DE102010012590A1 - Water-soluble copolymers - Google Patents

Abstract

Novel copolymers of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAS), glycerol allyl ether (GAE), glyceryl methacrylate (GMA), 3-sulfo-propylacrylate (SPA) or acrylic acid (AS) are described. A second group of copolymers is formed from glyceryl methacrylate (GMA) and methacrylic acid group copolymers is formed from methacrylic acid (MAS) and 3-sulfo-propylacrylate (SPA) or 2-hydroxyethyl acrylate (HEA). The copolymers have a molecular weight of less than 17,000 g / mol and, owing to their water solubility, water uptake and release kinetics, can be used in particular as wetting agents in cosmetic or dermatological preparations.

Description

The invention describes novel copolymers of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAS), glycerol allyl ether (GAE), glyceryl methacrylate (GMA), 3-sulfo-propyl 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-sulfo-propyl 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 humectants in cosmetic or dermatological preparations.

As water-soluble polymers, the person skilled in the art can select from a number of known polymers, such as polyvinyl alcohol, gelatin, polyacrylic acid, sodium polyacrylates, methylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, gum 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 in JP 2009040705 described, or crosslinked acrylic acid polymers or copolymer, 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 hydration. The gels include polyglyceryl methacrylate, which are water-soluble and water-absorbent used as a moisturizer.

WO 2008087119 describes styrenic acrylate diblock copolymers which are said to have skin moisturizing properties.

In trade, the polyglyceryl (meth) are arcrylate available as homopolymers or copolymer of acrylic acid or Metharcylsäure as Lubrajel ^® or Lubrasil ^®. The known polymers can generally be prepared by free-radical polymerization. The use of the method ranges from the presentation of polystyrene and polyvinyl chloride to polyacrylic acid, polyacrylamide and polyvinyl acetate. Different methods are used. In addition to the solution polymerization, emulsion, suspension and bulk polymerization are used.

EP 1195394 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 binding agents in pharmaceutical dosage forms.

For the preparation of the copolymers are hydroxy-alkyl (meth) acrylates, including HEMA, polymerized in the presence of PVA both by means 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'-azo-bis- (2-methylbutyronitrile). 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 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 the initiators mentioned used. The radical emulsion polymerization according to EP 1195394 preferably takes place in water with the concomitant use of polyvinyl alcohol, in the presence of free-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. The copolymers are obtained 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 water-soluble powders.

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

PVA is according to EP 1195394 used as a protective colloid. PVA prevents agglomeration of the 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 meeting of the Section "Macromolecular Chemistry" of the Society of German Chemists on "Polymers and Water" in Bad Nauheim on April 2 and 3, 1984 - disclosed.

Since the late 1930s, contact lenses made of polymeric materials have been used on the human eye. At present, a variety of contact lens materials are used 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, monomers such as N-vinyl pyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA) or glyceryl methacrylate (GMA) were 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 need for o. G. Monomers, given a cost-effective availability. Since the contact lenses today no longer consist only of a homopolymer, there are very extensive combination options 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.

However, the use of these contact lens polymers in cosmetic or dermatological administration forms or formulations is not possible 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-sulfo-propyl acrylate (SPA) and / or acrylic acid (AS).

(II) für HEMA-GAE-Copolymere

(III) für HEMA-GMA-Copolymere

(IV) für HEMA-SPA-Copolymere

(V) für HEMA-AS-Copolymere

Hereinafter referred to as HEMA-MAS, HEMA-GAE, HEMA-GMA, HEMA-SPA or HEMA-AS copolymer or only as HEMA copolymers with the respective structures (I) for HEMA-MAS copolymers

(II) for HEMA-GAE copolymers

(III) for HEMA-GMA 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).

(VII) für GMA-SPA-Copolymer

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-sulfo-propyl 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 radicals used in the preparation are characterized, which may represent, depending on the particular initiator, in particular sulfate, hydrogen and / or hydroxide radicals.

Z ⁺ is a cationic residue.

For the HEMA-MAS copolymers and MAS copolymers, a neutralized methacrylic acid (MAS) is used as the methacrylic acid. Ie. 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 C ₂ H. ₅ .

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

Unlike the in EP 1195394 As a result of the cationic radicals Z ⁺ and the initiator radicals, the copolymers according to the invention are polyelectrolytes which are and remain water-soluble.

Another difference is that copolymers according to the invention can not be prepared by emulsion polymerization and the addition of protective colloids, emulsifiers or non-aqueous solvents can be dispensed with in the case of a free-radical initiated polymerization in an aqueous solvent.

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 HEMA copolymers. The GMA copolymers according to the invention are therefore in particular obtainable 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 free-radical polymerization in solution, inorganic peroxy initiators are advantageously 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 = 4-12, 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 of the present invention is exemplified as follows for the HEMA-MAS copolymer.

The determination is carried out by means of ¹ H-NMR spectroscopy, as in - H spectrum of a HEMA-MAS copolymer - is shown.

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.

X

= Einbaurate des Methacrylats

(1 – X)

= Einbaurate des 2-Hydroxyethylacrylats

I_a

= Integralwert des Signals der Methylengruppe der HEMA-Einheit b.

I_b

= Integralwert des Signals der Methylengruppe der Polymerketten d, f (HEMA- und MA-Einheit)

The incorporation rate (stated 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 is recorded at 1.6-2.0 ppm (four protons).

X

= Incorporation rate of methacrylate

(1 - X)

= Incorporation rate of 2-hydroxyethyl acrylate

I _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, d. H. 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 installation ratio of HEMA 20% d. H. 3387 × 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% d. H. 3387 × 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 molar mass of the copolymer of HEMA-MAS of 6277 g / mol, the coefficients are 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 can fully exploit their advantageous 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. For most methods, however, reference substances are required to deliver the desired results.

M _n:

zahlenmittlere Molmasse

n_i:

Zahl der Makromoleküle in der Probe mit genau i Repetiereinheiten

M_i:

Molmasse i

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 average is the number average molecular weight (M _n ):

M _n :

number average molecular weight

n _i :

Number of macromolecules in the sample with exactly one repeating unit

M _i :

Molecular weight i

The number average molecular weight can be determined by colligative methods such. As the cryoscopy, membrane or Dampfdruckosmometrie determine and - if the number of end groups per molecule is known - by end group determination.

M _w:

gewichtsmittlere Molmasse

n_i:

Zahl der Makromoleküle in der Probe mit genau i Repetiereinheiten

M_i:

Molmasse i

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

M _w :

weight average molecular weight

n _i :

Number of macromolecules in the sample with exactly one repeating unit

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.

P

= Polydispersität

M _w:

Gewichtsmittlere Molmasse

M _n:

Zahlenmittlere Molmasse

From two of these average molecular weights, one can calculate the polydispersity (P) of a polymer shown:

P

= Polydispersity

M _w :

Weight-average molecular weight

M _n :

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.

v

= kinetische Kettenlänge

f

= Radikalausbeute

k_t

= Geschwindigkeitskonstante der Abbruchreaktion (Disproportionierung und Abbruch)

k_p

= Geschwindigkeitskonstante der Wachstumsreaktion

k_d

= Geschwindigkeitskonstante des Initiatorzerfalls

[M]

= Monomerkonzentration

[I]

= Initiatorkonzentration

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 are material and environmental constants, various effects can be achieved by changing the variables [M] and [I]. 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 inversely proportional to the root of the initiator concentration.

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

• – Initiatorresten * gewählt aus der Gruppe -H, -SO₄, -OH,
• – kationischen Reste Z⁺ gewählt aus H, Na, K, Ca, NH₄ oder Alkylammoniumverbindungen NR₃R₄R₅R₆ mit R₃–R₅ = H, CH₃ oder C₂H₅,
• – m = 2 bis 58, vorteilhaft im Bereich 2 bis 45,
• – n = 8 bis 105, vorteilhaft im Bereich 8 bis 75 oder
• – M _n < 17.000 g/mol, bevorzugt im Bereich < 10.000 g/mol, insbesondere im Bereich von 1.700–7.00 g/mol, und weisen vorteilhaft
• – eine Polydispersität P < 5 auf.

The copolymers according to the invention are preferred with

• Initiator residues * 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 ₅ = H, CH ₃ or C ₂ H ₅ ,
• M = 2 to 58, advantageously in the range 2 to 45,
• - n = 8 to 105, preferably in the range 8 to 75 or
• - M _n <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) of sodium bicarbonate (ACROS) were 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 Use ratio HEMA: MAS Lot of HEMA Amount of MAS Used amount of monomers [mmol] Amount of initiator based on Σ of the monomers HEMA + MAS [mol%] 75:25 6.0 mL (6.4 g, 49.5 mmol) 1.4 mL (1.4 g, 16.5 mmol) 66 20 50:50 4 mL (4.28 g, 33 mmol) 2.8 mL (2.84 g, 33 mmol) 66 20 40:60 3.2 mL (3.4 g, 26.4 mmol) 3.4 mL (3.4 g, 39.6 mmol) 66 20 30:70 2.4 mL (2.57 g, 19.8 mmol) 3.9 mL (4.0 g, 46 mmol) 66 20 20:80 1.6 mL (1.7 g, 13.3 mmol) 4.5 mL (4.5 g, 53 mmol) 66 20 10:90 0.8 mL (0.86 g, 6.6 mmol) 5.0 mL (5.1 g, 59 mmol) 66 20

Tables 2 to 4 reproduce the yields of the HEMA copolymers produced in this way by way of example. Table 2: copolymer Number average molar mass M _n [g / mol] polydispersity Amount of initiator used mol .- [%] appearance Weigh out / yield on Σ monomers HEMA: MAS 50:50 1529 (OAC) 4.92 20 crystalline 7.1g / 99% HEMA: MAS 50:50 1325 (OAC) 3:51 40 crystalline 7.0g / 98% Table 3: Amount of initiator based on Σ of the monomers HEMA + MAS [mol%] Yield obtained [g] Resultant yield [%] based on total monomers 20 7.1 99 40 7.0 98 Table 4: Use ratio HEMA: MAS Yield obtained [g] Resultant yield [%] based on total monomers 75:25 6.4 97 50:50 7.1 99 40:60 6.5 96 30:70 6.1 92 20:80 5.8 94 10:90 5.5 92

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

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

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 made up to 50 mL 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 flask and adjusting the stirring plate to 500 U / min, after 5 minutes of heating via a dropping funnel with pressure equalization over a period of 2 h 50 mL of a solution of 4 mL (4.28 g, 33 mmol) 2-hydroxyethyl methacrylate in 46 mL 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: Glycerolallylether monomer phase, water phase and sediment of 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-necked flask. The water contained in the reaction solution was removed with the aid of a rotary evaporator at 40 ° C water bath temperature under a rotary vane pump vacuum (2 × 10 ^-4 mbar) to dryness of the residue. 200 ml of distilled water were added to the dried reaction mixture in the flask. Ethanol (96%) and 15 min. pressureless in the heating bath of the rotary evaporator at 40 ° C water bath temperature rotated. After complete detachment of all piston adhesions, the filtration of the 40 ° C hot suspension was carried out. The filtrate was collected in a further 500 mL round bottom flask and all ethanol contained by means of rotary vane pump vacuum (2 × 10 ^-4 mbar) at 40 ° C water bath temperature removed and the residue for a further 30 min. dried 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:

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) 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) of sodium bicarbonate (ACROS) were dissolved in 50 mL of. Water is dissolved while stirring. Subsequently, the monomer mixtures were prepared from 5.1 mL (5.3 g, 33 mmol) GMA and 4 mL (4.28 g, 33 mmol) HEMA in the ratio 1: 1. The monomers were with the. Made up to 50 mL total volume and added dropwise over a period of 2 hours 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) of sodium peroxodisulfate and heated to 70 ° C for 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 of 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 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 of the monomers GMA + HEMA [mol%] Yield obtained [g] Resultant yield [%] based on 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:

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) 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) of sodium bicarbonate (ACROS) were dissolved in 50 mL of. Water is dissolved while stirring. Subsequently, the monomer mixtures were prepared from 5.1 mL (5.3 g, 33 mmol) GMA, and 2.8 mL (2.84 g 33 mmol) in a ratio of 1: 1 with 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, wherein the neutralization was followed by a pH electrode. The monomers were with the. Made up to 50 mL total volume and added dropwise over a period of 2 hours 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) of sodium peroxodisulfate and heated to 70 ° C for 1 h. 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 of 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 of. Water, the solution was neutralized using sodium hydroxide solution and pH electrode to pH = 7 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. Amount of initiator based on Σ of the monomers GLMA + MAS [mol%] Yield obtained [g] Resultant yield [%] based on total monomers 10 7.5 92 20 8.1 99 40 7.0 86

The production instructions and reaction schemes shown by way of example also apply correspondingly to the other copolymers, as is known to the person skilled 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 because the copolymers initiated by NaPS 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. Cation Z ⁺ Radius of the cation pH during the reaction Molar initiator amount based on total monomers [mol%] (NaPS) Water absorption in 8 h Water absorption in 48 h Na ⁺ 97 pm 7 15 72% 100% K ⁺ 133 pm 7 15 50% 59% NH ₄ ⁺ 148 pm 7 15 49% 53% Cs ⁺ 167 pm 7 15 42% 52%

The number average molecular weights and polydispersity of the exemplified HEMA copolymers are shown in Tables 8-11 below. Table 8: Determines molecular weights and polydispersities HEMA-MAS copolymer Number average molar mass M _n [g / mol] polydispersity Amount of initiator used mol .- [%] appearance Weigh out / yield on Σ monomers HEMA: MAS 20:80 3959 3.92 15 crystalline 6.0 g / 96% HEMA: MAS 20:80 5280 3.24 10 crystalline 6.1g / 97% Table 9: Determines molecular weights and polydispersities HEMA-GAE Copolymer Molar, used monomer ratio: GAE: HEMA Number average molar mass M _n [g / mol] polydispersity 5: 1 2061 2.97 3: 1 2331 2.89 2: 1 2744 2.23 1.5: 1 2274 2.31 1 1 2017 1.99 1: 2 1743 2:04 5: 1 2158 2.6 3: 1 2078 2.97 2: 1 4104 2:54 1 1 4646 2.63 2: 1 3836 2.17 4: 1 3729 1.99 6: 1 4471 1.93 8: 1 4562 1.87 Table 10: Determines molecular weights and polydispersities HEMA-GMA copolymer Number average molar mass M _n [g / mol] polydispersity GMA: HEMA 3: 1 3880 1.87 GMA: HEMA 1: 1 4088 2:06 GMA: HEMA 1: 3 1958 1.6 Table 11: Determines molecular weights and polydispersities HEMA-AS copolymer Number average molar mass M _n [g / mol] polydispersity AS: HEMA 8: 1 1715 1.81

Table 12 shows the molecular weights and polydispersities GMA-MAS copolymers copolymer Number average molar mass Mn [g / mol] polydispersity Amount of initiator used mol .- [%] appearance Weigh out / yield on Σ monomers GMA: MAS 50:50 - - 10 crystalline 7.5 g / 92% GMA: MAS 50:50 2381 (OAC) 5.62 20 crystalline 8.1g / 99% GMA: MAS 50:50 2330 (OAC) 2.91 40 crystalline 7.0 g / 86%

The residual monomer content was then determined by means of GC, as indicated in Table 13 below.

Monomers are known to sensitize, so that the lowest 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, ⌀ 320 μm, 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 for example HEMA-MAS (50 : 50) copolymer Amount of initiator based on Σ of the monomers [mol%] Determined residual monomers Amounts [%] HEMA: MAS 50:50 20 HEMA 1:34 MAS unknown HEMA: MAS 50:50 40 HEMA 0.94 MAS unknown

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 can be detected (below the detection limit about 0.05% by weight). Table 14: Residual monomer amounts determined by gas chromatography and HPLC HEMA-MAS (20:80) copolymer Amount of initiator based on Σ of the monomers [mol%] Determined residual monomers Quantities [% by weight] HEMA: MAS 20:80 20 HEMA <0.05 MAS <0.05 HEMA: MAS 20:80 15 HEMA <0.05 MAS 12:18 Table 15: Residual amounts of HEMA-GAE determined by gas chromatography and HPLC copolymer Determined residual monomers Amounts [%] GAE: HEMA 1: 1 GAE - HEMA 12:19 GAE: HEMA 2: 1 GAE - HEMA 12:17 GAE: HEMA 4: 1 GAE 12:14 HEMA - GAE: HEMA 6: 1 GAE 12:25 HEMA - GAE: HEMA 8: 1 GAE 12:28 HEMA -

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, the HEMA-MAS copolymers crosslinked with glycerol dimethacrylate (GDMA) and polyethylene glycol dimethacrylate (PEG-DMA (Mn: 550)) also show good properties such as good water solubility, moisture uptake and removal capacities as shown in Table 16 below: crosslinkers Crosslinker amount used Copolymer (use ratio) Water absorption in 8 h Water absorption in 48 h Residual water content after 8 h Glycerol dimethacrylate (GDMA) 1 mol% (based on the two monomers) HEMA-MAS (20:80) 71% 105% 25% Polyethylene glycol dimethacrylate (PEG-DMA) Mn = 550 0.5 mol% (based on the two monomers) HEMA-MAS- (20:80) 74% 103% 27%

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 at risk. 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 expected without any loss of moisture-regulating properties. The moisture kinetics and their advantages of the copolymers of the invention shown here will be explained in more detail below.

The GDMA and PEG-DMA crosslinked HEMA-MAS copolymers with a crosslinker content of up to 2 mol .-% are accordingly among the copolymers of the invention.

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 1700-7,000 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 according to the invention showed unpredictable properties in studies on moisture uptake and release as well as on solubility.

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 achieves maximum moisture uptake capacity, HEMA: MAS copolymers were prepared in various ratios and their moisture uptake capacity determined after 8 hours and 48 hours for this purpose.

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 110.8% 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: Solvent (5 mL) Amount of initiator based on Σ of the monomers [mol%] Solubility in 150 mg of polymer in 5 mL of solvent at RT [+/-] water 20 ++ 10% glycerol solution 20 ++ water 40 ++ 10% glycerol solution 40 ++ - = poorly soluble, + = mostly soluble, ++ = completely soluble

Table 18 shows the solubility of the copolymers HEMA-GAE in various solvents Amount used Copolymer [mg] solvent Solubility in 2.5 mL solvent at RT [+/-] Solubility in 2.5 mL solvent at> 30 ° C [+/-] 150 The 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 Solvent (5 mL) Polymer allyl ether: HEMA Solubility in 5 mL solvent at RT (3 mass% solution) [+/-] water 5: 1 ++ 10% glycerol solution 5: 1 ++ water 3: 1 ++ 10% glycerol solution 3: 1 ++ water 2: 1 ++ 10% glycerol solution 2: 1 ++ water 1 1 ++ 10% glycerol solution 1 1 ++ water 2: 1 ++ 10% glycerol solution 2: 1 ++ water 4: 1 ++ 10% glycerol solution 4: 1 ++ water 6: 1 ++ 10% glycerol solution 6: 1 ++ water 8: 1 ++ 10% glycerol solution 8: 1 ++

Table 20 shows the solubility of the copolymers HEMA-AS in different molar ratios in water and glycerin Solvent (5 mL) Polymer AS: HEMA [mol / mol] Solubility in 150 mg of polymer in 5 mL of 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 Solvent (5 mL) Amount of initiator based on Σ of the monomers [mol%] Solubility in 150 mg of polymer in 5 mL of solvent at RT [+/-] water 10 + 10% glycerol solution 10 + water 20 ++ 10% glycerol solution 20 ++ water 40 ++ 10% glycerol solution 40 ++

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 water solubility of the copolymers is required for the desired application, the poorly soluble or insoluble systems which result, for example, at higher molecular weights, must be excluded.

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). at The water release measurements showed that the copolymers containing methacrylic acid (pH = 7) gave 42.7 (GMA: MAS 50:50 pH = 7) and 43.7 (HEMA: MAS 50:50 pH = 7) over 8 h, while 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 when 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 chosen in the form of a cocktail shaker (dimensions L × W × H: 90 × 90 × 220 mm) and consists of an aqueous solution reservoir over which a plastic screen is placed. 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 contents at certain intervals, it is possible to track the water absorption of the polymer film.

Moisture uptake measurements were made according to the measurement parameters given in Table 22: Table 22: Moisture uptake parameters using HEMA-MAS as an example parameter used Initiator, buffer Sodium peroxodisulfate (NaPS), sodium bicarbonate (NaHCO ₃ ) Used monomers 2-hydroxyethyl methacrylate (HEMA), methacrylic acid (MAS) Used monomer ratios Monomer ratio 50:50, variable amounts of initiator; Monomer ratio 10:90 to 75:25, initiator amounts: 20 mol% polymerization 3 hours in water at 70 ° C workup Acidify the reaction solution to pH = 2, remove salts and water with ethanol (78 ° C), reneutralize to pH = 7 Weighing scale [mg] 100 (copolymers) Calculated layer thickness [mm] 0.1 (copolymers) measuring Cup 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

The to 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, such as shows.

The copolymers of structure (II), HEMA-GAE, also show good water absorbency, such as Tables 23, 24, 25 and demonstrate. Glycerol allyl ether - GAE may also be abbreviated to AE or allyl ether. Table 23: Water uptake of HEMA-GAE copolymers Molar monomer ratio used: GAE: HEMA Mass of one mole of substance [g] Water absorption [%] Ingestible amount of water [g] Ingestible amount of water [mol] per mole of 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 copolymer solvent Solubility of 150 mg of polymer in 2.5 mL of solvent at RT [+/-] Water uptake in 18 days [%] at 84% rel. Humidity and film thickness 1 mm GAE: HEMA 5: 1 The water ++ 91.4 10% glycerol solution ++ GAE: HEMA 3: 1 The water ++ 86.2 10% glycerol solution ++ GAE: HEMA 2: 1 The water ++ 82.7 10% glycerol solution ++ GAE: GMA 5: 1 The water ++ 87.9 Table 25: Water uptake of HEMA-GAE copolymers copolymer solvent Solubility of 150 mg of polymer in 2.5 mL of solvent at RT [+/-] Water uptake in 8 h [%] at 84% rel. Humidity and film thickness 0.5 mm GAE: HEMA 8: 1 The water ++ 15.6 10% glycerol solution ++ GAE: HEMA 6: 1 The water ++ 13.7 10% glycerol solution ++ GAE: HEMA 4: 1 The water ++ 16.3 10% glycerol solution ++ GAE: HEMA 2: 1 The water ++ 15.5 10% glycerol solution ++ GAE: HEMA 1: 1 The water ++ 12.6 10% glycerol solution ++

The copolymers of structure (III), HEMA-GMA, also show good water absorbency, such as and demonstrate.

Glyceryl methacrylate - GMA may also be abbreviated to GLMA.

Similarly, the copolymers of structure (VI), GM-MAS, also show good water absorbency, such as and demonstrate.

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 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 according to the measurement parameters given in Table 26 below, using the example of the HEMA-MAS copolymers: Table 26: Parameters of the Moisture Release Measurements Example of the HEMA-MAS Copolymers parameter used Initiator, buffer Sodium peroxodisulfate (NaPS), sodium bicarbonate (NaHCO ₃ ) Used monomers 2-hydroxyethyl methacrylate (HEMA), methacrylic acid (MAS) Used monomer ratios Monomer ratio 50:50, 10:90 to 75:25 variable initiator amounts: 10, 20 and 40 mol% polymerization 3 hours in water at 70 ° C workup Acidify the reaction solution to pH = 2, remove salts and water with ethanol (78 ° C), reneutralize to pH = 7 Weighing scale [mg] 100 (copolymers) Calculated layer thickness [mm] 0.1 (copolymers) 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

The to show by way of example the thus determined 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, such as setting out.

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 ratio Amount of initiator [mol%] Initial weight [mg] Layer thickness [mm] Water absorption in 8 h [%] Residual water content after 8 h [%] HEMA-MAS pH = 2 50:50 20 100 0.1 26.6 unknown HEMA-MAS pH = 7 50:50 20 100 0.1 60.0 16.3 Table 28: copolymer Amount of initiator [mol%] solvent Solubility of 150 mg of polymer in 2.5 mL of solvent at RT [+/-] Water absorption in 8 h at 84% rel. Humidity and film thickness 0.1 mm [%] Water uptake in 48 h at 84% rel. Humidity and film thickness 0.1 mm [%] Water release in 8 h at 43% rel. Humidity and film thickness 0.1 mm [%] HEMA: MAS 75:25 pH = 7 20 The water ++ 53.9 69.5 14.7 10% glycerol solution ++ HEMA: MAS 50:50 pH = 7 20 The water ++ 60.0 72.8 15.5 10% glycerol solution ++ HEMA: MAS 40:60 pH = 7 20 The water ++ 67.8 87.8 23.5 10% glycerol solution ++ HEMA: MAS 30:70 pH = 7 20 The water ++ 74.9 95.8 25 HEMA: MAS 20:80 pH = 7 20 The water ++ 80.9 110.8 31.2 10% glycerol solution ++ HEMA: MAS 10:90 pH = 7 20 The water ++ 30.5 39.1 8.0 10% glycerol solution ++ - = poorly soluble, + = largely soluble, ++ = completely soluble Table 29: Copolymer (monomer ratio HEMA: MAS) Initiator usage [mol%] Initial weight [mg] Layer thickness [mm] Water absorption in 8 h [%] Water absorption in 48 h [%] Residual water content after 8 h [%] HEMA MAS 20:80 pH = 7 20 100 0.1 81 111 31 HEMA MAS 20:80 pH = 7 15 100 0.1 72 100 30 HEMA MAS 20:80 pH = 7 10 100 0.1 64 90 17 HEMA MAS 20:80 pH = 7 5 100 0.1 65 88 23 Table 30: polymer monomer ratio Amount of initiator [mol%] Initial weight [mg] Layer thickness [mm] Water absorption in 8 h [%] Residual water content after 8 h [%] GMA-MAS 50:50 10 - - - - GMA-MAS pH = 2 50:50 20 100 0.1 28.4 unknown GMA-MAS pH = 7 50:50 20 100 0.1 59.0 16.3 GMA-MAS 50:50 40 100 0.1 52.6 unknown

The following Table 31 shows in the overview characteristic water absorption or release values of the copolymers according to the invention. Table 31: Monomer 1 Monomer 2 Copolymer (use ratio) Water absorption in 8 h Water absorption in 48 h Glycerol allyl ether (GAE) 2-hydroxyethyl methacrylate (HEMA) HEMA-GAE copolymer (1: 2) 34% (saturated) - Glyceryl methacrylate (GMA) 2-hydroxyethyl methacrylate (HEMA) GLMA-HEMA copolymer (50:50) 27% (saturated) - Glyceryl methacrylate (GMA) Methacrylic acid (MAS) GLMA-MAS copolymer (50:50) pH = 2 (as free acid) 28% (saturated) - Glyceryl methacrylate (GMA) Methacrylic acid (MAS) GLMA-MAS copolymer (50:50) pH = 7 (as sodium salt) 59% - 3-sulfo-propyl acrylate (SPA) 2-hydroxyethyl methacrylate (HEMA) SPA-HEMA copolymer (80:20) 46% 63% 3-sulfo-propyl acrylate (SPA) Methacrylic acid (MAS) SPA-MAS copolymer (50:50) pH = 7 (as sodium salt) 73% 90% 3-sulfo-propyl acrylate (SPA) Glyceryl methacrylate (GMA) SPA-GLMA copolymer (80:20) 43% 53% 2-hydroxyethyl methacrylate (HEMA) Acrylic acid (AS) HEMA-AS copolymer (80:20) 64% 77% 2-hydroxyethyl acrylate (HEA) Methacrylic acid (MAS) HEA-MAS copolymer (80:20) 70% 108%

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. One with 69.5% as well The HEMA: MAS 25:75 copolymer already has a remarkably high capacity. The HEMA: MAS copolymers from the monomer ratios 50:50 (72.8%), 40:60 (87.8%), 30:70 (95.8%) and 20:80 (110.8%) 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 off most of the HEMA: MAS 10: 90 copolymer with 31.1 the least in 8 hours.

The copolymers according to the invention, in particular those having an average molecular weight of less than 10,000 g / mol and a HEMA-MAS ratio in the range 75:25 to 10:90, are suitable as moisture regulators in various forms due to their water and glycerol solubility and the moisture absorption and release properties Areas and formulations usable. 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 raw material Condition at the beginning of the test begin after 6 h after 1 day after 1 week Condition at the end of the test 1.) Parteck Si 150 [98% sorbitol] powder 0 6 28 109 liquid 2.) Montanov 202 (Seppic) [Arachidyl alcohol 55% and Behenyl alcohol 30% and Arachidyl glucoside 15%] pellets 0 0 3 6 pellets 3.) Montanov L (Seppic) [C14-22 Alcohols 80% and C12-20 Alkyl Glucosides 20%] pellets 0 1 4 7 pellets 4.) Sisterna SP 30 [sucrose distearate] powder 0 3 6 9 powder 5.) Urea [Pure Urea] small balls 0 3 21 160 liquid 6.) Rain Forest FR 3410 [theobroma grandiflorum] greasy, pasty 0 0 0 0 greasy, pasty 7.) DMSO2 [99.7%] powder 0 0 0 -1 powder 8.) Glycerol 99 viscous 0 16 50 154 liquid 9.) Sisterna SP 70-C [sucrose stearate] powder 0 4 8th 11 powder 10. HEMA-MAS copolymer (20:80) powder 0 12 40 115 liquid 11. HEMA MAS Copolymer (75:25) powder 0 9 27 81 liquid

It can be seen that the copolymers according to the invention have an approximately good water absorption, such as the glycerol, sorbitol and urea known as humectants.

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. In the comparison of the water content in pig skin is shown. 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 wetting performance of the copolymers is even in the range of glycerol.

As a further proof of the skin moisturizing performance of the copolymers according to the invention, a long-term corneometry study using the example of the HEMA-MAS copolymers has 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 (t0), 7 days (t1) and 14 days after the first product application (t2), skin moisturization of the respective treated areas as well as of an untreated area of the forearm was measured by corneometry.

The respective coreometer unit differences t1-t0 and t2-t0 are in shown.

shows that the copolymer solutions have higher skin moisturization values 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 moisturization on the surface and film formation on the surface, which prevents the rapid evaporation of the 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 Use ratio HEMA: MAS Optical appearance odor test 75:25 White dust Minimal odor 50:50 White dust Minimal odor 40:60 White dust Minimal odor 30:70 White dust Minimal odor 20:80 White dust Minimal odor 10:90 White dust Minimal odor Table 34 Olfactic Properties HEMA-GAE Copolymers copolymer Amount of initiator based on Σ of the monomers [mol%] Optical appearance odor test GAE: HEMA 1: 1 3.7 White dust inconspicuous GAE: HEMA 2: 1 3.7 White dust inconspicuous GAE: HEMA 4: 1 3.7 White dust inconspicuous GAE: HEMA 6: 1 3.7 White dust inconspicuous GAE: HEMA 8: 1 3.7 White dust inconspicuous

As shown in Tables 33 and 34, the copolymers according to the invention can thus also be used as a cosmetic component for aesthetic / olfactory reasons. 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 the copolymers according to the invention is advantageously in the range from 1 to 20% by weight, in particular in the range from 2.5 to 10% by weight, 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. Especially from dry phases, such as emulsion residue on the skin or water-binding after water release 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 on the skin, a film may 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. Equally advantageous is their property of not being thickening in aqueous preparations or emulsions.

The non-gelation and the non-thickening action of the copolymers according to the invention makes a decisive difference to the polymers known from the prior art with (meth) acrylate building blocks.

The non-gelation and non-thickening effect of the copolymers of the invention was investigated by 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 11: O / W emulsion with glycerine and without HEMA-MAS copolymer: 5750 mPas
Example 13: O / W emulsion with glycerol and 5 wt.% 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 wt.% 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 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 according to the invention is possible in various dosage forms, ie preparations or agents. The copolymers according to the invention can be used in particular in water-based preparations in which water solubility, water introduction 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 preparation forms, 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, for. Preservatives, preservatives, bactericides, perfumes, anti-foaming agents, dyes and color pigments, thickeners, moisturizing 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 impair 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 β-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 transepidermal water loss (TEWL) after application or spreading on the skin surface) and / or hydrating the horny layer positively to influence.

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 of the company SOLABIA SA 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.

As is known, glycerol acts as a deep moisturizer in cosmetic or dermatological preparations and the copolymers as surface moisturizers.

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 the Moisturizing the skin caused by the copolymer (s) contained in comparison with a preparation containing the same ingredients without the copolymers being increased.

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 according to the invention have been 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 to the example preparations according to the invention. Examples ingredients 1 2 3 4 5 Cyclomethicone 5 5 5 5 5 Butyrospermum Parkii butter 1 1 1 1 1 glycerin 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 methylparaben 0.15 0.15 0.15 0.15 0.15 phenoxyethanol 0.4 0.4 0.4 0.4 0.4 Acrylates / C10-30 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 83.153 80.653 78.153 75.653 73.153 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 8th 9 10 Cyclomethicone 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 methylparaben 0.15 0.15 0.15 0.15 0.15 phenoxyethanol 0.4 0.4 0.4 0.4 0.4 Acrylates / C10-30 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 11 12 13 14 15 Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5 Ethylhexylglycerin 0.5 0.5 0.5 0.5 0.5 Caprylic / Capric Triglycerides 1 1 1 1 1 Cera Microcristallina + Paraffinum 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 benzoates 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 Stearates 0.8 0.8 0.8 0.8 0.8 glycerin 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 + 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 2.5 5 7.5 10 ingredients 16 17 18 19 20 Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5 Ethylhexylglycerin 0.5 0.5 0.5 0.5 0.5 Caprylic / Capric Triglycerides 1 1 1 1 1 Cera Microcristallina + Paraffinum 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 benzoates 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 Stearates 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 + 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 2.5 5 7.5 10 ingredients 21 22 23 24 25 Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5 Ethylhexylglycerin 0.5 0.5 0.5 0.5 0.5 Caprylic / Capric Triglycerides 1 1 1 1 1 Cera Microcristallina + Paraffinum 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 benzoates 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 Stearates 0.8 0.8 0.8 0.8 0.8 glycerin 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

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• JP 2009040705 [0008]
• US 6348199 [0009]
• US 5306498 [0009]
• WO 2008087119 [0010]
• EP 1195394 [0012, 0014, 0016, 0036]

Cited non-patent literature

• Production and Characterization of Hydrogels as Contact Lens Materials - Lecture at the Meeting of the Section "Macromolecular Chemistry" of the Gesellschaft Deutscher Chemiker on "Polymers and Water" in Bad Nauheim on April 2 and 3, 1984 [0019]

Claims (9)

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)

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. 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 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 2 to 45, n in the range 8 to 75 and / or M _n be selected in the range <10,000 g / mol, in particular in the range 1.700-7000 g / mol Water-based administration forms comprising one or more copolymers according to one of claims 1 to 2. Dosage form according to claim 3 as a cosmetic or dermatological preparation. Dosage form according to Claim 3 or 4, characterized in that the proportion by weight of the copolymers is up to 50% by weight, in particular in the range from 1 to 20% by weight, in particular in the range from 2.5 to 10% by weight, based on the total mass the dosage form is selected. Preparations according to claim 4 or 5 comprising one or more additional skin moisturizing agents, in particular glycerol. Use of the copolymers according to one of Claims 1 to 2 as moisture regulators. Use of the copolymers according to claim 7 in cosmetic or dermatological preparations for skin moisturization. Use according to claim 8, characterized in that one or more additional skin moisturizing agents, in particular glycerol, are added to the preparations.

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