (XI) can be obtained by reacting three or more diisocyanate compounds with aliphatic monoalcohols bearing a (meth)acrylate group. One isocyanate function of the diisocyanate compounds reacts with the -OH function of a C1-C6 hydroxyalkyl methacrylate. The second function of the diisocyanate compounds can also react with a chain extender R 6 a difunctional group, one of whose functional groups is capable of reacting with the isocyanate. This functional group can be an alcohol. The second functional group of the chain extender can react with a polyfunctional compound bearing R groups 7 and R 8 This second function of the chain extender can be a carboxylic acid that can react with the polyfunctional compound, which may be a polyol. A B2 multifunctional polyurethane poly(meth)acrylate monomer is thus obtained.

[0150] The diisocyanate compounds that can be used for the preparation of monomer B2 according to formulas (VIII), (IX), (X) and (XI) can be:

[0151] - aliphatics such as hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate,

[0152] - alicyclics such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicy-clohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane;

[0153] - aromatics such as naphthylene diisocyanate, toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate.

[0154] The so-called chain extender groups R 6that can be used for formulas (IX) and (XI) can be linear or branched difunctional aliphatic compounds bearing at the end of the chain a carboxylic acid function and at the other end an alcohol function such as glycolic acid, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, 5-hydroxypentanoic acid or 6-hydroxyhexanoic acid.

[0155] R chain extenders 6 They can also be reaction products between a diol and a dicarboxylic acid, or between a diol and a cyclic ester. Diols that can be used include diethylene glycol, 2,2'-dimethylpropan-1,3-diol, or 1,1'-[(1-methyl-1,2-ethanediyl)bis(oxy)]bis-2-propanol, while the dicarboxylic acid can be hexanedioic acid. Cyclic esters can be lactones such as propiolactone, butyrolactone, valerocaprolactone, or caprolactone. The R group 8is a multivalent group to which n groups, as given in the formulas, are attached by covalent bonds. It preferably comprises carbon and hydrogen atoms and may include one or more heteroatoms chosen from oxygen and nitrogen. The R group 8 can therefore include at least one function chosen from ether, car-bonyl, ester, or amine.

[0156] Polyfunctional compounds bearing R groups 7 and R 8 may be polyols such as alpha, alpha', alpha"-l, 2,3-propanetriyltris(omega-hydroxypoly(oxy(methyl-l,2-ethane-diyl))), pentaerythritol or dipentaerythritol.

[0157] In a third embodiment, monomer B is a B3 monomer selected from multi(meth)acrylates comprising 3, 4, 5, or 6 (meth)acrylate functionalities, such as epoxidized and (meth)acrylated soybean oil (CAS 91722-14-4), or poly(methacrylate) polyols modified with caprolactone motifs, for example, with at least two caprolactone motifs. Examples include dipentaerythritol hexaacrylate modified with 2 to 6 moles of caprolactone (DP2CAHA or DP6CAHA), notably the Etermer® products EM2692 (DP2CAHA) and EM2696 (DP6CAHA) marketed by Eternal.

[0158] It is possible to use binary mixtures of monomers B1 and B2, B1 and B3 or B2 and B3 as monomer B. It is also possible to use a ternary mixture of monomers Bl, B2 and B3 as monomer B.

[0159] Additional examples of multifunctional B monomers include, in particular:

[0160] - allyl methacrylate,

[0161] - N,N'-methylenebisacrylamide

[0162] - 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane,

[0163] - polyethylene glycol diglycidyl ether,

[0164] - N,N-diallylacrylamide

[0165] - 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane,

[0166] - Multifunctional acrylates such as dipentaerythritol pentaacrylate, 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane tri methacrylate,

[0167] - difunctional (meth)acrylated amines,

[0168] - ethylenediamine tetramethacrylate,

[0169] - pentaerythritol triacrylate,

[0170] - pentaerythritol tetraacrylate,

[0171] - acrylates also possessing another reactive function, such as propargyl methacrylate, 2-cyanoethyl acrylate,

[0172] - tricyclodecane dimethanol diacrylate,

[0173] - hydroxypropyl methacrylate,

[0174] - N-acryloxysuccinimide,

[0175] - N-(2-hydroxypropyl)methacrylamide, - N-(3-aminopropyl)methacrylamide hydrochloride,

[0176] - N-(t-BOC-aminopropyl)methacrylamide,

[0177] - 2-aminoethyl methacrylate hydrochloride,

[0178] - monoacryloxyethyl phosphate,

[0179] - o-nitrobenzyl methacrylate,

[0180] - acrylic anhydride,

[0181] - 2-(tert-butylamino)ethyl methacrylate,

[0182] - N,N-diallylacrylamide

[0183] - glycidyl methacrylate,

[0184] - 4-(2-acryloxyaehoxy)-2-hydroxybenzophenone,

[0185] - N-(Phthalimidomethyl)acrylamide,

[0186] - cinnamyl methacrylate.

[0187] In a first particular aspect of this particular embodiment, monomer A comprises a monomer of formula (I) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0188] In a second particular aspect of this particular embodiment, monomer A comprises a monomer of formula (II) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0189] In a third particular aspect of this particular embodiment, monomer A comprises a monomer of formula (III) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0190] In a fourth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (IV) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0191] In a fifth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (V) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 to 6 moles of caprolactone. In a sixth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (VI) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 to 6 moles of caprolactone.

[0192] In a seventh particular aspect of this particular embodiment, monomer A comprises a monomer of formula (VII) and monomer B is a linear alkylenediacrylate, in particular 1,6-hexanedioldiacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0193] In an eighth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (I) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Dimethacrylate or ethylenedimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0194] In a ninth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (II) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Dimethacrylate or ethylenedimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0195] In a tenth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (III) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Dimethacrylate or ethylenedimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0196] In an eleventh particular aspect of this particular embodiment, monomer A comprises a monomer of formula (IV) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Dimethacrylate or ethylenedimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0197] In a twelfth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (V) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Dimethacrylate or ethylenedimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0198] In a thirteenth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (VI) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Dimethacrylate or ethylenedimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0199] In a fourteenth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (VII) and monomer B is a linear alkylenedimethacrylate, in particular 1,6-Hexanediol Di methacrylate or ethylenedi methacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0200] In this first particular embodiment and its specific aspects, the polymer may comprise at most 10%, preferably at most 5% by weight, more particularly at most 2% by weight, for example from 1% to 2% by weight, or from 2% to 3% by weight, or from 3% to 4% by weight, or from 4% to 5% by weight, relative to the total weight of the polymer, of units corresponding to the multifunctional monomer B. In this particular embodiment, the polymer generally comprises at least 0.1% by weight, more particularly at least 0.5% by weight relative to the total weight of the polymer, of units corresponding to the multifunctional monomer B.

[0201] Monomer C

[0202] In a second particular embodiment, the polymer further comprises units corresponding to a monofunctional monomer C. Monomer C typically comprises a single polymerizable function with groups included in monomer A and / or monomer B, in particular with -OH, -COOH, and / or (meth)acrylic groups. Monomer C is distinguished from monomer A. The monofunctional monomer C may be selected, for example, from monomers bearing a function chosen from the group consisting of acrylate, methacrylate, vinyl ether, N-vinyl ether, mercaptoester, thiolene, siloxane, epoxy, oxetane, urethane, isocyanate, and peroxide.

[0203] Advantageously, the monofunctional monomer C is a (meth)acrylate.

[0204] Advantageously, the monofunctional monomer C is an alkyl (meth)acrylate comprising a single methacrylate group, which may also be designated as an alkyl mono(meth)acrylate. It may be selected from linear or branched C1-C22 alkyl acrylates, or linear or branched C3-C22 alkenyl acrylates, or linear or branched C1-C22 alkyl methacrylates, or linear or branched C3-C22 alkenyl methacrylates, the term "alkenyl" denoting a hydrocarbon group which includes at least one unsaturation.

[0205] These may include, for example, linear or branched C2-C22 alkyl acrylates, or linear or branched C2-C22 alkenyl acrylates, or linear or branched C2-C22 alkyl methacrylates, or linear or branched C2-C22 alkenyl methacrylates.

[0206] It can in particular be chosen from C12-C22 alkyl acrylates, linear or branched, or C12-C22 alkenyl acrylates, linear or branched, or C12-C22 alkyl methacrylates, linear or branched, or C12-C22 alkenyl methacrylates, linear or branched.

[0207] Examples include C16-C18 alkyl acrylates, such as stearyl acrylate, or C16-C18 alkyl methacrylates.

[0208] Examples also include C20-C22 alkyl acrylates, such as behenyl acrylate, or C20-C22 alkyl methacrylates.

[0209] Examples also include C12-C14 alkyl acrylates, such as lauryl acrylate, or C12-C14 alkyl methacrylates.

[0210] Other examples include C2-C10 alkyl acrylates or methacrylates, such as ethyl, propyl, n-butyl, tert-butyl, isobornyl, or 2-ethylhexyl acrylates or methacrylates.

[0211] In a particular embodiment, the monofunctional monomer C is stearyl acrylate.

[0212] In a first aspect of this second particular embodiment, the polymer comprises less than 50% by weight, more particularly at most 20% by weight relative to the total weight of the polymer, of units corresponding to the monofunctional monomer C. In this particular embodiment, the polymer generally comprises at least 5% by weight, more particularly a content greater than or equal to 10% by weight relative to the total weight of the polymer, of units corresponding to the monofunctional monomer C.

[0213] In a second aspect of this second particular embodiment, the polymer generally comprises at least 50% by weight, more particularly at least 55% by weight relative to the total weight of the polymer, of units corresponding to the monofunctional monomer C. According to a particular option, the polymer comprises from 60% to 80% or from 65% to 75% by weight of units corresponding to the monomer C relative to the total weight of the polymer.

[0214] Polymer

[0215] In a particular embodiment, the polymer comprises units corresponding to monomer A and units corresponding to monomer B. In a particular embodiment, the polymer comprises units corresponding to monomer A and units corresponding to monomer C. In a particular embodiment, the polymer comprises units corresponding to monomer A, units corresponding to monomer B, and units corresponding to monomer C.

[0216] In a first particular embodiment of the invention, the polymer comprises units corresponding to monomer A and units corresponding to monomer Bl.

[0217] The multifunctional character allows these units to crosslink, by linking them, typically linear macromolecular chains, where appropriate having a comb-like structure, formed of units corresponding to monomer A and possibly other units corresponding to other monofunctional or multifunctional monomers, different from Bl.

[0218] In this embodiment, the monomer Bl can be a monomer B2 as described above, if said monomer B2 is a di(meth)acrylate, that is to say, it has exactly two (meth)acrylate groups.

[0219] It is mentioned that in this first embodiment other units, corresponding to other monomers, noted as D monomers, may be present.

[0220] In a particular embodiment and according to a particular first aspect, monomer A comprises a monomer of formula (I) and monomer Bl is a linear alkylenedi(meth)acrylate, in particular 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,10-decanedioldiacrylate or 1,10-decanediol dimethacrylate, or a polyol-multi(meth)acrylate modified by caprolactone motifs, in particular a dipentaerythritol hexaacrylate modified by 2 moles to 6 moles of caprolactone.

[0221] In a second particular aspect of this particular embodiment, monomer A comprises a monomer of formula (I) such that RI is a hydrogen.

[0222] In a third particular aspect of this particular embodiment, monomer A comprises a monomer of formula (I) such that RI is a methyl.

[0223] In a fourth particular aspect of this particular embodiment, monomer A comprises a monomer of formula (II).

[0224] It is mentioned that the polymer may include groups corresponding to a photoinitiator. The polymer may, for example, contain from 0.1% to 5% by weight of such groups, relative to the total weight of the polymer.

[0225] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0226] from 50% to 99.9% by weight of units corresponding to monomer A,

[0227] from 0% to 10% by weight of units corresponding to monomer B,

[0228] from 0% to 10% by weight of units corresponding to monomer C,

[0229] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0230] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0231] from 75% to 99.9% by weight of units corresponding to monomer A,

[0232] from 0% to 10% by weight of units corresponding to monomer B,

[0233] from 0% to 10% by weight of units corresponding to monomer C,

[0234] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0235] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0236] from 75% to 99.9% by weight of units corresponding to monomer A,

[0237] from 0% to 10% by weight of units corresponding to monomer B, from 0% to 10% by weight of units corresponding to monomer C,

[0238] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0239] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0240] from 90% to 99.9% by weight of units corresponding to monomer A,

[0241] from 0% to 10% by weight of units corresponding to monomer B,

[0242] from 0% to 10% by weight of units corresponding to monomer C,

[0243] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0244] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0245] from 90% to 99.9% by weight of units corresponding to monomer A,

[0246] from 1% to 5% by weight of units corresponding to monomer B,

[0247] from 0% to 10% by weight of units corresponding to monomer C,

[0248] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0249] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0250] from 75% to 99.9% by weight of units corresponding to monomer A,

[0251] from 1% to 5% by weight of units corresponding to monomer B,

[0252] from 1% to 10% by weight of units corresponding to monomer C,

[0253] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0254] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0255] from 90% to 99.9% by weight of units corresponding to monomer A,

[0256] from 1% to 5% by weight of units corresponding to monomer B,

[0257] from 1% to 5% by weight of units corresponding to monomer C,

[0258] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0259] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0260] from 85% to 99.8% by weight of units corresponding to monomer A,

[0261] from 0.1% to 10% by weight of units corresponding to the Bl monomer,

[0262] from 0.1% to 5% by weight of groups corresponding to a photoinitiator.

[0263] In one embodiment, the polymer comprises, relative to the total weight of polymer:

[0264] from 93% to 96% by weight of units corresponding to monomer A,

[0265] from 3.9% to 6% by weight of units corresponding to the Bl monomer,

[0266] from 0.1% to 1% by weight of groups corresponding to a photoinitiator.

[0267] An example of an embodiment is derived from 1,6-hexanediol diacrylate or dipentaerythritol hexaacrylate modified with 2 to 6 moles of caprolactone, used as monomer B1, and monomer of formula (VII) as monomer A. In this example, monomer B1 preferably represents 3% to 7% by weight, preferably 4% to 6% by weight, and monomer A preferably represents 93% to 97% by weight of the mixture of monomers A and B1 used for the synthesis of the microparticles. In this example, the polymer preferably consists mainly of monomer A, monomer B1, and the photoinitiator.

[0268] The invention also relates to the polymer described above, particularly in the form of particles, for example microparticles.

[0269] The microparticles generally comprise at least 50% by weight of the polymer, as described above, relative to the total weight of the microparticles. Preferably, the polymer content is at least 75% by weight relative to the total weight of the microparticles. A polymer content of at least 90% by weight relative to the total weight of the microparticles is particularly preferred. In certain advantageous aspects, the polymer content reaches 95% by weight, or even 99% by weight relative to the total weight of the microparticles.

[0270] Microparticles

[0271] The median volumetric size of the microparticles of the invention is preferably between 1 pm and 50 pm, preferably between 1 pm and 20 pm, for example between 1 pm and 5 pm or between 5 pm and 10 pm or between 5 pm and 10 pm, or between 10 pm and 15 pm, or between 15 pm and 20 pm, or between 20 pm and 30 pm, or between 30 pm and 40 pm, or between 40 pm and 50 pm.

[0272] The microparticles according to the invention generally exhibit substantial biodegradability.

[0273] This is, for example, assessed according to OECD guidelines 301 or 302. They may exhibit biodegradability according to one of OECD guidelines 301A, 301B, 301C, 301D, 301E, 301F, or 302C, for example, greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. The appropriate assessment can be chosen depending on the field of application.

[0274] In particular, they may have a biodegradability value defined according to the OECD guidelines for testing chemicals, following the method described in test no. 301F "Manometric respirometry test" (in particular the document in its version with a single correction of 26 July 2013, available at the following address: https: / / www.oecd.org / content / dam / oecd / fr / publications / reports / 1992 / 07 / test-no-301-ready-biodegradability_g1gh2913 / 9789264070356-fr.pdf), which allows a substance to be classified as "readily biodegradable" if its biodegradability rate reaches at least 60% in an interval of 10 days during the 28 days of the test.

[0275] For example, microparticles may exhibit substantial biodegradability according to OECD guideline 301F, specifically 301F, at 28 days, exceeding 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. Concentrated compositions

[0276] Microparticles can be included in a concentrated composition, solid, liquid or in viscous form, for example in the form of a gel.

[0277] The concentrated composition often comprises at least 15%, for example at least 30% by weight, or at least 40% by weight relative to the total weight of the microparticle composition. It may comprise 15% to 20% by weight of the microparticles, or 20% to less than 30% by weight of the microparticles, or 30% to 40% by weight of the microparticles, or 40% to 50% by weight of the microparticles. Preferably, the concentrated composition comprises at least 50% by weight relative to the total weight of the microparticle composition. In some aspects, the concentrated composition comprises at least 60% or even 80% by weight relative to the total weight of the microparticles composition. In one particular preferred aspect, the concentrated composition comprises at least 90% or even at least 95% by weight relative to the total weight of the microparticles composition.

[0278] At least one other compound that may be present in the concentrated composition can be chosen, for example, from liquid or viscous dispersion carriers or media, such as liquid dispersants, for example an aqueous or oily medium, from particles other than the microparticles according to the invention, for example organic particles, in particular polymeric particles, or inorganic particles, or from compounds introduced during the manufacture of the microparticles. These compounds may be intentionally introduced in order to retain them, at least partially, in the concentrated composition. For example, they may be manufacturing residues from the microparticles according to the invention. The manufacturing residues may be chosen, for example, from unreacted monomers and, where applicable, from at least one constituent of a phase used for the manufacture of the microparticles.A particular example of a phase used for the manufacture of microparticles is the C3 phase described below in the context of the process according to the invention, of which at least one specific constituent may be present in the concentrated composition, for example as a manufacturing residue.

[0279] The content of at least one other compound in the concentrated composition is generally 85% by weight, for example, less than 70% by weight relative to the total weight of the composition. Preferably, this content is less than 50% by weight relative to the total weight of the composition. In some aspects, the content of the other compound in the composition according to the invention is less than 10% by weight, or even less than 5% by weight relative to the total weight of the composition.

[0280] This content may be, in particular, 80% to 85% by weight, or more than 70% to 80% by weight, or 60% to 70% by weight, or 50% to 60% by weight. At least one other compound may be a compound that impregnates the microparticles, partially, totally, or possibly in excess. This may include at least one hydrophobic compound. For example, it may be a viscous compound, possibly a lubricant and / or plasticizer, such as glycerol or an oil.

[0281] In a first specific embodiment, the concentrated composition is in solid form, particularly in powder form. The microparticles of the invention may also be in powder form. When the concentrated composition, or more simply the microparticles, is in solid form, particularly in powder form, it preferably comprises at least 90% by weight relative to the total weight of the composition of microparticles, or of the solid. In this first specific embodiment, the concentrated composition, or more simply the microparticles, may comprise at least 95% or even 99% by weight relative to the total weight of the composition, or of the solid. In a particular aspect of this first specific embodiment, the concentrated composition consists of the microparticles and optionally of microparticle manufacturing residues.The first specific embodiment is particularly advantageous when the concentrated composition includes the massive microparticles as described above.

[0282] In a second specific embodiment, the concentrated composition can also be in the form of a dispersion of microparticles in a liquid medium, in particular an aqueous phase. In this case, it preferably comprises at least 50% by weight relative to the total weight of the microparticle composition.

[0283] In a third embodiment, the concentrated composition may also be in the form of a continuous medium comprising microparticles, which are impregnated, or otherwise swollen, with at least one other compound as described above, preferably to saturation, said compound then filling interstices between the microparticles. In this third embodiment, the concentrated composition may, for example, be in viscous form, for example, in the form of a gel.

[0284] Process

[0285] The invention also relates to a method for preparing microparticles according to the invention, comprising the following steps:

[0286] A) the preparation of an emulsion comprising droplets comprising a hydrophobic phase comprising a monomer composition comprising at least monomer A and a polymerization initiator in a continuous aqueous phase,

[0287] B) polymerization by activation of the polymerization initiator, in order to obtain microparticles comprising the polymer, and

[0288] C) Optionally, washing and / or concentration of the microparticles. The droplets are generally a continuous hydrophobic phase, preferably comprising a monomer composition including at least monomer A and the initiator. In other words, each droplet consists of this continuous hydrophobic phase; the droplets are typically monophasic, typically without any other phase dispersed within them.

[0289] In the process according to the invention, the monomer composition comprises at least one monomer A as described above. Generally, the content of monomer A, expressed as a percentage by weight relative to the total weight of the monomer composition, corresponds to the content of A units in the polymer, as described above. For clarity, the weight of the monomer composition C includes the weight of the initiator.

[0290] In one aspect of the process according to the invention, the monomer composition further comprises at least one monomer B as described above. In this case, the content of monomer B, expressed as a percentage by weight relative to the total weight of the monomer composition, generally corresponds to the content of B units in the polymer, as described above.

[0291] In another aspect of the process according to the invention, the monomer composition further comprises at least one monomer C as described above. In this case, the content of monomer C, expressed as a percentage by weight relative to the total weight of the monomer composition, generally corresponds to the content of C units in the polymer, as described above.

[0292] The invention also relates to the composition of monomers described above, hereinafter referred to as C2.

[0293] In one aspect of the process according to the invention, the polymerization initiator is a photoinitiator. In this case, the polymerization is generally activated by UV light. The photoinitiators usable according to the present invention are known in the art and are described, for example, in "Photoinitiators in the crosslinking of coatings," G. Li Bassi, Double Liaison - Chimie des Peintures, No. 361, November 1985, pp. 34-41; "Industrial applications of photoinduced polymerization," Henri Strub, L'Actualité Chimique, February 2000, pp. 5-13; and "Photopolymers: theoretical considerations and setting reaction," Marc, JM

[0294] Abadie, Double Bond - Chemistry of Paints, No. 435-436, 1992, pp. 28-34.

[0295] These photoinitiators include:

[0296] - o-hydroxyketones, such as 2-hydroxy-2-methyl-l-phenyl-l-propanone, initially marketed for example under the names DAROCUR® 1173 and 4265, IRGACURE® 184, 2959, and 500 by BASF, and ADDITOL® CPK by CYTEC;

[0297] - o-aminoketones, in particular 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-1, initially marketed for example under the names IRGACURE® 907 and 369 by the company BASF;

[0298] Aromatic ketones, marketed for example under the name ESACURE® TZT by LAMBERTI; or thioxanthones, initially marketed for example under the name ESACURE® ITX by LAMBERTI, and quinones. These aromatic ketones most often require the presence of a hydrogen-donating compound such as tertiary amines, and in particular alkanolamines. One example is the tertiary amine ESACURE® EDB, initially marketed by LAMBERTI.

[0299] - o-Dicarbonyl derivatives, the most common representative of which is benzyldimethylketal, initially marketed under the name IRGACURE® 651 by BASF and by the company LAMBERTI under the name ESACURE® KB1, and

[0300] acylphosphine oxides, such as bis-acylphosphine oxides (BAPO) initially marketed for example under the names IRGACURE® 819, 1700, and 1800, DAROCUR® 4265, LUCIRIN® TPO, and LUCIRIN® TPO-L by BASF.

[0301] Among the photoinitiators, we can also mention aromatic ketones such as benzophenone, phenylglyoxylates, such as phenylglyoxylic acid methyl ester, oxime esters, such as [l-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, sulfonium salts, iodonium salts and oxime sulfonates.

[0302] In the process according to the invention, the concentration of initiator, in particular photoinitiator, is generally 0.5% to 5% by weight, often 1% to 4% by weight relative to the total weight of the C2 monomer composition.

[0303] In the process according to the invention, the emulsion droplets generally have a median volume size of between 1 µm and 100 µm, preferably between 1 and 50 µm.

[0304] According to one embodiment of the microparticle preparation process, a process is implemented comprising the following steps:

[0305] a') the addition under stirring of a monomer composition C2 according to the invention into a composition C3, the compositions C2 and C3 not being miscible with each other, the viscosity of composition C2 being between 30 mPa.s and 100000 mPa.s at 25°C and at a shear rate of 10 s -1, for example between 30 and 150 mPa.s or between 150 mPa.s and 500 mPa.s, and preferably greater than the viscosity of composition C3,

[0306] the viscosity of composition C3 being between 50 mPa.s and 100000 mPa.s at 25°C, and preferably being greater than the viscosity of composition C2,

[0307] by which a simple emulsion (E2') is obtained comprising drops of composition C2 dispersed in composition C3;

[0308] b 7 ) where appropriate, the application of emulsion shear (E2'), and

[0309] c 7 ) the polymerization of composition C2, which results in massive microparticles dispersed in composition C3. Preferably, the viscosity of composition C2 at 25°C and a shear rate of 10 s 1 is between 100 mPa.s and 50000 mPa.s, preferably between 200 mPa.s and 25000 mPa.s, and for example between 300 mPa.s and 15000 mPa.s.

[0310] Viscosity is measured using a Haake Rheostress™ 600 rheometer equipped with a 60 mm diameter cone with a 2-degree angle, and a temperature control cell set at 25°C. The viscosity value is read at a shear rate of 10 s 1 .

[0311] During step a'), composition C2 is preferably at a temperature between 15°C and 60°C. During step a'), composition C3 is preferably at a temperature between 15°C and 60°C.

[0312] Under the addition conditions of step a'), compositions C2 and C3 are not miscible with each other, which means that the amount (by weight) of composition C2 capable of being solubilized in composition C3 is less than or equal to 5%, preferably less than 1%, and preferably less than 0.5%, relative to the total weight of composition C3, and that the amount (by weight) of composition C3 capable of being solubilized in composition C2 is less than or equal to 5%, preferably less than 1%, and preferably less than 0.5%, relative to the total weight of composition C2.

[0313] Thus, when composition C2 comes into contact with composition C3 under agitation, the latter is dispersed in the form of drops, called simple drops, the dispersion of these drops of composition C2 in the continuous phase C3 being called emulsion (E2').

[0314] To implement step a'), any type of agitator commonly used to form emulsions can be used, such as a mechanical paddle agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloidal mill, a high-shear disperser, or a high-speed homogenizer.

[0315] According to one embodiment, the viscosity of composition C3 at 25°C is greater than the viscosity of composition C2 at 25°C.

[0316] The viscosity of composition C3 at 25°C is preferably between 500 mPa.s and 100,000 mPa.s.

[0317] Preferably, the viscosity of composition C3 at 25°C is between 3000 mPa.s and 100000 mPa.s, preferably between 5000 mPa.s and 80000 mPa.s, for example between 7000 mPa.s and 70000 mPa.s.

[0318] A very high viscosity of composition C3 can ensure the stability of the emulsion (E2 7 ) obtained at the end of step b').

[0319] Preferably, the interfacial tension between compositions C2 and C3 is low. The low interfacial tension between compositions C2 and C3 also advantageously ensures the stability of the emulsion (E2') obtained at the end of step a').

[0320] The volume fraction of composition C2 in C3 can be varied from 0.05 to 0.5 in order to improve production yield and to vary the average diameter of the microparticles. At the end of this step, the size distribution of the emulsion (E2') is relatively broad.

[0321] According to one embodiment, the ratio between the volume of composition C2 and the volume of composition C3 varies between 1:20 and 20:1, for example between 1:10 and 10:1. Preferably, this ratio is between 1:9 and 3:1, preferably between 1:9 and 1:1.

[0322] According to one embodiment, composition C3 further comprises at least one branched polymer, preferably with a molecular weight greater than 5000 g / mol -1 , and / or at least one polymer with a molecular weight greater than 5000 g / mol -1 , and / or solid particles such as silicates.

[0323] According to one embodiment, composition C3 comprises, at least as a manufacturing intermediate, a polymer with a molecular weight greater than 5000 g / mol -1 , preferably between 10000 g. mol 1 and 500,000 g / mol 1 , for example between 50,000 g. soft 1 and 300,000 g / mol 1 .

[0324] As a polymer with a molecular weight greater than 5,000 g / mol 1 usable in composition C3, we can mention the following compounds, used alone or mixed together: - cellulose derivatives, such as cellulose ethers: methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or methylhydroxypropyl cellulose;

[0325] - polyacrylates (also called carbomers), such as polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly(hydroxyethyl methacrylate) (pHEMA), poly(N-2-hydroxypropyl methacrylate) (pHPMA);

[0326] - polyacrylamides such as poly(N-isopropylacrylamide) (PNIPAM);

[0327] - polyvinylpyrrolidone (PVP) and its derivatives;

[0328] - polyvinyl alcohol (PVA) and its derivatives;

[0329] - poly(ethylene glycol), poly(propylene glycol) and their derivatives, such as poly(ethylene glycol) acrylate / methacrylate, poly(ethylene glycol) diacrylate / di methacrylate, polypropylene carbonate;

[0330] - polysaccharides such as carrageenans, locust bean gum or tara gum, dextran, xanthan gums, chitosan, agarose, hyaluronic acids, gellan gum, guar gum, gum arabic, tragacanth gum, diutan gum, oat gum, karaya gum, ghatti gum, curdlan gum, pectin, konjac gum, starch;

[0331] protein derivatives such as gelatin, collagen, fibrin, polylysine, albumin, casein;

[0332] - silicone derivatives such as polydimethylsiloxane (also called dimethicone), alkyl silicones, aryl silicones, alkyl aryl silicones, polyethylene glycol dimethicones, polypropylene glycol dimethicone;

[0333] - waxes, such as diester waxes (alkanediol diesters, hydroxylacid diesters), wax triesters (triacylglycerols, alkane-l,2-diol, ω-hydroxy acid and fatty acid triesters, hydroxymalonic acid, fatty acid and alcohol esters, hydroxylacid, fatty acid and fatty alcohol triesters, fatty acid, hydroxylacid and diol triesters) and polyester waxes (fatty acid polyesters).The fatty acid esters that can be used as waxes in the context of the invention are, for example, cetyl palmitate, cetyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, cetyl stearate, stearyl stearate, myristyle stearate, cetyl myristate, isocetyl stearate, glyceryl trimyristate, glyceryl tripalmitate, glyceryl monostearate or cetyl glyceryl palmitate; - fatty acids usable as waxes such as cerotic acid, palmitic acid, stearic acid, dihydroxystearic acid, behenic acid, lignoceric acid, arachidic acid, myristic acid, lauric acid, tridecyclic acid, pentadecyclic acid, margaric acid, nonadecyclic acid, heneicosylic acid, tricosylic acid, pentacosylic acid, heptacosylic acid, montanic acid or nonacosylic acid;.

[0334] - fatty acid salts, in particular aluminum salts of fatty acids such as aluminum stearate, hydroxy aluminum bis(2-ethylhexanoate);

[0335] - isomerized jojoba oil;

[0336] - hydrogenated sunflower oil;

[0337] - hydrogenated coconut oil;

[0338] - hydrogenated lanolin oil;

[0339] - castor oil and its derivatives, in particular modified hydrogenated castor oil or compounds obtained by esterification of castor oil with fatty alcohols;

[0340] polyurethanes and their derivatives;

[0341] - styrenic polymers such as styrene butadiene; and

[0342] polyolefins such as polyisobutene.

[0343] According to one embodiment, composition C3 comprises, as a manufacturing intermediate, at least one polymer with a molecular weight greater than 5000 g / mol 1and solid particles. Any mixture of the compounds mentioned above can be used. Step b') of the process consists of refining the size of the emulsion droplets. This may include a fragmentation step.

[0344] This step may consist of applying a homogeneous controlled shear to the emulsion, said applied shear rate being between 10 s 1 and 100,000 seconds 1 .

[0345] According to one embodiment, the drops obtained in step a 7 ) are subjected to a size refinement consisting of subjecting them to a shearing process capable of fragmenting them into new drops of homogeneous and controlled diameters.

[0346] According to one embodiment, in step b 7), the emulsion is subjected to shear in a mixer, which applies a homogeneous controlled shear. Thus, according to this embodiment, step b') consists of applying a homogeneous controlled shear to the emulsion, said applied shear rate being between 1000 s 1 and 100,000 seconds 1 .

[0347] According to this embodiment, in a mixer, the shear rate is said to be controlled and homogeneous, regardless of time, when it reaches a similar maximum value for all parts of the emulsion at a given instant, which may vary from one point in the emulsion to another. The exact configuration of the mixer is not essential according to the invention, provided that the entire emulsion has been subjected to the same maximum shear rate upon exiting the device. Mixers adapted to perform step b 7 ) are described in particular in document US 5,938,581.

[0348] According to this embodiment, during step b'), the emulsion is introduced into the mixer and is then subjected to shear which results in the formation of an emulsion (E2"), which is chemically identical to (E2').

[0349] The difference between (E2') and (E2") is the drop size variance: the drops of (E2 7 ) are polydisperse in size while the (E2") drops are monodisperse, thanks to the fragmentation mechanism described above.

[0350] Preferably, according to this embodiment, the emulsion (E2') is introduced continuously into the mixer, which means that the quantity of emulsion (E2 7 ) introduced at the mixer inlet is the same as the quantity of emulsion (E2") at the mixer outlet.

[0351] According to another embodiment, step b 7 ) consists of applying a shear rate of less than 1000 s to the emulsion (E2) 1This embodiment may be preferred for a viscosity of composition C3 greater than 200 mPa.s, preferably 2000 mPa.s, at 25°C and a shear time of 10 s 1 .

[0352] According to this embodiment, the fragmentation step b') can be carried out using any type of mixer commonly used to form emulsions with a shear speed of less than 1000 s 1 . It is possible to operate in particular under conditions such as those described in patent application FR 1661787.

[0353] According to this embodiment, in step b 7 The emulsion, consisting of polydisperse droplets dispersed in a continuous phase, is subjected to shear, for example in a mixer, at a low shear rate, namely less than 1000 s -1 .

[0354] According to this embodiment, the shear rate applied in step b 7) is, for example, between 10 s 1 and 1000s 1 Preferably, the shear rate applied in step b') is strictly less than 1000 s 1 .

[0355] According to this embodiment, the emulsion droplets can only be efficiently fragmented into fine and monodisperse droplets if a high shear stress is applied to them. The shear stress s applied to an emulsion droplet is defined as the tangential force per unit droplet area resulting from the macroscopic shear applied to the emulsion during its agitation.

[0356] The shear stress σ (expressed in Pa), the viscosity of the C2 composition h (expressed in Pa·s) and the shear rate g (expressed in s⁻¹) -1 ) applied to the emulsion (E2') during its agitation in step b') are related by the following equation:

[0357] s = hg

[0358] Thus, according to this embodiment, the high viscosity of composition C3 allows a very high shear stress to be applied to the emulsion droplets in the mixer, even if the shear rate is low and the shear is inhomogeneous.

[0359] To implement step b') according to this embodiment, any type of agitator commonly used to form emulsions can be used, such as a mechanical paddle agitator, a static emulsifier, an ultrasonic homogenizer, a membrane homogenizer, a high-pressure homogenizer, a colloidal mill, a high-shear disperser or a high-speed homogenizer.

[0360] According to a preferred embodiment, a simple emulsifier such as a mechanical paddle stirrer or a static emulsifier is used to implement step b'). This is possible because this embodiment requires neither controlled shear nor shear greater than 1000 s⁻¹. 1 .

[0361] Step c') of the process consists of the polymerization of the monomers contained in composition C2.

[0362] According to one embodiment, when composition C2 includes a photoinitiator, step c 7 ) is a photopolymerization step consisting of exposing the emulsion (E2") to a light source suitable for initiating the photopolymerization of composition C2, in particular to a UV light source emitting preferably in the wavelength range between 100 nm and 450 nm, and in particular for a duration of less than 15 minutes.

[0363] Step c') is preferably implemented in such a way as to obtain a monomer conversion rate, by weight, greater than 90%, preferably 95%, for example greater than 99%. The operating conditions can be adapted for this purpose, in particular the quantities and / or types of photoinitiator and / or the wavelengths used.

[0364] According to this embodiment, step c') consists of subjecting the emulsion to photopolymerization, which will allow the photopolymerization of composition C2.

[0365] According to one embodiment, step c 7 ) consists of exposing the emulsion (E2") to a light source capable of initiating the photopolymerization of composition C2.

[0366] Preferably, the light source is a UV light source. According to one embodiment, the UV light source emits in the wavelength range between 100 nm and 450 nm.

[0367] According to one embodiment, the emulsion is exposed to a light source for a period of less than 15 minutes, and preferably for 5 to 10 minutes.

[0368] According to another embodiment, when composition C2 does not include a photoinitiator, step c') is a polymerization step, the duration of this step c 7 ) polymerization time preferably being between 8 hours and 100 hours and / or this step c') is carried out at a temperature between 20°C and 80°C.

[0369] According to this embodiment, polymerization is initiated, for example, by exposure to heat (thermal initiation), or by simply bringing the monomers, polymers, and crosslinking agents into contact with each other, or with a catalyst. The polymerization time is then generally longer than several hours.

[0370] Preferably, step c') of polymerization of composition C2 is carried out for a period of time between 2 hours and 100 hours, for example at a temperature between 20°C and 80°C.

[0371] At the end of step c 7 ), we obtain microparticles, typically massive, dispersed in the C3 composition.

[0372] The process may include a step C) of washing and / or concentrating the microparticles. This step typically follows step c 7 ). Thus, according to one embodiment, step c 7 ) is typically followed by a step of 7The washing process involves removing intermediate manufacturing compounds included in C3. This can be done by centrifugation and washing with water or another organic compound as a solvent to purify the microparticles and remove impurities, such as residual monomers. Examples of organic compounds include solvents such as methanol, ethanol, propanol, isopropanol, acetone, MEK, ethyl acetate, and THF. These steps are known to those skilled in the art. The washing process can be carried out in several stages to control the purity of the microparticles, for example, in a manner adapted to the application of the microparticles, particularly from a regulatory standpoint.Several washing and / or purification steps can be performed using an aqueous and / or organic solvent, for example, by resuspension and decantation, by successive cycles of dilution-resuspension-separation, by filtration (e.g., under vacuum, through a membrane, microfiltration / ultrafiltration, or tangential flow filtration), by centrifugation (batch or continuous), by gravity or assisted sedimentation, by column washing (fixed bed or fluidized bed), by co-current or counter-current washing, by dialysis, by liquid-liquid extraction, and / or by washing assisted by mechanical agitation, ultrasound, or any combination of these techniques. This allows for the dispersion of microparticles in an aqueous or organic phase, typically dispersed within such a phase. This can constitute a concentrated composition as described above.According to one embodiment, step c') and / or the washing step is followed by a concentration and / or drying step to obtain a concentrated composition, optionally in powder form. Such steps are known to those skilled in the art. Examples include fixed bed drying, tray / oven drying, vacuum drying, freeze-drying, spray drying, fluidized bed drying, flash / pneumatic drying, drum or belt drying, thin film drying (drop or wipe film), microwave or infrared drying, and processes using supercritical CO2.

[0373] In one embodiment, washing is carried out with ethanol and drying is achieved by spraying a dispersion in water, ethanol, or a mixture. This embodiment makes it possible to obtain high purity, particularly with regard to the quantity of residual monomers such as monomer A, as well as high distensibility in downstream formulations.

[0374] According to one embodiment, the microparticles obtained at the end of step c 7 ) are devoid of surfactant.

[0375] Also described are the microparticles that are obtained or are likely to be obtained by the process that has just been presented.

[0376] Uses

[0377] Microparticles, or the concentrated compositions in which they may be included, can be used in downstream formulations, which are useful in various application areas. In this context, downstream formulations are understood as compositions comprising microparticles or concentrated compositions, used as ingredients, mixed or combined with other compounds and ingredients useful for the application. The microparticles or concentrated compositions are thus introduced into the downstream formulation through mixing processes. Therefore, the weight concentration of microparticles in the downstream formulation is generally lower than the weight concentration of microparticles in the concentrated composition. Specifically, the weight concentration may be less than 30%, 20%, 10%, or 5%. It may also be greater than 0.1% or 1%.

[0378] Examples of downstream formulations or application areas include lubricants, fuels, raw material extraction, purification, materials and coatings (e.g., for construction or industrial products), household care compositions, plant protection products, optics, electronics, textile fibers, textile coatings, adhesives, thermal or acoustic insulation, inks for substrates, electronic inks, flexible substrates (e.g., cellulosic substrates such as paper or cardboard), and packaging plastics (e.g., films or containers). In some areas and applications, microparticles can be used to deliver so-called active compounds, for example, impregnated within the microparticles or as a coating on them.The active compounds may be hydrophilic or hydrophobic, volatile or non-volatile. They may be solid or liquid. They may be in solid or liquid form at a temperature of 25°C and a pressure of 1013 hPa. The compounds impregnated within the microparticles may, together with the microparticles, constitute a concentrated composition, particularly if they are in excess of the microparticles' absorption capacity.

[0379] In one embodiment, the impregnated compounds serve as formulation or manufacturing aids or adjuvants, facilitating the preparation of the final formulations. Examples include solvents or oils. Solvents include aliphatic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, glycol ethers, alcohols, chlorinated solvents, or mixtures thereof. Polar or nonpolar oils or oily phases include vegetable oils such as linseed oil. Examples include ethanol, isopropanol, butyl glycol, isobutanol, ethyl acetate, methoxypropyl acetate, methylamyl ketone, isoamyl ketone, glycerol, and mixtures and combinations thereof.

[0380] In one embodiment, the impregnated compounds have a specific use or activity for an application. These may include active compounds having an effect, particularly in a field selected from the group comprising the therapeutic, agricultural, household cleaning, chemical, paint, fuel, lubricant, bitumen, and drilling muds or fluids fields. They may also include chemical or biological substances, compounds, or materials. They may be selected from, for example, an oil or solvent such as those mentioned above, which can be used as a lubricant, plasticizer, or surface treatment.

[0381] - a crosslinking agent, a hardener, a curing agent (such as a urea derivative), a curing accelerator (such as amide, amine or imidazole derivatives), an organic or metallic catalyst (such as an organometallic or inorganometallic complex of platinum, palladium, titanium, molybdenum, copper or zinc, or salts of metal complexes dissolved in polyethylene glycol or polyethylene glycol derivatives) used to polymerize formulations of polymers, elastomers, rubbers, paints, adhesives, sealants, mortars, varnishes or coatings;

[0382] - a colorant or pigment intended for formulations of elastomers, paints, coatings, adhesives, sealants, mortars or papers;

[0383] - a sunscreen or light protection agent, particularly against UV radiation, for example triazines or screened amines, used especially for improved resistance or tolerance or preservation of properties of downstream formulations or substrates to which they are applied, for example for household care compositions, coating compositions, material compositions,

[0384] - a fragrance, for example intended for detergents such as laundry detergents, household care products,

[0385] - an aroma, a vitamin, an amino acid, a protein, a lipid, a probiotic, an antioxidant, a pH adjuster, a preservative for food compositions and animal feed,

[0386] - a plant extract or an essential oil derivative,

[0387] - a fabric softener, a hydrophilicating agent, a surface treatment agent for detergents, laundry products,

[0388] - an anti-color alteration agent (such as an ammonium derivative), an anti-foaming agent (such as an alcohol ethoxylate, an alkylbenzene sulfonate, a polyethylene ethoxylate, an alkyl ethoxysulfate or an alkyl sulfate) intended for detergents, laundry products and household care products;

[0389] - an optical bleaching agent, also called a color activator (such as a stilbene derivative, a coumarin derivative, a pyrazoline derivative, a benzoxazole derivative or a naphthalimide derivative) intended for detergents, laundry products;

[0390] - a biologically active compound such as an enzyme, a vitamin, a protein, a plant extract, a disinfectant, an antibacterial agent, or an anti-UV agent. Examples of such biologically active compounds include vitamins A, B, C, D, and E, para-aminobenzoic acid, alpha-hydroxy acids (such as glycolic acid, lactic acid, malic acid, tartaric acid, or citric acid), isopropyl isostearate, isopropyl palmitate, oxybenzone, salicylic acid, sorbic acid, sorbitol, triclosan, and tyrosine.

[0391] - a disinfectant agent, an antibacterial agent or an anti-UV agent intended for paints and coatings,

[0392] - a fertilizer, herbicide, insecticide, pesticide, fungicide, repellent or disinfectant intended for use in plant protection products,

[0393] - a flame retardant (such as a brominated polyol like tetrabromobisphenol A, a halogenated or non-halogenated organophosphate compound, a chlorinated compound, a perfluorinated compound, an ammonium polyphosphate, aluminium hydroxide, an antimony oxide, a zinc borate, red phosphorus, melamine or magnesium hydroxide) intended for use in plastics, coatings, paints and textiles,

[0394] - a photonic crystal or photochromophore intended for use in paints, coatings, and polymeric materials forming curved and flexible screens; and - a phase change material (PCM) capable of absorbing or releasing heat during a phase change, intended for energy storage. Examples of PCMs include molten aluminum phosphate, ammonium carbonate, ammonium chloride, cesium carbonate, cesium sulfate, calcium citrate, calcium chloride, calcium hydroxide, calcium oxide, calcium phosphate, calcium saccharate, calcium sulfate, cerium phosphate, iron phosphate, lithium carbonate, lithium sulfate, magnesium chloride, magnesium sulfate, manganese chloride, manganese nitrate, manganese sulfate, potassium acetate, potassium carbonate, potassium chloride, potassium phosphate,rubidium carbonate, rubidium sulfate, disodium tetraborate, sodium acetate, sodium bicarbonate, sodium bisulfate, sodium citrate, sodium chloride, sodium hydroxide, sodium nitrate, sodium percarbonate, sodium persulfate, sodium phosphate, sodium propionate, sodium selenite, sodium silicate, sodium sulfate, sodium tellurate, sodium thiosulfate, strontium hydrophosphate, zinc acetate, zinc chloride, sodium thiosulfate, paraffinic hydrocarbon waxes, and polyethylene glycols.

[0395] Coatings

[0396] The downstream formulation can be, in particular, a coating composition. Microparticles can thus be incorporated into a coating on a substrate. This can notably be a solvent-based coating formulation. Microparticles can be used, in particular, for the gelation, structuring, or rheological modification of solvent-based coating compositions. In such applications, the microparticles are introduced into an organic medium such as a solvent, oil, or mixture, and interact physically and / or chemically with the medium in such a way as to increase viscosity, induce gelation, or impart thixotropic or yield stress behavior suitable for the coating application.Solvent-based coatings can be intended for application by spraying, brushing, rolling, dipping, curtaining or any other conventional coating application technique, and can be formulated for decorative, protective, functional or industrial purposes.

[0397] The medium may comprise one or more organic solvents commonly used in coating formulations, including, but not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, glycol ethers, alcohols, chlorinated solvents, or mixtures thereof. The coating composition may further comprise one or more film-forming polymers or binders dissolved or dispersed in the medium, such polymers including, but not limited to, acrylic, methacrylic, vinyl, polyester, alkyd, polyurethane, polyurea, epoxy, phenolic, silicone, and fluoropolymer polymers, or combinations thereof.Microparticles can be present in sufficient quantity to impart a gel-like or structured behavior to the liquid coating composition prior to application, while allowing the formation of a film upon removal of the medium, for example by evaporation of a solvent.

[0398] In addition to the solvent and polymeric binder, solvent-based coating compositions may optionally contain pigments, fillers, extenders, corrosion inhibitors, UV stabilizers, antioxidants, wetting agents, dispersants, defoamers, flow and leveling additives, adhesion promoters, catalysts, crosslinking agents, or other conventional coating additives. Microparticles can be incorporated during formulation by simple mixing, high-shear dispersion, or other known methods, without requiring chemical modification of the polymeric binder.

[0399] In one embodiment, microparticles are used in solvent-based coating compositions using alkyd resins. Such compositions may comprise one or more alkyd resins derived from polyols, polybasic acids, and fatty acids or oils, optionally modified with urethane, acrylic, or silicone segments. The alkyd resin may be dissolved in one or more organic solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, mineral spirits, white spirits, naphthas, esters, or mixtures thereof. The microparticles may be dispersed within the alkyd-solvent system to control sagging, provide anti-sedimentation properties, or adjust application viscosity, while remaining compatible with the oxidative drying or crosslinking mechanisms typical of alkyd coatings.

[0400] In one embodiment, microparticles are used in solvent-based coating compositions of polyurethanes or polyureas. Such compositions may comprise one or more polyurethane or polyurea polymers formed from polyols and isocyanates, including aliphatic or aromatic isocyanates, and may be single-component or multi-component systems. The solvent phase may comprise ketones, esters, aromatic hydrocarbons, glycol ethers, acetates, or mixtures thereof. The microparticles may be present in the solvent phase before or after polymer formation, conferring controlled rheology, storage stability, or appropriate application behavior without interfering with curing or crosslinking reactions.

[0401] In one embodiment, the microparticles are incorporated into solvent-based coating compositions of acrylic or methacrylic polymers. Such coatings may comprise polymers or copolymers of esters of acrylic acid, methacrylic acid, or related monomers, optionally functionalized with hydroxyl, carboxyl, epoxy, or other reactive groups. The solvent system may include esters, ketones, aromatic hydrocarbons, alcohols, or glycol ethers. The microparticles can be used to gel or structure the acrylic solution, enabling, in particular, high-solids formulations, improved application control, or reduced pigment sedimentation.

[0402] In one embodiment, microparticles are used in solvent-based coating compositions using epoxy resins. Such compositions may include bisphenol A-based epoxy resins, bisphenol F-based epoxies, novolac epoxies, or similar structures, optionally combined with curing agents or hardeners. The solvent phase may include ketones, glycol ethers, aromatic hydrocarbons, esters, or mixtures thereof. The microparticles can provide viscosity control or anti-sedimentation effects in the epoxy solutions or dispersions prior to curing, while remaining compatible with subsequent crosslinking.

[0403] In one embodiment, microparticles are used in solvent-based coating compositions based on polyesters or vinyl polymers. Polyester resins may include saturated or unsaturated polyesters dissolved in organic solvents such as esters, ketones, or aromatic hydrocarbons, while vinyl coatings may comprise systems based on vinyl chloride, vinyl acetate, vinyl esters, or associated copolymers. Microparticles may be dispersed within such polymer-solvent systems to impart gel-like properties, control flow during application, or improve formulation stability.

[0404] In another embodiment, microparticles are used in solvent-based coating compositions containing silicone resins, fluoropolymers, or other specialty coating systems. Such coatings may include silicone resins, fluoropolymers, or hybrid systems dissolved in aromatic solvents, esters, ketones, or specific solvents. Microparticles can be used to structure these formulations to improve application behavior, film uniformity, or storage stability, without limiting the chemical nature of the binder or solvent system.

[0405] Household care compositions

[0406] The household care composition may include a laundry detergent composition, a fabric softener composition, a dishwashing composition (manual or machine), a hard surface cleaning composition, a disinfectant composition, a stain remover or pre-treatment composition for laundry, an air or textile freshening composition, or a specialized composition for domestic maintenance.

[0407] In addition to microparticles, the laundry detergent composition typically includes one or more anionic, non-ionic, cationic and / or amphoteric surfactants, such as sodium dodecyl sulfate, ethoxylated alcohols or betaines, and / or one or more enzymes selected from proteases, amylases, lipases, cellulases and mannanases, and / or bleaching agents such as sodium percarbonate, peroxide compounds and / or optical brighteners, and / or sequestrants such as EDTA, phosphonates and / or citric acid, and / or anti-redeposition polymers, as well as common adjuvants such as perfumes, colorants, preservatives, fillers and structuring agents.

[0408] In addition to microparticles, the textile softening composition typically includes one or more cationic softening agents, including esterquats and / or long-chain quaternary ammonium compounds, and / or dispersing or emulsifying agents, and / or thickening agents such as xanthan gum or carboxymethylcellulose, and / or free and / or encapsulated perfumes, for example in the form of microcapsules releasing the perfume upon rubbing, as well as preservatives, colorants and other formulation auxiliaries.

[0409] In addition to microparticles, the composition intended for cleaning dishes, whether by hand or automatic dishwasher, typically includes one or more anionic and / or non-ionic surfactants, and / or alkaline agents such as carbonates and / or silicates, and / or selected enzymes, particularly proteases and amylases, and / or anti-limescale and sequestering agents such as polycarboxylates and / or phosphonates, and / or foaming and / or anti-foaming agents, as well as perfumes, colors, preservatives and other usual additives.

[0410] In addition to microparticles, the composition for cleaning hard surfaces typically includes one or more water-soluble solvents, such as ethanol, isopropanol and / or glycol ethers, and / or non-ionic and / or amphoteric surfactants, and / or alkaline and / or acidic agents, such as sodium hydroxide, citric acid and / or formic acid, and / or mild abrasive agents such as precipitated silica, and / or antimicrobial agents such as benzalkonium chloride, alcohol and / or organic acids, as well as perfumes, colorants, preservatives and thickening agents.

[0411] In addition to microparticles, the disinfectant composition typically includes one or more broad-spectrum antimicrobial agents, including ethyl alcohol, isopropyl alcohol, hydrogen peroxide, sodium hypochlorite and / or quaternary ammonium compounds, and / or surfactants promoting wettability, and / or thickening agents such as cellulose derivatives and / or carbomers, and / or humectants or softening agents such as glycerin and / or propylene glycol, as well as perfumes and preservatives.

[0412] In addition to microparticles, the stain-removing or pre-treatment composition for laundry typically includes one or more organic solvents such as alcohols and / or glycol ethers, and / or high-concentration enzymes, and / or powerful surfactants, and / or chelating agents improving enzymatic stability, and / or thickening or gelling agents allowing localized application on the textile.

[0413] In addition to microparticles, the refreshing composition of ambient air or textiles typically includes one or more free and / or encapsulated perfumes, notably in the form of essential oils or scented mixtures, and / or volatile solvents such as ethanol and / or dipropylene glycol, and / or odor neutralizers such as zinc ricinoleate and / or sodium bicarbonate, and / or film-forming polymers promoting adhesion to textiles, as well as diffusion systems such as gels, aerosols, impregnated porous supports and / or scented capsules.

[0414] In addition to microparticles, the specialized composition for domestic maintenance may be intended for the cleaning and protection of metals, and include mild abrasives, complexing agents and / or organic acids; for the maintenance of wood and / or leather, and include waxes, vegetable oils, film-forming polymers and / or light solvents; for the removal of limescale, and include organic and / or mineral acids; for the control of molds, and include authorized fungicides and / or biocides; or for the cleaning of household appliances, and include descaling agents, dispersants, corrosion inhibitors, foaming agents and / or antifoaming agents.

[0415] Other details or advantages of the invention may become apparent from the examples below, without limitation.

[0416] Examples

[0417] Polymer microparticles are prepared according to the process detailed below. The raw materials and quantities used are listed as a percentage by weight. They are then subjected to characterization and / or testing according to the protocols detailed below.

[0418] Process

[0419] In a first step, the components of a C2 pre-composition are mixed together.

[0420] In a second step, pre-composition C1 is added to pre-composition C3 until a ratio of C2:C3 = 10:90 is reached, then it is mixed for 1 minute at 2000 rpm allowing the formation of a monodisperse C2-in-C3 emulsion.

[0421] In a third step, the C2-in-C3 monodisperse emulsion is passed through a UV chamber to polymerize the droplets of the C2 pre-composition by photopolymerization at a wavelength between 360 nm and 450 nm for 30 to 240 seconds, enabling the formation of microparticles from the photopolymerization of the C2 pre-composition. In a fourth step, the microparticles obtained by photopolymerization of the C2 pre-composition are extracted from the continuous phase C3 by centrifugation and washed in distilled water in which the continuous phase is soluble, purified with ethanol, and then dried either at room temperature ("Process 1", unless otherwise specified) or by spray drying in ethanol ("Process 2", if specified). The resulting product is then ground to obtain a white powder containing approximately 100% microparticles by weight.

[0422] Particle Size Protocol

[0423] The microparticles in powder form are dispersed before measurement. In a 50 mL Eppendorf tube, a mixture is prepared by combining the powder and a surfactant in a 1:1 ratio. The surfactant used could be, for example, Kophanios® surfactant, available from Laboratoire Anios. The mixture is subjected to ultrasonic analysis using a probe. The ultrasonic probe amplitude is set at 35% with 3 cycles. The particle size distribution is then analyzed on a Mastersizer 3000 instrument.

[0424] The volume dimensions are reported in the tables below: the cumulative volume distribution of microparticle size is measured and then expressed as a cumulative percentage by volume. Dv10 corresponds to the maximum value of 10% by volume of the microparticle sample volume; Dv50 corresponds to the maximum value of 50% by volume of the microparticle sample volume; and Dv90 corresponds to the maximum value of 90% by volume of the microparticle sample volume.

[0425] Biodegradability assessment protocol

[0426] The biodegradability of microparticles is assessed by exposing samples to bacteria from sewage sludge containing a variable population of microorganisms, according to the protocol of guideline 301F, with the difference that the sludge concentration is 100 ppm. According to this protocol, the biodegradability of a material is characterized by the rate at which it is converted into biomass.

[0427] The tests are organized into campaigns, using the same sludge. Each sample is tested in at least two non-disqualified campaigns, with at least three replicates. In each campaign, to ensure the sludge's activity, a positive control sample of sodium benzoate is tested. A monomer sample of formula (VII) is also tested (normalization sample). If the positive control sample is not biodegradable, the campaign is disqualified. The absolute percentage of biodegradability at 28 days, according to the protocol in guideline 301F, is recorded.

[0428] Monomer formula (VII) exhibits an absolute biodegradability of 68% (average over more than 7 campaigns). This monomer demonstrates high biodegradability.

[0429] A relative percentage of biodegradability is normalized for samples tested during a campaign according to the formula below: % normalized = (absolute % of biodegradability noted for the sample) / (absolute % of biodegradability of the formula VII monomer for the normalization sample) * 68. The average normalized biodegradability value for all campaigns is calculated, and a biodegradability score is assigned to the tested microparticles, thus qualifying their biodegradability. The score is determined as follows:

[0430] Rating Qualifying Range (% normalized)

[0431] 0 Non-biodegradable [0-20]

[0432] 1 Moderate biodegradability [20-35]

[0433] 2 Significant biodegradability [35-65]

[0434]

[0435] 3 High biodegradability [65-100]

[0436] Example 1 - Preparation of polymer microparticles

[0437] Example 1.1

[0438] (Table 1)

[0439] Example 1.1 Raw materials Percentages

[0440] mass

[0441] Pre-composition C2 Monomer of formula (VII) 96%

[0442] Ethyl phenyl(2,4,6-4% trimethylbenzoyl)phosphinate

[0443] (Photoinitiator)

[0444] TOTAL pre-composition C2 100%

[0445] Pre-composition C3 Associative thickening agent 0.5%

[0446] Newtonian

[0447] Carboxymethyl Cellulose 6%

[0448] Water 93.5%

[0449] TOTAL pre-composition C3 100%

[0450] Polymerization in 4 minutes - 405 nm

[0451] UV

[0452] Time - length

[0453] wave

[0454] Particle size (pm) DvlO: 2.48pm

[0455] Dv50: 5.56 pm

[0456]

[0457] Dv90: 13.0 pm Example 1.2

[0458] (Table 2)

[0459] Example 1.2 Raw materials Mass percentages Pre-composition C2 Monomer of formula (VII) 94.5%

[0460] Hexanediol diacrylate (HDDA) 5.0% Ethyl phenyl(2,4,6- 0.5% trimethylbenzoyl)phosphinate

[0461] (Photoinitiator)

[0462] TOTAL pre-composition C2 100

[0463] Pre-composition C3 Sodium sulfite lignosulfonate 0.02%

[0464] 0.15% Newtonian associative thickening agent

[0465] Carboxymethyl Cellulose 6%

[0466] Water 93.83% TOTAL pre-composition C3 100% Polymerization in 30 s - 405 nm

[0467] UV

[0468] Time - length

[0469] wave

[0470] Particle size (pm) DvlO: 2.15

[0471] Dv50: 3.72

[0472] Dv90: 6.71

[0473]

[0474] Example 1.3

[0475] (Table 3)

[0476] Example 1.3 Raw materials Mass percentages Pre-composition C2 Monomer of formula (VII) 99.5%

[0477] Ethyl phenyl(2,4,6- 0.5% trimethylbenzoyl)phosphinate

[0478] (Photoinitiator)

[0479] TOTAL pre-composition C2 100% Pre-composition C3 Associative thickening agent 0.15%

[0480] Newtonian

[0481] Sodium sulfite lignosulfonate 0.01% Carboxymethyl Cellulose 6%

[0482] Water 93.84% TOTAL pre-composition C3 100% Polymerization in 30 seconds - 405 nm

[0483] UV

[0484] Time - length

[0485] wave

[0486] Particle size (pm) Dv10: 2.2

[0487] Dv50: 4.2

[0488]

[0489] Dv90: 9.94 Example 1.4

[0490] (Table 4)

[0491] Example 1.4 Raw materials Mass percentages Pre-composition C2 Monomer of formula (VII) 86%

[0492] Stearyl Acrylate 10% Ethyl phenyl(2,4,6-4% trimethylbenzoyl)phosphinate

[0493] (Photoinitiator)

[0494] TOTAL pre-composition C2 100% Pre-composition C3 Associative thickening agent 0.2%

[0495] Newtonian

[0496] Carboxymethyl Cellulose 8%

[0497] Water 91.8% TOTAL pre-composition C3 100% Polymerization in 4 minutes - 405 nm

[0498] UV

[0499] Time - length

[0500] wave

[0501] Particle size (pm) Dv10: 2.42μm

[0502] Dv50: 5.61 μm

[0503]

[0504] Dv90: 14.0 μm Example 1.5

[0505] (Table 5)

[0506] Example 1.5 Raw materials Mass percentages Pre-composition C2 Placel® FA5 marketed by 96%

[0507] Daicel Chem

[0508] Ethyl phenyl(2,4,6-4% trimethylbenzoyl)phosphinate

[0509] (Photoinitiator)

[0510] TOTAL pre-composition C2 100% Pre-composition C3 Associative thickening agent 0.5%

[0511] Newtonian

[0512] Carboxymethyl Cellulose 6%

[0513] Water 93.5% TOTAL pre-composition C3 100% Polymerization in 4 minutes - 405 nm

[0514] UV

[0515] Time - length

[0516] wave

[0517] Particle size: A measurement on a Mastersizer 3000 device indicates a Dv50

[0518]

[0519] between 1 and 50 pm Example 1.6

[0520] (Table 6)

[0521] Example 1.6 Raw materials Mass percentages Pre-composition C2 Placel® FM5 marketed by 96%

[0522] Daicel Chem

[0523] Ethyl phenyl(2,4,6-4% trimethylbenzoyl)phosphinate

[0524] (Photoinitiator)

[0525] TOTAL pre-composition C2 100% Pre-composition C3 Associative thickening agent 0.5%

[0526] Newtonian

[0527] Carboxymethyl Cellulose 6%

[0528] Water 93.5% TOTAL for the pre-composition C3 100% Polymerization per 4 minutes - 405 nm

[0529] UV

[0530] Time - length

[0531] wave

[0532] Particle size: A measurement using a Mastersizer 3000 device indicates a Dv50

[0533]

[0534] between 1 and 50 pm Example 1.7

[0535] (Table 7)

[0536] Example 1.7 Raw Materials Percentages

[0537] mass

[0538] Pre-composition C2 Monomer of formula (VII) 94.5%

[0539] dipentaerythritol Hexaacrylate 5.0%

[0540] Ethyl phenyl(2,4,6- 0.5% trimethylbenzoyl)phosphinate

[0541] (Photoinitiator)

[0542] TOTAL pre-composition C2 100%

[0543] Pre-composition C3 Associative thickening agent 0.5%

[0544] Newtonian

[0545] Carboxymethyl Cellulose 6%

[0546] Water 93.5%

[0547] TOTAL for the C3 pre-composition 100%

[0548] Polymerization in 30 seconds - 405 nm

[0549] UV

[0550] Time - length

[0551] wave

[0552] Particle size (pm) Dv10: 2.64

[0553] Dv50: 5.55

[0554]

[0555] Dv90: 10.3

[0556] Analyses of the mechanical properties of massive microparticles by nanoindentation technique show a predominantly viscoelastic behavior, without significant creep after stressing.

[0557] Biodegradability tests of microparticles according to OECD 301F guidelines show that microparticles exhibit substantial biodegradability.

[0558] Impregnation tests with hydrophilic or hydrophobic active substances demonstrate a significant and versatile absorption capacity of such substances, both in their mass and / or on their surface, typically at least 10% by weight and even at least 20%. Example 1.8

[0559] (Table 8)

[0560] Example 1.8 Raw materials Mass percentages Pre-composition C2 Monomer of formula (VII) 95.0%

[0561] modified dipentaerythritol hexaacrylate 0.5% per 6 moles of caprolactone (DP6CAHA)

[0562] Ethyl phenyl(2,4,6-4% trimethylbenzoyl)phosphinate

[0563] (photoinitiator)

[0564] TOTAL pre-composition C2 100% Pre-composition C3 Associative thickening agent 0.5%

[0565] Newtonian

[0566] Carboxymethyl Cellulose 6%

[0567] Water 93.5% TOTAL pre-composition C3 100% UV polymerization 2 minutes - 405 nm

[0568] Time - length

[0569] wave

[0570] Procedure Procedure 2

[0571] Particle size (pm) Dv10: 1.82μm

[0572] Dv50: 5.14 μm

[0573]

[0574] Dv90: 9.55 μm Example 1.9

[0575] (Table 9)

[0576] Example 1.8 Raw Materials Percentages

[0577] mass

[0578] Pre-composition C2 Monomer of formula (VII) 91.0%

[0579] modified dipentaerythritol hexaacrylate 5%

[0580] by 6 moles of caprolactone

[0581] (DP6CAHA)

[0582] Ethyl phenyl(2,4,6-4% trimethylbenzoyl)phosphinate

[0583] TOTAL pre-composition C2 100%

[0584] Pre-composition C3 Associative thickening agent 0.5%

[0585] Newtonian

[0586] Carboxymethyl Cellulose 6%

[0587] Water 93.5%

[0588] TOTAL pre-composition C3 100%

[0589] UV curing in 2 minutes - 405 nm

[0590] Time - length

[0591] wave

[0592] Procedure Procedure 2

[0593] Particle size (pm) Dv10: 1.82μm

[0594] Dv50: 5.14 μm

[0595]

[0596] Dv90: 9.55 μm

[0597] Example 2 - Preparation of polymer microparticles and evaluations

[0598] Other microparticles are prepared in the same way as in example 1.1 by modifying the pre-com position C2 as indicated in Table 10. The photoinitiator is Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.

[0599] For each sample, a particle size measurement according to a Mastersizer 3000 device indicates a Dv50 between 1 and 50 pm.

[0600] (Table 10)

[0601] Example Polymer Composition Note (Pre-composition C2) Biodegradability Example 2.1 Formula Monomer (VII): 96% 2

[0602]

[0603] Photoinitiator: 4% Example 2.2 Formula Monomer (VII): 91% 2 HDDA: 5%

[0604] Photoinitiator: 4%

[0605] Example 2.3 Monomer of formula (VII): 86% 2

[0606] HDDA: 10%

[0607] Photoinitiator: 4%

[0608] Example 2.4 Monomer of formula (VII): 91% 2

[0609] DP2CAHA: 5%

[0610] Photoinitiator: 4%

[0611] Example 2.5 Monomer of formula (VII): 86% 1

[0612] DP2CAHA 10%

[0613] Photoinitiator: 4%

[0614] Example 2.6 Monomer of formula (VII): 91% 1

[0615] DP6CAHA 5%

[0616] Photoinitiator: 4%

[0617] Example 2.7 Monomer of formula (VII): 86% 1

[0618] DP6CAHA 10%

[0619] Photoinitiator: 4%

[0620] Example 2.8 Placel FA5: 91% 2

[0621] HDDA: 5%

[0622] Photoinitiator: 4%

[0623] Example 2.9 Placel FA5: 86% 2

[0624] HDDA: 10%

[0625] Photoinitiator: 4%

[0626] Example 2.10 Placel FA5: 91% 2

[0627] DP2CAHA: 5%

[0628] Photoinitiator: 4%

[0629] Example 2.11 Placcel FA5: 86% 1

[0630] DP2CAHA: 10%

[0631] Photoinitiator: 4%

[0632] Example 2.12 Placcel FA5: 86% 2

[0633] DP6CAHA: 10%

[0634] Photoinitiator: 4%

[0635] Example 2.13 Placcel FA5 61% 2

[0636] Formula monomer (VII): 30%

[0637] HDDA: 5%

[0638]

[0639] Photoinitiator: 4%Example 2.14 Placcel FM5 61% 2

[0640] Formula monomer (VII): 30%

[0641] HDDA: 5%

[0642] Photoinitiator: 4%

[0643] Example 2.15 Monomer of formula (V) where x=2: 48% 2

[0644] Formula monomer (VII): 48%

[0645]

[0646] Photoinitiator: 4%

[0647] Examples 1 and 2 show that it is possible to prepare microparticles based on monomers of formula (I) and / or (II) and that these microparticles exhibit biodegradability of interest.

[0648] Example 3: Impregnation Test

[0649] An impregnation test is carried out by adding and mixing increasing quantities of the compounds indicated in Table 11 to the microparticles of Example 1.1 in powder form. The behavior of the mixture is observed.

[0650] For each compound, three phases are observed during the addition process:

[0651] Phase 1: the microparticles absorb the compound, with which they are impregnated, the mixture being in powder form.

[0652] Phase 2: the mixture forms a medium whose viscosity increases with additions but remains fluid by flow test on a spatula placed vertically.

[0653] Phase 3: the mixture forms a gel and no longer flows when tested by a spatula placed vertically.

[0654] Table 11 shows the quantity by weight, relative to the weight of a mixture, from which phase 3 is observed, as the gelation threshold.

[0655] (Table 11)

[0656] Example Impregnation compound Gelation threshold (%) Example 3.1 Ethanol 40

[0657] Example 3.2 Isopropanol 40

[0658] Example 3.3 Isobutanol 50

[0659] Example 3.4 Ethyl acetate 27.5

[0660] Example 3.5 MPa 30

[0661] Example 3.6 MAK 40

[0662]

[0663] Example 3.7 Glycerol 30

[0664] Example 3 demonstrates, in particular, the impregnation capacity of microparticles by compounds used in coating formulations. Example 4: Concentrated composition

[0665] 30% by weight of the microparticles from example 1.1 are mixed with 70% by weight of glycerol. This results in a concentrated composition in the form of a slightly opaque, viscous, smooth gel.

[0666] Example 5: Household care products

[0667] Household care formulations are prepared. The formulations are identified in the tables below, where the quantities of ingredients are indicated by weight.

[0668] Example 5.1 - Wardrobe fragrance sachet

[0669] (Table 12)

[0670] Ingredient %

[0671] Microparticles according to example 1.1 40

[0672]

[0673] Jasmine / Vanescence Perfume 60

[0674] The formulation is packaged in a fabric sachet.

[0675] Example 5.2 - Lemon deodorizing gel

[0676] (Table 13) _

[0677] Ingredient %

[0678] Microparticles according to example 1.1 30

[0679] HE lemon 35

[0680]

[0681] DPG 35

[0682] The formulation is packaged in a jar.

[0683] Example 5.3 - Cleaning and disinfecting powder

[0684] (Table 14)

[0685] Ingredient %

[0686] Sodium lauryl sulfoacetate 51

[0687] Xanthan Gum 20

[0688] Microparticles according to example 1.1 14

[0689] He eucalyptus radiata 6

[0690] Zinc oxide 9

[0691]

[0692] Blue dye Qsp _

[0693] Example 5.4 - Deodorizing soap (Table 15)

[0694] Ingredient %

[0695] Glycerin Melt & Pour Aloe 70 Soap Base

[0696] Vera BIO, marketed by Aroma-zone.

[0697] https: / / www.aroma-zone.com / info / fiche-technique / base-melt-pour-laloe-vera-bio

[0698] Microparticles according to example 1.1 24

[0699] Zinc ricinoleate 6

[0700]

[0701] Perfume Qsp _

[0702] The formulation is packaged in a box or in folded paper.

Claims

Demands 1. Massive polymeric microparticles with a median volume size between 1 µm and 100 µm, preferably between 1 and 50 µm, characterized in that: - the microparticles comprise at least one polymer comprising at least 50% by weight relative to the total weight of the polymer of units corresponding to at least one monomer A, of formula (I): CH2=CR 1 (COO-R 2 O-[-CO-CH2-CH2-CH2-CH2-CH2-O-] x -H) (I) in which - R 1 is a hydrogen atom or a methyl group, - R 2 is a linear or C1-C6 branched alkylene group, preferably an ethylene group, and - x is a real number between 1 and 10, preferably between 1 and 3, or (II) C H2=CR 1 (CO-[O-CH2-CH2-CH2-CH2-CH2-CO-] x -OH) (II) in which: - R1 is a hydrogen atom or a methyl group, And - x is a real number between 1 and 10, preferably between 1 and 3.

2. Microparticles according to claim 1, characterized that they comprise at least 50% by weight, relative to the total weight of the microparticles, of the polymer, preferably at least 75% by weight, particularly preferably at least 90% by weight.

3. Microparticles according to any one of the preceding claims, characterized in that the polymer comprises at least 75% by weight relative to the total weight of the polymer, preferably at least 95% by weight of units corresponding to monomer A.

4. Microparticles according to any one of the preceding claims, characterized in that monomer A is at least one monomer of formula (I).

5. Microparticles according to claim 4, wherein the monomer A has formula (VII): CH2=CH(COO-CH2-CH2-O-[-CO-CH2-CH2-CH2-CH2-CH2-O-]2-H) (VII).

6. Microparticles according to any one of the preceding claims, characterized in that the polymer comprises at least 90% by weight relative to the total weight of the polymer, preferably at least 99%, preferably at least 99.5%, of units corresponding to monomer A.

7. Microparticles according to any one of claims 1 to 5, characterized in that the polymer comprises units corresponding to a multifunctional monomer B.

8. Microparticles according to claim 7, characterized in that the multifunctional monomer is a di(meth)acrylate or a polyol-multi(meth)acrylates modified by caprolactone motifs.

9. Microparticles according to any one of claims 7 or 8, characterized in that the polymer comprises at most 5% by weight relative to the total weight of the polymer of units corresponding to the multifunctional monomer B.

10. Microparticles according to any one of the preceding claims, characterized in that the median volumetric size of the microparticles is between 1 pm and 20 pm.

11. Microparticles according to any one of claims 1 to 10 characterized in that they are included in a concentrated composition, comprising at least 15%, preferably at least 30% by weight of microparticles, relative to the total weight of the composition, preferably at least 50% by weight.

12. Microparticles according to claim 11, characterized in that the composition is in powder form and preferably comprises at least 90% by weight relative to the total weight of the composition of microparticles.

13. Microparticles according to any one of claims 11 or 12, characterized in that the composition is in the form of a dispersion of microparticles in an aqueous phase, and preferably comprises at least 50% by weight relative to the total weight of the composition of microparticles.

14. A method for preparing microparticles according to any one of the preceding claims, comprising the following steps: a) preparation of an emulsion comprising droplets comprising a hydrophobic phase comprising a monomer composition including at least monomer A and a polymerization initiator in a continuous aqueous phase, b) polymerization by activation of the polymerization initiator, in order to obtain microparticles comprising the polymer, and c) optionally washing and / or concentration of microparticles.

15. A method according to claim 14, characterized in that the droplets are a continuous hydrophobic phase.

16. A process according to any one of claims 14 or 15, characterized in that the polymerization initiator is a photoinitiator, and in that the polymerization is activated by UV.

17. A method according to any one of claims 14 to 16, characterized in that the droplets of the emulsion have a median volume size of between 1 pm and 100 pm, preferably between 1 and 50 pm.

18. Use of microparticles according to any one of the preceding claims in formulations of lubricants, fuels, raw material mining, purification, materials, coatings, household care, plant protection compositions, optical compositions, compositions for electronic use, textile fiber compositions, textile coatings, adhesives, thermal or acoustic insulation, substrate inks, or electronic inks.

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