WO2011117150A1

WO2011117150A1 - Water-soluble copolymers

Info

Publication number: WO2011117150A1
Application number: PCT/EP2011/054123
Authority: WO
Inventors: Cécile RATSCHOW; Jörg SCHIEMANN; Hans-Ulrich Moritz; Christiane Meyer; Jörg SCHREIBER; Min-Zae Oh
Original assignee: Beiersdorf Ag
Priority date: 2010-03-23
Filing date: 2011-03-18
Publication date: 2011-09-29
Also published as: DE102010012590A1

Abstract

Novel copolymers of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAA), glycerol allyl ether(GAE), glyceryl methacrylate (GMA), 3-sulfopropyl acrylate (SPA) or acrylic acid (AA) are described. A second group of copolymers is formed from glyceryl methacrylate (GMA) and methacrylic acid (MAA) or 3-sulfopropyl acrylate (SPA). A third group of copolymers is formed from methacrylic acid (MAA) and 3-sulfopropyl acrylate (SPA) or 2-hydroxyethyl acrylate (HEA). The copolymers have a molar mass of less than 17 000 g/mol and, on the basis of their water solubility, and water absorption and release kinetics, are usable especially as humectants in cosmetic or dermatological formulations.

Description

Water-soluble copolymers

The invention describes novel copolymers of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAS), glycerol allyl ether (GAE), glyceryl methacrylate (GMA), 3-sulfopropyl acrylate (SPA) or acrylic acid (AS). A second group of copolymers is formed from glyceryl methacrylate (GMA) and methacrylic acid (MAS) or 3-sulfo-propyl acrylate (SPA). A third group of copolymers is formed from methacrylic acid (MAS) and 3-sulfopropyl acrylate (SPA) or 2-hydroxyethyl acrylate (HEA). All copolymers have a low molecular weight and are water-soluble.

Due to their water solubility, water absorption and release kinetics, the copolymers can be used in particular as moisturizers in cosmetic or dermatological preparations.

As water-soluble polymers, the person skilled in the art from a number of known polymers such as polyvinyl alcohol, gelatin, polyacrylic acid, sodium polyacrylates, methyl cellulose,

Select carboxymethylcellulose, polyvinylpyrrolidone, rubber and other crosslinkable polymers, and mixtures thereof.

The disadvantage here is that these polymers act predominantly as thickeners for the water phase.

Furthermore, the proportion of water-soluble polymers in cosmetic preparations is often limited to fractions of up to 1 or 2% by weight, since the polymers are soluble only to a small extent in water and, in addition, thicken the solution.

The disadvantage is that at these low proportions only little water absorption by the polymers is possible.

Another disadvantage of conventional polymers is their odor, caused by monomer residues and / or unsuitable for cosmetics solvents.

Known water-soluble polymers in cosmetics are, for example, carboxyvinyl polymers, as described in JP 2009040705, or crosslinked acrylic acid polymers or copolymers which are commercially available as pemulen Tr-1, carbopols or carbomers.

US 6348199 and US 5306498 describe clear and stable gels for skin treatment, especially skin moisturization. The gels include polyglyceryl methacrylate, which are water-soluble and water-absorbent used as a moisturizer. WO 20080871 19 describes styrene-acrylate diblock copolymers which are said to have skin-moisturizing properties.

The polyglyceryl (meth) acrylates are commercially available as homopolymers or copolymers with acrylic acid or methacrylic acid as Lubrajel® or Lubrasil®.

The known polymers can generally be prepared by free-radical polymerization. Here, the use of the method of the polystyrene and

Polyvinyl chloride on polyacrylic acid, polyacrylamide to polyvinyl acetate. Different methods are used. In addition to the solution polymerization, emulsion, suspension and bulk polymerization are used.

EP 1 195394 describes the preparation of water-soluble copolymers by free-radically initiated polymerization of hydroxy-alkyl (meth) acrylates with optionally alkyl (meth) acrylates or vinyl esters and polyvinyl alcohol (PVA).

The copolymers thus prepared are used as coating or binder in

used pharmaceutical dosage forms.

For the preparation of the copolymers hydroxy-alkyl (meth) acrylates, u.a. also HEMA, polymerized in the presence of PVA both with the help of radical-forming initiators and by the action of high-energy radiation, which is to be understood as the action of high-energy electrons. To initiate the

Emulsion polymerization radical initiators are used. The amounts used of initiator or initiator mixtures based on the monomer used are between 0.01 and 10 wt.%. Depending on the type of solvent used, both organic and inorganic peroxides or azo initiators such as azo-bis-isobutyronitrile, azo-bis (2-amidopropane) dihydrochloride or 2,2'-azobis (2-methylbutyronitrile) are suitable. , Examples of peroxidic initiators are dibenzoyl peroxide,

Diacetyl peroxide, succinyl peroxide, tert-butyl perpivalate, tert-butyl 2-ethylhexanoate, tert-butyl permalate, bis (tert-butyl peroxy) cyclohexane, tert-butyl peroxide

Butyl peroxiisopropyl carbonate, tert-butyl peracetate, 2,2-bis- (tert-butylperoxy) -butane,

Dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide and mixtures of the initiators mentioned. The free-radical emulsion polymerization according to EP 1 195394 preferably takes place in water with concomitant use of

Polyvinyl alcohol, in the presence of radical-forming polymerization initiators,

optionally emulsifiers, optionally further protective colloids, optionally molecular weight regulators, optionally buffer systems and optionally

subsequent pH adjustment by means of bases or acids instead. The copolymers are as aqueous dispersions or aqueous solutions having a viscosity of less than 500 mPas or after removal of the water content, as water-dispersible or

won water-soluble powder.

Since these copolymers should be usable in aqueous dispersions, no salts or electrolytes are suitable for this purpose.

PVA is used according to EP 1 195394 as protective colloid. PVA prevents the

Agglomeration of non-water-soluble monomer droplets or polymer particles. Since PVA is used in large quantities here, the polymers thus produced are additionally grafted with PVA, which apparently results in better film formation.

A disadvantage of the known poly (meth) acrylates and copolymers is their property often to swell in water to form gels and / or to act thickening.

From another field of technology - the contact lenses - methacrylic acid copolymers are known, which are characterized by water absorption and oxygen permeation, such as in - production and characterization of hydrogels as

Contact Lens Materials - Lecture on the occasion of the Section Meeting "

Macromolecular Chemistry "of the Gesellschaft Deutscher Chemiker on" Polymers and Water "in Bad Nauheim on 2 and 3 April 1984 - disclosed.

Since the late 1930s, contact lenses made of polymeric materials have been used on the human eye. At present, a variety of

Used contact lens materials, which consist of long-chain and interconnected more or less polar polymer chains. The contact lenses currently on the market are divided into two main groups due to their material. The first group comprises the contact lenses, which consist of copolymers with ionic proportions. These copolymers are mostly made with constituents of methacrylic acid. However, the ionic components in a contact lens cause some unpleasant side effects, so that the abandonment of the ionic components was the logical step, especially for long-term lenses. This is how contact lenses made of materials that no longer contained ionic components were created. For this second large group were monomers such as N-vinyl-pyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA) or

Glyceryl methacrylate (GMA) used. The advantage of these polymer materials is that they are classified by the US Food and Drug Administration (FDA) and approved for human use. Furthermore, due to the industrial demand for the above-mentioned monomers, cost-effective availability is given. Since the contact lenses today no longer consist only of a homopolymer, there are very extensive Possible combinations for adjusting the moisture content of a lens.

In the meantime, contact lenses with ionic components, as well as those with exclusively nonionic components, achieve in vitro moisture contents of more than 50%. In addition to the required optical properties, the contact lens materials further have high gas permeabilities and very high moisture contents.

The use of these contact lens polymers in cosmetic or dermatological

Dosage forms or formulations are, however, prohibited, since these lens polymers are not soluble in water but only swellable. The non-solubility is based primarily on it, since they are composed of long and highly interconnected polymer chains.

For use in cosmetics or other topically applied compositions, therefore, there was a desire for water-soluble polymers that are very soluble in water, have a high water absorption capacity and also show a high rehydration effect after application.

It is also desirable to provide polymers which do not gel and / or thicken in water.

It is also desirable to expand the range of skin moisturisers to better meet the individual needs of consumers.

The invention includes copolymers of 2-hydroxyethyl methacrylate (HEMA) and

Methacrylic acid (MAS), glycerol allyl ether (GAE), glyceryl methacrylate (GMA), 3-sulfopropyl acrylate (SPA) and / or acrylic acid (AS).

Hereinafter referred to as HEMA-MAS, HEMA-GAE, HEMA-GMA, HEMA-SPA or HEMA-AS copolymer or HEMA copolymers with the respective structures

(I) for HEMA MAS copolymers

(II) for HEMA-GAE copolymers

(IV) for HEMA-SPA copolymers

(V) for HEMA-AS copolymers

The copolymers with glyceryl methacrylate (GMA) as the base polymer are formed with 3-sulfo-propyl acrylate (SPA) and / or methacrylic acid (MAS).

Hereinafter referred to as GMA-MAS or GMA-SPA copolymer or only as GMA copolymers with the respective structures (VI) for GMA-MAS copolymer

(VII) for GMA-SPA copolymer

The invention further includes copolymers of methacrylic acid (MAS) and 3-sulfopropyl acrylate (SPA) or 2-hydroxyethyl acrylate (HEA).

Hereinafter referred to as MAS-SPA or MAS-HEA copolymer or only as MAS copolymers with the respective structures (VIII) for MAS-HEA copolymer

With ^* the initiator residues used in the preparation are characterized, which in

Depending on the particular initiator, in particular sulfate, hydrogen and / or hydroxide radicals can represent.

Z ⁺ is a cationic residue.

For the HEMA-MAS copolymers and MAS copolymers, the methacrylic acid used is preferably a neutralized methacrylic acid (MAS). That is, Z ⁺ then forms the cationic residue of the base used.

Depending on which is neutralized with which bases, Z is preferably selected from H, Na, K, Ca, NH ₄ or other alkyl ammonium NR ₃ R ₄ R ₅ R ₆ with R ₃ -R ₆ = H, CH ₃ or

Preference is given to Z = Na, since methacrylic acid neutralized with sodium hydroxide solution or the copolymers forming exhibit better moisture absorption capacity.

In contrast to the copolymers shown in EP 1 195394, the

copolymers of the invention is due to the cationic radicals Z ⁺ and Initiatoresten ^* polyelectrolytes which are water soluble and remain so.

Another difference is that copolymers of the invention do not have a

Emulsion polymerization are prepared and at a free-radical initiated

Polymerization in an aqueous solvent can be dispensed with the addition of protective colloids, emulsifiers or nonaqueous solvents.

The copolymers of the invention are therefore in particular obtainable from the free-radical solution polymerization of 2-hydroxyethyl methacrylate (HEMA) and Methacrylic acid (MAS), glycerol allyl ether (GAE), glyceryl methacrylate (GMA), 3-sulfopropyl acrylate (SPA) or acrylic acid (AS) for the HEMA copolymers. The

GMA copolymers according to the invention are therefore obtainable, in particular, from the free-radical solution polymerization of glyceryl methacrylate (GMA) and methacrylic acid (MAS) or 3-sulfopropyl acrylate (SPA).

The MAS copolymers according to the invention are preferably obtainable from the free-radical solution polymerization of methacrylic acid (MAS) and 3-sulfopropyl acrylate (SPA) or 2-hydroxyethyl acrylate (HEA).

In the radical polymerization in solution are advantageously inorganic

Peroxoinitiatoren used. This is mainly due to the low cost and the excellent water solubility.

When peroxodisulfates are used as initiator, it is advantageous to buffer the reaction solution to achieve the optimum radical yield.

The copolymers according to the invention are characterized by the coefficients n (MAS, GAE, GMA, SPA, AS) and m (HEMA) for the HEMA copolymers.

n (MAS, SPA) and m (GMA) for the GMA copolymers and n (MAS) and m (SPA, HEA) for the MAS copolymers.

According to the invention, the two coefficients n and m are in the range from m = 2 to m = 58, in particular m = 2 to m = 45, more preferably m = 4 to 12, very particularly preferably m is in the range from 5 to 10.

n is chosen in the range n = 8 to n = 105, in particular n = 8 to 75, in particular n is in the range 25 to 65, very particularly preferably n is in the range from 31 to 59.

The incorporation ratios of HEMA are preferably between 10 and 75 mol% of the HMA-MAS copolymers and between 25 and 90 mol% of MAS. Mol.% Is here as well as below in each case based on the total number of moles of the monomers used.

The quantitative determination of the incorporation ratios of the monomers in the

Copolymers according to the invention are described as follows by way of example for the HEMA-MAS copolymer.

The determination is carried out by means of ¹ H-NMR spectroscopy, as shown in Figure 1 - H spectrum of a HEMA-MAS copolymer. The signals of the methylene group of the 2-hydroxylethyl radicals (HEMA unit, b) and the methylene groups of the polymer chain (both HEMA and MA unit, d and f) can be clearly assigned. On the basis of the resulting integration ratio of the two signals so the installation rate can be calculated.

The incorporation rate (expressed in mol.%) Of the methacrylates is calculated according to equation (1). The integral value of the signal of the methylene group b is calibrated to 1 at 3.7 ppm (two protons) and the corresponding integral value of the signals of the

Methylene groups d, f recorded at 1.6 - 2.0 ppm (four protons).

2 (1 - X) _ 2X + 2 (1 - X) χ ^~ 2I _a + 2I _b

2I _b

X = incorporation rate of the methacrylate

(1-X) = incorporation rate of 2-hydroxyethyl acrylate

l _a = integral value of the signal of the methylene group of the HEMA unit b.

I _b = integral value of the signal of the methylene group of the polymer chains d, f (HEMA and MA unit)

The incorporation ratios of the two monomers both in the HEMA copolymers and in the GMA and MAS copolymers surprisingly agree approximately with the ratios of the starting monomers used in the preparation.

The advantage is that the two monomers can be used selectively in the desired ratio in order to achieve desired property of the polymer and remain after the polymerization no excess residual monomers, which must be additionally removed.

The molecular weight of the copolymer is determined by the coefficients n and m, i. On the basis of the molar mass and installation conditions one can calculate n and m and vice versa from the numbers n and m the molar mass.

For example, the number average molecular weight HEMA-MAS is 3387 g / mol (20:80) for the preferred ratio of the two monomers. The molar mass HEMA is 130.14 g / mol, the molar mass MAS is 86.09 g / mol. The determination of the coefficients m and n then takes place via the incorporation ratio of HEMA 20% ie 3387 ^χ 0.2 = 677.4 g / mol divided by the molar mass of HEMA 677.4 +130.14 g / mol = 5.2.

The installation ratio of MAS 80% ie. 3387 ^χ 0.8 = 2709.6 g / mol divided by the

Molar mass of MAS 2709.6 +86.09 g / mol = 31.47

This results in m (HEMA) ~ 5 and n (MAS) ~ 31.

(ignoring the remainders, marked as ^* in the formulas)

With an average molecular weight of the copolymer of HEMA-MAS from 6277 g / mol, the coefficients to give m (HEMA) = 10 (9.6) and n (MAS) ^"58 (58.3).

The number-average molar mass of the copolymers is therefore advantageously below 17,000 g / mol, more preferably below 10,000 g / mol, in particular in the range from 1700 to 7000 g / mol.

By characterizing the copolymers according to the invention via the coefficients n and m, the incorporation ratios and / or molar mass, in particular in the ranges specified, it is ensured that the copolymers have their advantageous properties

Be able to fully exploit properties.

Many methods are available for determining a molecular weight of a polymer. The most common methods for this are viscometry, light scattering or

Gel permeation chromatography. However, for most methods are

Reference substances required to deliver the desired results.

All polymers investigated for their molecular weight are characterized by specific parameters. The literature contains mean values with which a polymer is characterized. The most important mean is the number average molecular weight (M _n ):, - ^Σ

J \ _/ [: number average molecular weight

n _; : Number of macromolecules in the sample with exactly

repeating

M.: molecular weight i The number average molecular weight can be determined by colligative methods such as cryoscopy, membrane or vapor pressure osmometry and - if the number of

End groups per molecule is known - by end group determination.

As a further parameter, the weight average molecular weight (M _w ) is used:

M '■ weight-average molecular weight

". : Number of macromolecules in the sample with exactly i

repeating

M _i : molecular weight i

The weight average is obtained by methods that take into account the size and shape of a molecule in solution, e.g. static light scattering, small angle X-ray scattering and sedimentation equilibrium measurements.

From two of these average molar masses, the polydispersity (P) of a polymer represented can be calculated: _{p =} »

M "

P = polydispersity Weight-average molecular weight

Number average molecular weight

The polydispersity (P) is indicative of the nonuniformity of a polymer. The greater the polydispersity, the wider a polymer is distributed. In living polymerizations or polycondensations only very small polydispersities are achieved, while in free radical polymerizations significantly higher polydispersities are expected. The kinetic chain length is defined as follows and allows approximate statements about the expected chain length of a polymer.

v = kinetic chain length

f = radical yield

k _t = rate constant of the termination reaction (disproportionation and termination) k _p = rate constant of the growth reaction

k _d = rate constant of the initiator decay

[M] = monomer concentration

[I] = initiator concentration

While the constants for initiator decay, termination and growth reaction substance resp. Environment constants are, can be achieved by changing the variables [M] and [I] different effects. Thus, a halving of the initiator concentration causes an increase in the chain length by about 40%. Halving the monomer concentration while maintaining the initiator concentration, however, causes a reduction in the chain length by about half. The kinetic chain length is therefore the root of the

Initiator concentration inversely proportional.

With these methods shown copolymers of the invention can be clearly characterized.

The copolymers according to the invention are preferred with

Initiator radicals ^* selected from the group -H, -SO ₄ , -OH,

cationic radicals Z ⁺ selected from H, Na, K, Ca, NH ₄ or

Alkylammonium compounds NR ₃ R ₄ R ₅ R ₆ with R ₃ -R ₆ HH, CH ₃ or C ₂ H _5, m = 2 to 58, advantageously in the range from 2 to 45,

n = 8 to 105, preferably in the range 8 to 75 or

M ^" <17,000 g / mol, preferably in the range <10,000 g / mol, in particular in the range of 1,700 - 7,00 g / mol, and have advantageous

a polydispersity P <5. The preparation of the HEMA-MAS copolymers according to the invention is advantageously carried out according to the reaction equation:

It is advantageous to proceed according to the following example production instructions.

The amounts of 1 .57 g (6.6 mmol) or 3.14 g (13.2 mmol) or 6.28 g, (26.4 mmol) of sodium peroxodisulfate (10.20 and 30 mol% based on the sum of the monomers used) and 0.55 g (6.5 mmol ) or 1.1 g (13 mmol) or 2.2 g (26 mmol)

Sodium bicarbonate (ACROS) was dissolved in 50 mL of. Water is dissolved while stirring. Subsequently, the monomer mixtures were prepared from 4 mL (4.28 g, 33 mmol) HEMA, and 2.8 mL (2.84 g 33 mmol) in a ratio of 1: 1 by means of sodium hydroxide to pH 7 neutralized methacrylic acid. The neutralization of the methacrylic acid was carried out in water with the addition of saturated aqueous sodium hydroxide solution. The monomers were with the. Made up to 50 mL total volume and added dropwise over a period of 2 h to the temperature at 70 ° C initiator solution. After completion of the addition, the reaction solution was treated with another 1.1 g (4.4 mmol) of sodium peroxodisulfate and heated to 70 ° C for 2 h. Subsequently, the reaction mixture was acidified to pH = 2 using dilute sulfuric acid. After removing the water, the residue was taken up in ethanol and stirred for 30 minutes at 80 ° C bath temperature to separate the copolymer from the salt residues. The suspension was then filtered and the filtrate was freed from ethanol under vacuum. After dissolving the polymer residue in the. Water, the solution was neutralized with sodium hydroxide solution to pH = 7 and the water removed. Table 1 shows the exemplary monomer feed levels

Tables 2 to 4 below represent examples of the yields of the HEMA copolymers produced in this way.

Table 2:

Copolymer Poly-appearance

Used weights / number average dispersity

amount of initiator

Molecular weight M _n yield

Mol - [%]

[G / mol]

on Σ monomers

HEMA: MAS 1529 (OAc) 4.92 crystalline 7.1 g / 99%

20

50:50

HEMA: MAS 1325 (OAc) 3.51 crystalline 7.0 g / 98%

40

50:50 Table 3:

The preparation of the HEMA-GAE copolymers according to the invention (protected) is advantageously carried out in accordance with the reaction equation:

In each case amounts of 0.79 g (3.3 mmol) of sodium peroxodisulfate and 0.5 g (6.5 mmol) of sodium bicarbonate were dissolved in 10 ml of. Water is dissolved while stirring.

This was followed by the addition of 5, 10, 20, 30 and 40 ml (5.35, 10.7, 21.4, 42.8 g, 31- 248 mmol) of 2,2-dimethyl-4 - [(2-propyloxy) methyl] -1,3 dioxolane. With the. Water was on 50 ml_ filled and immersed in a 200 ml Erlenmeyer flask in the water bath of the 6-fold apparatus. The water bath was heated to 70 ° C. by means of a immersion circulator. After immersing the Erlenmeyer flasks and adjusting the stirring plate to 500 rpm, 50 ml of a solution of 4 ml (4.28 g, 33 mmol) of 2-hydroxyethyl methacrylate in 46 ml were added after 5 minutes of heating via a dropping funnel with pressure compensation over a period of 2 h. the. Water added dropwise. The reaction solution was heated for a further hour at 70 ° C under reflux after completion of the addition. After cooling the reaction solution to room temperature, it was stored in the refrigerator (+4 ° C) until complete phase separation. It formed 3 phases: glycerol allyl ether monomer phase, water phase and sediment from partially precipitated

Copolymer. The amount of precipitated copolymer increases with increasing glycerol allyl ether use. Subsequently, the Erlenmeyer flask was cooled in the freezer for 2 h at -20 ° C to freeze the water phase. The monomer layer (top) which was liquid at -20 ° C. could then be decanted. After thawing the aqueous reaction solution with the polymer base, they were first thoroughly mixed and then extracted with 2 times 100 ml of petroleum ether 50/70. The well-mixed reaction solution was transferred to a 500 ml one-neck flask. The water contained in the reaction solution was by means of a rotary evaporator at 40 ° C water bath temperature

Rotary vane pump vacuum (2 x 10 ^"4 mbar) to dryness the residue removed. To the located in the piston dried reaction mixture of ethanol were 200 least ml. (96%) and 15 min. Depressurized rotating water bath temperature in the heating bath of the rotary evaporator at 40 ° C. After complete detachment of all piston adhesions, the suspension was filtered at 40 ° C. The filtrate was collected in a further 500 ml round bottom flask and all ethanol contained was removed by rotary vane pump vacuum (2 × 10 ^-4 mbar) at 40 ° C. water bath temperature and the residue was more Dried for 30 minutes under a rotary vane pump vacuum.

The preparation of the HEMA-GMA copolymers according to the invention is advantageously carried out according to the reaction equation:

Sodium bicarbonate (ACROS) was dissolved in 50 ml of the. Water is dissolved while stirring. Subsequently, the monomer mixtures were prepared from 5.1 ml (5.3 g, 33 mmol) of GMA and 4 ml (4.28 g, 33 mmol) of HEMA in a ratio of 1: 1. The monomers were with the. Water to 50 ml_ total volume filled and added dropwise over a period of 2 h by means of dropping funnel to the tempered to 70 ° C initiator solution. To

When the addition was complete, the reaction solution was admixed with a further 1 .1 g (4.4 mmol) of sodium peroxodisulfate and the temperature was maintained at 70 ° C. for a further 1 h. After removal of the water by means of a rotary evaporator at 40 ° C bath temperature and rotary vane vacuum, the residue was taken up in 200 ml_ ethanol and 30 minutes on

Rotary evaporator stirred at 80 ° C bath temperature to separate the copolymer from the salt residues. The suspension was then filtered hot and the filtrate was freed from ethanol on a rotary evaporator under a rotary vane vacuum.

Table 5 shows the yield determined in the reaction HMA-GMA:

Amount of initiator based on Σ obtained yield [g] Resultant yield [%] of the monomers GMA + HEMA based on

[Mol%] total monomers

10 9.3

97

20 9.5 99

40 9.0 94 The preparation of the GMA-MAS copolymers according to the invention is advantageously carried out according to the reaction equation:

The amounts of 1.57 g (6.6 mmol) or 3.14 g (13.2 mmol) or 6.28 g, (26.4 mmol) Natnumperoxodisulfat (10.20 and 30 mol% based on the sum of the monomers used) and 0.55 g (6.5 mmol) or 1.1 g (13 mmol) or 2.2 g (26 mmol) of sodium bicarbonate (ACROS) were dissolved in 50 ml of the. Water is dissolved while stirring. Subsequently, the monomer mixtures were prepared from 5.1 ml (5.3 g, 33 mmol) of GMA, and 2.8 ml (2.84 g, 33 mmol) in the ratio 1: 1 were neutralized with sodium hydroxide to pH 7 with neutralized methacrylic acid. The neutralization of the methacrylic acid was carried out in water with the addition of saturated aqueous sodium hydroxide solution, wherein the neutralization was followed by a pH electrode. The monomers were with the. Water to 50 ml_ total volume filled and added dropwise over a period of 2 h by means of dropping funnel to the tempered to 70 ° C initiator solution. After completion of the addition, the reaction solution was treated with a further 1.1 g (4.4 mmol) Natnumperoxodisulfat and tempered for 1 h at 70 ° C. Subsequently, the reaction mixture was acidified to pH = 2 using dilute sulfuric acid and using a pH electrode. After removal of the water by means of a rotary evaporator at 40 ° C bath temperature and rotary vane vacuum, the residue was taken up in 200 ml_ ethanol and stirred for 30 minutes on a rotary evaporator at 80 ° C bath temperature to separate the copolymer from the salt residues. The suspension was subsequently filtered and the filtrate was freed from ethanol on a rotary evaporator under rotary vane vacuum. After dissolving the clean polymer residue in 100 ml_ the. Water, the solution was neutralized to pH = 7 using sodium hydroxide solution and pH electrode and the water on a rotary evaporator at 40 ° C bath temperature and rotary vane vacuum removed.

Table 6 shows the yields determined in reaction GMA-MAS.

The exemplified Herstell regulations and reaction schemes are also applicable to the other copolymers, as is known in the art.

The molar masses of the copolymers produced are also dependent on the amount of initiator used.

The more initiator used, the more small polymers (shorter chain length) can be produced in the reaction. Halving the initiator concentration causes an increase in the chain length of about 40%.

Suitable initiators are water-soluble substances.

For example, inorganic peroxides and water-soluble azo initiators from Wako (sodium, potassium and ammonium peroxodisulfates, 2,2'-azobis (2-methylpropionamidines) dihydrochlorides (V-50), 2,2'-azobis [2] have been used. (2-imidazolin-2-yl) propanes] dihydrochloride (VA-44) and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-57)).

Sodium peroxydisulfate (NaPS) has been found to be the most advantageous

as the NaPS-initiated copolymers were able to absorb the most moisture.

The initiators can advantageously be used in the range from 1 to 40 mol%, preferably in the range from 5 to 20 mol%, based on the total number of moles of the monomers used.

In addition to the inorganic peroxodisulfates, it is also possible, for example, to use water-soluble azo initiators for the preparation of the copolymers. This is followed by only appropriate purification steps. The sodium peroxodisulfate (NaPS) initiator is preferably used in a preferred use range of 5 to 20 mol%, based on the total molar amount of the monomers used.

Table 7 below shows the influence of the different cations in the HEMA-MAS copolymer (20:80) on the water absorption capacity of the copolymers.

The number-average molar masses and polydispersity of the HEMA copolymers prepared by way of example are shown in Tables 8-1 1 below.

Table 8: Determines molecular weights and polydispersities HEMA-MAS

Copolymer Obtained Poly Appearance

Used weights / number average dispersity

amount of initiator

Molecular weight M _n yield

Mol - [%]

[G / mol]

on Σ monomers

HEMA: MAS 3959 3.92 crystalline 6.0 g / 96%

15

20:80

HEMA: MAS 5280 3.24 crystalline 6.1 g / 97%

10

20:80 Table 9: Determines molecular weights and polydispersities HEMA-GAE

Table 10: Determines molecular weights and polydispersities HEMA-GMA

Copolymer Number average polydispersity

Molecular weight M _n [g / mol]

GMA: HEMA 3: 1 3880 1.87

GMA: HEMA 1: 1 4088 2.06

GMA: HEMA 1: 3 1958 1.6

Table 1 1: Determines molecular weights and polydispersities HEMA-AS

Copolymer Number average polydispersity

Molecular weight M _n [g / mol]

AS: HEMA 8: 1 1715 1.81 Table 12 shows the molecular weights and polydispersities GMA-MAS copolymers

By GC, the residual monomer content was then determined, as in the

Table 13 below.

Monomers are known to sensitize, so that as low as possible

Monomer content is desired, which is advantageously achieved according to the invention.

The residual monomer analysis is carried out by GC under the conditions:

Column Varian VCOT Fused silica, L. 50 m, 0 320 μΐη, detector FID,

Detector / injector temperature 250 ° C, temperature program start 60 ° C (3 min), heating 20 ° C / min to 100 ° C (5 min.), 10 ° C / min. up to 200 ° C (10 min.), 20 ° C / min. up to 240 ° C (2 min.), column pressure 50 KPa (constant), carrier gas H ₂ , N ₂ , device name Crompack CP-9003, evaluation software Chrompack CP Maestro 2.

Table 13: Determined by gas chromatography residual monomer amounts in the example HEMA-MAS (50:50)

The residual monomers can be determined both by GC and by HPLC. In order to reduce the residual monomer contents, initiator is additionally added after the polymerization in order to allow the residual monomers to react.

After this step, no or only small amounts of residual monomer

be detected (below the detection limit about 0.05% by weight)

Table 14: Residual monomer amounts HEMA determined by gas chromatography and HPLC

MAS (20:80)

Table 15: Residual amounts of HEMA-GAE determined by gas chromatography and HPLC

The copolymers according to the invention can additionally be crosslinked with small amounts of crosslinker. The proportion of crosslinker is preferably limited to 0.1 to 2 mol%, based on the monomers used.

For example, those with glycerol dimethacrylate (GDMA) and

Polyethylene glycol dimethacrylate (PEG-DMA (Mn: 550)) crosslinked HEMA-MAS copolymers also good properties, such as good water solubility, moisture absorption capacity as shown in Table 16 below:

In principle, crosslinking of copolymers is often not recommended. The

Crosslinking often leads to so-called clumping of the polymers and the desired

Water solubility is thus put on play. However, as shown by the investigations in Table 16, crosslinking fractions of up to 2 mol% of the copolymers according to the invention can be reasonably feared without any loss of moisture-regulating properties. The moisture kinetics presented here and their advantages of

Copolymers of the invention will be explained in more detail below.

Also, the GDMA and PEG-DMA crosslinked HEMA-MAS copolymers with a

Crosslinker content of up to 2 mol.% Accordingly belong to the invention

Copolymers.

The copolymers of the invention are surprisingly soluble in water and glycerol. Surprisingly, high dosages of the inventive copolymers in the water phase of water-based delivery systems such as emulsions, gels are thus possible.

Surprisingly, the copolymers according to the invention are neither gel-forming in water nor do they have a thickening effect. The preparation of copolymers having small molecular weights in the range of less than 17,000 g / mol, in particular less than 10,000 g / mol and especially in the range of 1,700 to 7,000 g / mol, ensures that the negative properties of polymers mentioned in the prior art, such as gelation and thickening, not occur according to the invention.

The copolymers dissolve transparently in water, which makes their use in cosmetic or dermatological preparations also interesting for optical reasons.

These solubility properties are important for use in cosmetic or dermatological preparation, because the copolymers according to the invention may be part of an emulsion as a later component and must therefore be able to mix rapidly with the other components of the water phase as part of the water phase.

In emulsions, the copolymers show the properties to bind the residual water from the emulsion and so increase the skin moisture and / or to bind the glycerol from the emulsion and thus to increase the skin moisture as shown by the studies mentioned.

As was also shown there, the copolymers according to the invention have an advantageous moisture uptake and release capacity.

Thus, the copolymers of the invention have been shown in studies to

Moisture uptake and release as well as solubility unpredictable

Properties.

For example, the copolymer HEMA: MAS (pH = 7) can absorb 59% or 60% of its own weight in water. This offers completely new applications for use as a component of cosmetics.

To determine which monomer combination of HEMA: MAS is a maximum

Moisture uptake capacity were achieved for this purpose HEMA: MAS copolymers produced in various proportions and their

Moisture absorption capacity determined after 8 hours and 48 hours.

Advantageous moisture kinetics showed the copolymers with molar ratios HEMA to MAS in the range of 75:25 to 10:90. It was found that the copolymer of HEMA: MAS 20:80 (pH = 7) with 1 10.8% of its own weight can absorb the maximum amount of water, which represents amazing capacity. Table 17 shows the solubility of the copolymers HEMA-MAS in water and glycerol:

- = poorly soluble, + = mostly soluble, ++ = completely soluble

Table 18 shows the solubility of the copolymers HEMA-GAE in various

solvents

Solvent used Solubility in 2.5 mL Solubility in 2.5 mL Copolymer [mg] Solvent at RT Solvent at>

[+/-] 30 ° C [+/-]

150 dem. Water ++

150 methanol ++

150 ethanol

150 2-propanol

150 2-butanol

150 ethylene glycol ++

150 glycerol + ++

(Anhydrous)

Table 19 shows the solubility of the copolymers HEMA-GAE in different molar ratios in water and glycerin

Table 20 shows the solubility of the copolymers HEMA-AS in different molar ratios in water and glycerin

Solvent (5 mL) Polymer AS: HEMA solubility in of 150 mg

[mol / mol] polymer in 5 mL

Solvent at RT [+/-]

Water 3: 1 +

10% glycerol solution 3: 1 +

Water 1: 1 +

10% glycerol solution 1: 1 +

Water 1: 3 +

10% glycerol solution 1: 3 + Table 21 shows the solubility of the copolymers GMA-MAS

The water solubilities of the copolymers according to the invention are surprisingly good, as the preceding tables show, and the copolymers can therefore be used advantageously as water-containing administration forms.

Since a water solubility of the copolymers is required for the desired application, the poorly or insoluble systems are excluded, resulting, for example, at higher molecular weights.

Furthermore, it was found that in particular the copolymers (20 mol% initiator) which contained the methacrylic acid in neutralized form (pH = 7) had good water solubility. The copolymers containing the methacrylic acid in protonated form (pH = 2) were not only largely soluble in water but also had significantly lower moisture uptake capacities. While the GMA: MAS 50:50 pH = 7 copolymer was able to take up 59% of its own weight, the capacity of the GMA: MAS 50:50 pH = 2 copolymer was only half the capacity at 28.4%. An analogous behavior was observed for HEMA: MAS 50:50 pH = 7 (60%) and HEMA: MAS 50:50 pH = 2 copolymers (16.3%). Furthermore, the copolymers of HEMA-GMA 50:50 (20 mole% initiator), 26.6%, had significantly lower moisture uptake capacities than the copolymers containing methacrylic acid (pH = 7). The water release measurements showed that the copolymers containing methacrysic acid (pH = 7) gave 42.7 (GMA: MAS 50:50 pH = 7) and 43.7 (HEMA: MAS 50:50 pH = 7) over 8 h, whereas the GMA : HEMA 50:50 copolymer gives off only 18.5% water. A very important aspect of this series of experiments is the fact that doubling the amount of initiator from 20 to 40% mol%, both in the GMA: HEMA 50:50 (26.6 to 20.4%) and in the GMA: MAS 50:50 pH = 7 copolymers (59.0 to 52.6%) a decrease in moisture absorption capacity is observed. To measure the moisture absorption capacity of the copolymers, a defined amount of the copolymers prepared in each case was weighed into a weighing dish by dissolving the respective amount in 5 ml of water and then quantitatively transferring it to the weighing dish. The weighing dish filled in this way with the polymer solution was placed in a drying oven heated to 40 ° C. for exactly 12 ± 1 hour, so that a uniform polymer film was formed. After reaching the weight constancy, the small bowl and its contents are transferred to a special device for determining the moisture absorption capacity.

The moisture absorption device was in the form of a cocktail shaker

(Dimensions LxWxH: 90x90x220 mm) and consists of a reservoir for aqueous solutions above which a plastic sieve is attached. On this sieve, which is about 10 cm above the liquid, the weighing dish is placed and closed the shaker with a lid.

The liquid used is a saturated aqueous solution of potassium chloride, which produces an air humidity of 84.3% at 25 ° C. The humidity set in this way corresponds to the humidity averaged over the year in Germany.

By differential weighing the weight of the weighing pan with its content in certain

Time intervals it is possible to track the water absorption of the polymer film.

Moisture uptake measurements were performed according to the measurement parameters given in Table 22:

Table 22: Parameters of the moisture absorption measurements using the example HEMA-MAS

Parameter Used

Initiator, buffer sodium peroxodisulfate (NaPS), sodium bicarbonate

(NaHCO ₃ )

2-Hydroxyethyl methacrylate (HEMA), methacrylic acid (MAS) monomers used

Used monomer ratio 50:50, variable amounts of initiator;

Monomer ratios Monomer ratio 10:90 to 75:25, initiator amounts: 20

mol%

Polymerization time 3 hours in water at 70 ° C

Workup Acidify the reaction solution to pH = 2, remove

Salts and water with ethanol (78 ° C), reneutralization to pH = 7

Weighing Scale [mg] 100 (Copolymers)

Calculated layer thickness 0.1 (copolymers)

[Mm] Measuring vessel shaker, 8 measurements at intervals of 1 h or 48 h

Moisture solution 150 ml saturated potassium chloride solution in water,

Humidity 84.3% at 25 ° C

Figures 2 to 6 show the moisture absorbency of the HEMA-MAS copolymers. Both dependencies on the pH, the monomer ratio and the amount of initiator have been investigated.

It turns out that while the pH, monomer ratio and amount of initiator exert an influence on the water absorption capacity of the copolymers, the capacities are all in the range according to the invention.

The HEMA-MAS copolymer (20:80) according to the invention can, for example, take up 72% or 100% of the intrinsic weight of water in 8 hours, as shown in FIG. 6.

The copolymers of structure (II), HEMA-GAE, also show good

Water absorbency, as shown in Tables 23, 24, 25 and Figure 7.

Glycerol allyl ether - GAE may also be abbreviated to AE or allyl ether.

Table 23: Water uptake of HEMA-GAE copolymers

Molar, mass of water uptake Ingestible Ingested One Mol [%] Amount of Water Amount of Water Monomer Ratio: Substance [g] [g] [mol] per mole of GAE: HEMA Copolymer

1: 1 4646 12.6 585 32

2: 1 3836 15.5 595 33

4: 1 3729 16.3 608 34

6: 1 4471 13.7 613 34

8: 1 4562 15.6 712 40 Table 24: Water uptake of HEMA-GAE copolymers

Table 25: Water uptake of HEMA-GAE copolymers

Solubility of 150 mg water uptake in 8 h polymer in 2.5 mL [%] at 84% rel.

Copolymer solvent

Solvent at RT [+/- humidity and] film thickness 0.5 mm

The water ++ 15.6

GAE: HEMA 8: 1

10%

++

glycerol solution

The water ++ 13.7

GAE: HEMA 6: 1

10%

++

glycerol solution

The water ++ 16.3

GAE: HEMA 4: 1

10%

++

glycerol solution

The water ++ 15.5

GAE: HEMA 2: 1

10%

++

glycerol solution

Dem. Water ++ 12.6

GAE: HEMA 1: 1

10%

++

glycerol solution The copolymers of structure (III), HEMA-GMA, also show good

Water absorbency, as shown in Figures 8 and 9.

Glyceryl methacrylate - GMA may also be abbreviated to GLMA.

In the same way, the copolymers of structure (VI), GM-MAS, also show a good water absorption capacity, as shown in FIGS. 10 and 11.

The moisture release measurement was made following the 8-48 hour moistening of the polymer films by means of a saturated potassium carbonate sesquihydrate solution. For this purpose, the saturated potassium chloride solution was removed from the shaker and this filled after thorough cleaning and drying with the saturated potassium carbonate solution. The

The weighing dish together with the polymer film was now placed in the shaker and exposed in this way to an interior atmosphere with a relative humidity of 43.2%. The

Measurements were made over 8 hours with hourly recording.

The moisture release measurement was carried out in accordance with the measurement parameters given in Table 26 below, using the example of the HEMA-MAS copolymers:

Table 26: Parameters of Moisture Delivery Measurements Example of HEMA-MAS Copolymers

Parameter Used

Initiator, buffer sodium peroxodisulfate (NaPS), sodium bicarbonate

(NaHCO ₃ )

2-Hydroxyethyl methacrylate (HEMA), methacrylic acid (MAS) monomers used

Used monomer ratio 50:50, 10:90 to 75:25 variable

Monomer ratios Initiator amounts: 10, 20 and 40 mol%

Polymerization time 3 hours in water at 70 ° C

Workup Acidify the reaction solution to pH = 2, remove

Salts and water with ethanol (78 ° C), reneutralization to pH = 7

Weighing Scale [mg] 100 (Copolymers)

Calculated layer thickness 0.1 (copolymers)

[Mm]

Measuring vessel shaker, 8 measurements at intervals of 1 h

Moisture solution 150 ml saturated potassium carbonate solution in water,

Humidity 43.2% at 25 ° C Figures 12 to 18 show by way of example the thus obtained moisture release values of the HEMA-MAS, the HEMA-GMA, GMA-MAS and HEMA-AS copolymers.

From the measurements again the influence of the monomer ratios and amount of initiator becomes clear.

The particularly preferred copolymer HEMA-MAS 80:20 according to the invention still retains 30% of its own weight in residual moisture after 8 hours, as Figure 15 shows.

The use of the copolymers according to the invention as a long-term moisturizer is thus possible.

Tables 27 to 30 below show a comparison of moisture kinetics.

Table 27:

Polymer Monomer InitiatorOne scale layerWaterWater ratio Amount [mg] Thickness in residual content

[Mol%] [mm] 8 h [%] after 8 h

[%]

HEMA- 50:50 20 100 0.1 26.6 unknown MAS

pH = 2

HEMA- 50:50 20 100 0.1 60.0 16.3 MAS

pH = 7

Table 28:

Copolymer Initiator Solubility Solubility WaterWaterwater of 150mg uptake in 8h quantity of polymer in 8h at 48h at 43% rel. [Mol%] 2.5ml_ 84% rel. 84% rel. Luftfeuchtigke

Solvent Humidity Humidity and El at RT [+/- speed and film and film thickness 0.1] Film thickness Film thickness mm [%]

0.1 mm [%] 0.1 mm [%]

HEMA: MA 20 Dem. ++ 53.9 69.5 14.7

P 75:25 Water

pH = 7 10% ++

glycerin

-solution

HEMA: MA 20 Dem. ++ 60.0 72.8 15.5

S 50:50 water

pH = 7 10% ++

glycerin

-solution

HEMA: MA 20 Dem. ++ 67.8 87.8 23.5

S 40:60 water

pH = 7 10% ++

glycerin

-solution

HEMA: MA 20 Dem. ++ 74.9 95.8 25

S 30:70 Water

pH = 7

HEMA: MA 20 Dem. ++ 80.9 1 10.8 31 .2

P 20:80 Water

pH = 7 10% ++

glycerin

-solution

HEMA: MA 20 Dem. ++ 30.5 39.1 8.0

S 10:90 water pH = 7 10% ++

Glycerinl

-ösung

- = poorly soluble, + = mostly soluble, ++ = fully soluble 1

Table 29:

Table 30:

[Mol%] [mm] 8 h [%] after 8 h

[%]

GMA- 50:50 10

MAS

GMA 50:50 20 100 0.1 28.4 unknown

MAS

pH = 2

GMA- 50:50 20 100 0.1 59.0 16.3

MAS

pH = 7

The following Table 31 shows in the overview characteristic water uptake or release values of the copolymers according to the invention.

Table 31:

Monomer 1 Monomer 2 Copolymer Water up to (use ratio) in 8 h in 48 h

Glycerol 2-hydroxy-HEMA-GAE - 34%

allyl ether ethyl methacrylate copolymer (1: 2) (saturated)

(GAE) (HEMA)

Glyceryl 2-hydroxy GLMA HEMA 27%

methacrylate ethyl methacrylate copolymer (saturated)

(GMA) (HEMA) (50:50)

Glyceryl methacrylic acid GLMA-MAS- 28%

methacrylate (MAS) copolymer (saturated)

(GMA) (50:50)

pH = 2 (as free

Acid)

Glyceryl methacrylic acid GLMA-MAS- 59%

methacrylate (MAS) copolymer

(GMA) (50:50)

pH = 7 (as

Sodium salt)

3-sulfo-2-hydroxy-SPA-HEMA 46% 63% propyl acrylate ethyl methacrylate copolymer

(SPA) (HEMA) (80:20)

3-sulfo-methacrylic acid SPA-MAS- 73% 90% propyl acrylate (MAS) copolymer

(SPA) (50:50)

pH = 7 (as

Sodium salt) 3-sulfo-glyceryl-SPA-GLMA-43% 53% propyl acrylate methacrylate copolymer

(SPA) (GMA) (80:20)

2-hydroxyacrylic acid HEMA-AS- 64% 77% ethyl methacrylate (AS) copolymer

(HEMA) (80:20)

2-Hydroxy-methacrylic acid HEA-MAS 70% 108% ethyl acrylate (MAS) copolymer

(HEA) (80:20)

It was found that the moisture absorption capacity depends on the monomer ratios. From the HEMA: MAS 25: 75 copolymer to the HEMA: MAS 20: 80 copolymer, a steadily increasing moisture absorption capacity was found. The maximum is not as expected for the HEMA: MAS 10: 90 copolymer, but for the HEMA: MAS 20: 80 ratio. A 69.5% equally high capacity already has the HEMA: MAS 25: 75 copolymer. The HEMA: MAS copolymers from the monomer ratios 50:50 (72.8%), 40:60 (87.8%), 30:70 (95.8%) and 20:80 (1 10.8%) have an increasing capacity.

The moisture release measurement carried out after reaching saturation gave an analogous result. Thereafter, the HEMA: MAS 20:80 copolymer with 79.6% gives the most, the HEMA: MAS 10: 90 copolymer with 31.1 the least water within 8 hours.

The copolymers of the invention, in particular those with a middle

Molar weight less than 10,000 g / mol and a HEMA-MAS ratio in the range of 75: 25 to 10:90, are also useful as moisture regulators in various fields and formulations due to their water and glycerin solubility and moisture uptake properties. In particular, the copolymers according to the invention can be used as moisture regulators in cosmetic or dermatological preparations in that they can advantageously help to improve skin moisturization.

The further comparative investigations also confirm the water absorption capacity of the copolymers according to the invention. Thus, water absorption tests at 32 ° C were carried out by various cosmetics known in cosmetics, such as moisturizers and emulsifiers, after 6 hours, 1 day and 1 week. 32 ° C represents the usual skin surface temperature. The following Table 32 shows the water absorption at 32 ° C and 100% rel.

Humidity. The increase was determined gravimetrically in relation to the starting weight.

Table 32: Water intake capacities

It turns out that the copolymers according to the invention are approximately good

Water absorption such as glycerol known as wetting agents, sorbitol and Ha have. In a further comparative study, the water content in pig skin was determined, which represents a more application-oriented method of determining the moistening performance of cosmetic substances.

The determination was carried out by means of ATR-IR spectroscopy. Figure 19 shows the comparison of water content in pigskin. For comparison, the water content in pigskin was measured with glycerol and against untreated.

The water absorption and moistening performance of the copolymers according to the invention in the skin is thus shown. Surprisingly, the humidifying performance of

Copolymers even in the range of glycerol.

As further evidence for the skin moisturizing performance of the copolymers of the invention is a long-term corneometry study using the example of HEMA-MAS copolymers

Have been carried out. For this purpose, two 5% aqueous solutions of the HEMA-MAS copolymers (copolymer with Mn = 3387 g / mol and copolymer with Mn = 6277 g / mol) 2 times a day for 2 weeks applied to the forearms of subjects. Before the first

Product application (tO), 7 days (t1) and 14 days after the first product application (t2), the skin moisturization of the respective treated areas as well as an untreated area of the forearm was measured by corneometry.

Coreanometer unit differences t1 -t0 and t2-t0 are shown in Figure 20.

Figure 20 shows that the copolymer solutions have higher skin moisturization than the untreated areas.

The copolymer solutions moisturize the skin and are thus advantageously usable as skin moisturizing agents in cosmetic or dermatological preparations.

The copolymers are thus excellently suitable as a skin moisturizer with the

Benefits of skin hydration on the surface and film formation on the surface

Surface that prevents the rapid evaporation of water on the skin surface and protects the skin from environmental influences.

In addition, the olfactory properties of the copolymers according to the invention have also been investigated, as shown in Tables 33 and 34 below. Table 33 Olfactory Properties HEMA-MAS Copolymers

Table 34 Olfactic Properties HEMA-GAE Copolymers

As Tables 33 and 34 show, the copolymers of the invention are as

Cosmetic component thus also for aesthetic / olfactory reasons applicable. This is often not the case with the conventional polymers of the prior art.

Due to their very good solubility in water, the copolymers according to the invention make it possible that their proportion in water-based delivery systems, such as, for example, gels or emulsions, is far beyond the usual proportions of the polymers of the prior art.

Advantageously, the copolymers according to the invention can be added to a proportion of up to 50% by weight of the preparation. In particular, the proportion by weight of

Copolymers of the invention advantageously in the range of 1 to 20 wt.%, In particular in the range of 2.5 to 10 wt.%, Based on the total mass of the preparation.

The copolymers according to the invention have relatively small molecular weights of less than 17,000 g / mol, advantageously less than 10,000 g / mol and in particular in the range of 3,000 to 7,000 g / mol, and are nevertheless extremely good at absorbing water. In particular from dry phases, such as as emulsion residue on the skin or

water-binding after release of water at 40% relative humidity (dry rooms).

As the investigations have shown, for example, the copolymer still retains 30% residual moisture (at 43% relative humidity) 8 hours after application, which can further moisturize the skin. A long-term humidifying effect is thus given.

The copolymers are water-soluble. Water-soluble is to be understood as the solubility of at least 10 g of copolymer per 100 g of water at a temperature of 20 ° C.

Despite the low tackiness of the copolymers when the water-soluble polymer is applied to the skin and the water evaporates slowly, leaving only the

Polymer residue remains on the skin, a film can form on the skin surface.

The copolymers according to the invention in water do not form gels makes them universally applicable without having to consider additional viscosity problems of the final preparations. In the same way is advantageous to see their property in aqueous

Preparations or emulsions not thickening effect.

The non-gelation as well as the non-thickening effect of the invention

Copolymers makes a decisive difference to the polymers known from the prior art with (meth) acrylate.

The non-gelation and non-thickening action of the copolymers according to the invention was investigated by means of viscosity measurements of Example Preparations 11, 13, 16 and 18. The viscosity was determined using a Viscotester VT-02 from Haake at 20 ° C. with the aid of the rotating body 1 or 2 and reading the scale 1 or 2 (corresponds to a shear rate of 10 Pa / s).

The following viscosities were evident:

Example 1 1: O / W emulsion with glycerol and without HEMA-MAS copolymer: 5750 mPas Example 13: O / W emulsion with glycerol and 5% by weight HEMA-MAS copolymer: 4200 mPas

Example 16: O / W emulsion without glycerol and without HEMA-MAS copolymer: 5800 mPas Example 18: O / W emulsion without glycerol and with 5% by weight HEMA-MAS copolymer: 3950 mPas.

The viscosity data show that the addition of copolymer does not increase the viscosity of the preparations. The copolymers therefore have no gel-forming or thickening effect in aqueous preparations. Likewise, a gelation or thickening is also not visible optically.

On the contrary, the viscosity measurements show that the viscosity of the preparations with HEMA-MAS copolymers is surprisingly lower than the comparable ones

Preparations without HEMA-MAS copolymers. The HEMA-MAS copolymer may even make the system slightly more fluid, lower viscous.

The use and the use of the copolymers of the invention is in various dosage forms, i. Preparations or means possible. The copolymers according to the invention can be used in particular in water-based preparations in which water solubility, water absorption or release is advantageous and an influence on the viscosity of the preparations should be avoided (avoidance of gel formation or thickening).

The copolymers of the invention can be used in particular in any customary

Forms of preparation are used, such as W / O emulsions, O / W emulsions,

Hydrodispersions, gels, alcoholic preparations, cosmetic sprays, pads, cloth, plaster, W / S, b / w, microemulsion, nanoemulsion, mousse, foam, PIT emulsion, hydrogel, hydrodispersion gel, multiple emulsion, ointment, cream gel, cream Lotion, in particular W / O, O / W or W / O / W emulsions. The copolymers according to the invention can also be used in gel preparations, the gel then naturally not being formed on the basis of the copolymers but on the basis of the customary gel preparation ingredients.

Preference is given to cosmetic or dermatological preparations to which the copolymers according to the invention can be added. The preparations according to the invention may then further contain cosmetic adjuvants and other active ingredients such as are commonly used in such preparations, e.g. Preservatives, preservatives, bactericides, perfumes, foaming inhibitors, colorants and pigments, thickeners, wetting and / or

moisturizing substances, fats, oils, waxes or other common ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives, provided that the additive does not affect the required properties.

Advantageously, the cosmetic or dermatological preparations comprise active ingredients and / or derivatives thereof, such as. Alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, fumaric acid esters, ectoine and its derivatives, tea extracts, folic acid, arginine and its salts, taurine, glyceryl glucose and / or beta-alanine. These active ingredients may be contained in a proportion of 0.001 to 10% by weight, based on the total weight of the preparation, advantageously in this.

In addition to its own moistening performance, which is imparted to the formulations by the use of the copolymers, it is possible to add further moisturizers, so-called moisturizers, to the preparations.

Moisturizers are substances or mixtures of substances which give cosmetic or dermatological preparations the property of reducing the moisture release of the horny layer (also called trans-epidermal water loss (TEWL) after application or spreading on the skin surface) and / or hydrating the skin Horny layer to influence positively.

The proportion of additional skin moisturizing agents is preferably in the range from 1 to 20% by weight, based on the total mass of the preparation.

Advantageous moisturizers for the purposes of the present invention are in particular glycerol. However, furthermore, lactic acid, butylene glycol, sorbitol, pyrrolidonecarboxylic acid, polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gellable polysaccharides can be used as moisturizers. Particularly advantageous are, for example, short-chain hyaluronic acid (<50,000 daltons) and long-chain hyaluronic acid (> 50,000 daltons), chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registry number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available.

In particular in combination with the known moisturizers, such as glycerol, a double wetting effect can be achieved with the copolymers according to the invention.

Glycerin acts in cosmetic or dermatological preparations

known as a deep moisturizer and the copolymers as Oberflächenbefeuchter.

Due to their properties, the copolymers according to the invention increase the care and / or active power of cosmetic or dermatological preparations. According to the invention, an increase in the care or active power means that the care or active power, such as, for example, the moistening of the skin, is caused by the copolymer (s) contained is increased in comparison to a preparation containing the same ingredients without the copolymers.

The preparations according to the invention can be formulated for topical application. According to the invention, topically administrable preparations are, in particular, lotions, gels, emulsions, aerosol mousses, pumpable preparations, creams and wipes, pads or patches impregnated or loaded with the preparations.

The following examples show cosmetic preparations in which the

Copolymers of the invention were incorporated. The numbers refer to parts by weight based on the total mass of the respective preparation.

Examples 1, 6, 11 and 16 are comparative examples which are not according to the invention and which have a reduced moisture performance compared with the example preparations according to the invention.

Examples

Ingredients 1 2 3 4 5

Cyclomethicones 5 5 5 5 5

Butyrospermum Parkii Butter 1 1 1 1 1

Glycerol 3,477 3,477 3,477 3,477 3,477

Butylene Glycol 2 2 2 2 2

Aqua + Sodium 0.52 0.52 0.52 0.52 0.52

Methyl paraben 0, 15 0, 15 0, 15 0, 15 0, 15

Phenoxyethanol 0.4 0.4 0.4 0.4 0.4

Acrylates / C 10-30 Alkyl Acrylate Crosspolymer 0.8 0.8 0.8 0.8 0.8

Ammonium acryloyldimethyltaurate / VP

Copolymer 0.2 0.2 0.2 0.2 0.2

83,15 80,65 78, 15 75,65 73, 15

Aqua 3 3 3 3 3

Alcohol Denat, 3 3 3 3 3

Perfume 0.3 0.3 0.3 0.3 0.3

Polymer HEMA-MAS (20:80) Mn = 3387 g / mol 0 2.5 5 7.5 10 Ingredients 6 7 8 9 10

Cyclomethicones 5 5 5 5 5

Butyrospermum Parkii Butter 1 1 1 1 1

Butylene Glycol 2 2 2 2 2

Aqua + Sodium Hydroxide 0.52 0.52 0.52 0.52 0.52

Methyl paraben 0, 15 0, 15 0, 15 0, 15 0, 15

Phenoxyethanol 0.4 0.4 0.4 0.4 0.4

Acrylates / C 10-30 Alkyl Acrylate Crosspolymer 0.8 0.8 0.8 0.8 0.8

Ammonium Acryloyldimethyltaurate / VP Copolymer 0.2 0.2 0.2 0.2 0.2

Aqua 86.63 84, 13 81, 63 79.13 76.63

Alcohol Denat. 3 3 3 3 3

Perfume 0.3 0.3 0.3 0.3 0.3

Polymer HEMA-MAS (20:80) Mn = 3387 g / mol 0 2.5 5 7.5 10

O / W emulsions

Ingredients 1 1 12 13 14 15

Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5

Ethylhexylglycerol 0.5 0.5 0.5 0.5 0.5

Caprylic / Capric Triglycerides 1 1 1 1 1

Cera Microcristallina + Paraffin Liquidum 3 3 3 3 3

Cetearyl Alcohol 4 4 4 4 4

Dimethicone 0.5 0.5 0.5 0.5 0.5

C12-15 alkyl benzoate 2 2 2 2 2

Butyrospermum Parkii Butter 3 3 3 3 3

Glyceryl Stearate 2.6 2.6 2.6 2.6 2.6

PEG-40 Stearate 0.8 0.8 0.8 0.8 0.8

Glycerine 8,693 8,693 8,693 8,693 8,693

Aqua + Sodium Hydroxide 0.6 0.6 0.6 0.6 0.6

Ethylparaben 0, 1 0, 1 0.1 0, 1 0.1

Methylparaben 0.2 0.2 0.2 0.2 0.2

Propylparaben 0, 1 0, 1 0.1 0, 1 0.1

Phenoxyethanol 0.4 0.4 0.4 0.4 0.4

Methylpropanediol 4 4 4 4 4

Carbomer 0.1 0, 1 0.1 0, 1 0.1

Chondrus Crispus 0,2 0,2 0,2 0,2 0,2 Aqua 55,457 52,957 50,457 47,957 45,457

Aqua + Trisodium EDTA 1 1 1 1 1

Ethylhexyl methoxycinnamate + BHT 7 7 7 7 7

Butyl methoxydibenzoylmethane 2 2 2 2 2

Phenylbenzimidazole sulfonic acid 1, 5 1, 5 1, 5 1, 5 1, 5

Titanium Dioxide + Trimethoxycaprylyisilane 0,5 0,5 0,5 0,5 0,5

Perfume 0.25 0.25 0.25 0.25 0.25

Polymer HEMA-MAS (20:80) Mn = 3387 g / mol 0 2.5 5 7.5 10

Ingredients 16 17 18 19 20

Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5

Ethylhexylglycerol 0.5 0.5 0.5 0.5 0.5

Caprylic / Capric Triglycerides 1 1 1 1 1

Cera Microcristallina + Paraffin Liquidum 3 3 3 3 3

Cetearyl Alcohol 4 4 4 4 4

Dimethicone 0.5 0.5 0.5 0.5 0.5

C12-15 alkyl benzoate 2 2 2 2 2

Butyrospermum Parkii Butter 3 3 3 3 3

Glyceryl Stearate 2.6 2.6 2.6 2.6 2.6

PEG-40 Stearate 0.8 0.8 0.8 0.8 0.8

Aqua + Sodium Hydroxide 0.6 0.6 0.6 0.6 0.6

Ethylparaben 0.1 0.1 0.1 0.1 0, 1

Methylparaben 0.2 0.2 0.2 0.2 0.2

Propylparaben 0.1 0.1 0.1 0.1 0, 1

Phenoxyethanol 0.4 0.4 0.4 0.4 0.4

Methylpropanediol 4 4 4 4 4

Carbomer 0, 1 0.1 0.1 0.1 0, 1

Chondrus Crispus 0,2 0,2 0,2 0,2 0,2

Aqua 64, 15 61, 65 59, 15 56.65 54, 15

Aqua + Trisodium EDTA 1 1 1 1 1

Ethylhexyl methoxycinnamate + BHT 7 7 7 7 7

Butyl methoxydibenzoylmethane 2 2 2 2 2

Phenylbenzimidazole sulfonic acid 1, 5 1, 5 1, 5 1, 5 1, 5

Titanium Dioxide + Trimethoxycaprylyisilane 0,5 0,5 0,5 0,5 0,5

Perfume 0.25 0.25 0.25 0.25 0.25 Polymer HEMA-MAS (20:80) Mn = 3387 g / mol 0 2.5 7.5 10

Ingredients 21 22 23 24 25

Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5

Ethylhexylglycerol 0.5 0.5 0.5 0.5 0.5

Caprylic / Capric Triglycerides 1 1 1 1 1

Cera Microcristallina + Paraffin Liquidum 3 3 3 3 3

Cetearyl Alcohol 4 4 4 4 4

Dimethicone 0.5 0.5 0.5 0.5 0.5

C12-15 alkyl benzoate 2 2 2 2 2

Butyrospermum Parkii Butter 3 3 3 3 3

Glyceryl Stearate 2.6 2.6 2.6 2.6 2.6

PEG-40 Stearate 0.8 0.8 0.8 0.8 0.8

Glycerine 8,693 8,693 8,693 8,693 8,693

Aqua + Sodium Hydroxide 0.6 0.6 0.6 0.6 0.6

Ethylparaben 0, 1 0, 1 0.1 0, 1 0.1

Methylparaben 0.2 0.2 0.2 0.2 0.2

Propylparaben 0, 1 0, 1 0.1 0, 1 0.1

Phenoxyethanol 0.4 0.4 0.4 0.4 0.4

Methylpropanediol 4 4 4 4 4

Carbomer 0.1 0, 1 0.1 0, 1 0.1

Chondrus Crispus 0,2 0,2 0,2 0,2 0,2

Aqua 50,457 52,957 50,457 47,957 45,457

Aqua + Trisodium EDTA 1 1 1 1 1

Ethylhexyl methoxycinnamate + BHT 7 7 7 7 7

Butyl methoxydibenzoylmethane 2 2 2 2 2

Phenylbenzimidazole sulfonic acid 1, 5 1, 5 1, 5 1, 5 1, 5

Titanium Dioxide + Trimethoxycaprylylsilane 0.5 0.5 0.5 0.5 0.5

Perfume 0.25 0.25 0.25 0.25 0.25

Polymer HEMA-MAS (20:80) Mn = 3387 g / mol 0 1, 5 0 0 1

Polymer HEMA-GAE (50:50) Mn = 2017 g / mol 5 1 2.5 0 5

Polymer HEMA-GMA (75:25) Mn = 1958 g / mol 0 0 1, 5 0 0

Polymer HEMA-SPA (20:80) 0 0 0 7,5 0

Polymer HEMA-AS (10:90) Mn = 1715 g / mol 0 0 0 0 4

Polymer GMA-MAS (50:50) 0 0 1, 0 0 0

Claims

Claims. Copolymers of 2-hydroxyethyl methacrylate and methacrylic acid (I), glycerol allyl ether (II), glyceryl methacrylate (III), 3-sulfopropyl acrylate (IV) or acrylic acid (V), copolymers of glyceryl methacrylate and 3-sulfopropyl acrylate (VI) or methacrylic acid ( VII) or copolymers of methacrylic acid and 3-sulfo-propyl acrylate or 2-hydroxyethyl acrylate (VIII)

(I)

IVI)

(VIII)

characterized in that ^* initiator radicals and Z ^{+ represent} cationic radicals and the coefficients m in the range m = 2 to 58 and n = 8 to 105 are selected and the average molecular weight of the copolymers is less than 17,000 g / mol.

2. Copolymers according to claim 1, characterized in that

the initiator radicals ^{* are} selected from the group -H, -SO ₄ , -OH,

the cationic radicals Z ^{+ are} selected from H, Na, K, Ca, NH ₄ or

Alkylammonium compounds NR ₃ R ₄ R ₅ R ₆ with R ₃ -R ₆ = H, CH ₃ or C ₂ H _5, m in the range from 2 to 45,

n in the range 8 to 75 and / or

M ^"j _m the range of <10,000 g / mol, in particular in the range from 1700 to 7000 g / mol are chosen

3. Water-based administration forms comprising one or more copolymers according to one of claims 1 to 2.

4. dosage form according to claim 3 as a cosmetic or dermatological preparation.

5. Dosage form according to claim 3 or 4, characterized in that the

Weight fraction of the copolymers up to 50 wt.%, In particular in the range of 1 to 20 Wt.%, In particular in the range of 2.5 to 10 wt.%, Based on the total mass of the dosage form, is selected.

6. Preparations according to claim 4 or 5 comprising one or more additional

Skin moisturizer, especially glycerin.

7. Use of the copolymers according to one of claims 1 to 2 as

Feuchtigskeitsregulatoren.

8. Use of the copolymers according to claim 7 in cosmetic or dermatological preparations for skin moisturization.

9. Use according to claim 8, characterized in that one or more

additional skin moisturizers, in particular glycerol, to which preparations have been added.