Thickened polymer

Abstract

The invention relates to a polymer which can be obtained by radical emulsion polymerization of at least one acidic vinyl monomer or salt thereof, at least one non-ionic vinyl monomer, in particular preferably a hydrophobic non-ionic vinyl monomer, at least one monomer containing an unsaturated terminal group and a polyoxyalkyene portion, at least one crosslinking monomer, optionally a protective colloid, and is characterized in that the polymerization is controlled such that the gelling effect occurs at least at times, which is achieved by the monomer addition (dosing time) taking place for 40 minutes, particularly preferably for 30 minutes.

Claims

1. A polymer which is obtained by free-radical emulsion polymerization of monomers comprising (A) at least one acidic vinyl monomer or salt thereof, (B) at least one nonionic vinyl monomer, (C) at least one monomer comprising an unsaturated end group and a polyoxyalkylene portion, (D) at least one crosslinking monomer, and (E) optionally, a protective colloid, wherein no associative monomers are present, the polymerization being controlled such that at least at times a gel effect arises, achieved by monomer addition (dosing time) taking place over not more than 40 minutes.

2. The polymer of claim 1, wherein (B) comprises hydrophobic at least one of a C.sub.12 alkyl acrylate and a C.sub.18 alkyl acrylate.

3. The polymer of claim 1, wherein the monomer addition takes place over not more than 30 minutes.

4. The polymer of claim 1, wherein (A) comprises one or more monomers selected from vinyl monomers having carboxyl groups and alkali, alkaline earth, ammonium, and alkylammonium salts thereof.

5. The polymer of claim 1, wherein (A) comprises one or more monomers selected from acrylic acid, methacrylic acid, and alkali, alkaline earth, ammonium, and alkylammonium salts thereof.

6. The polymer of claim 1, wherein (B) comprises one or more monomers selected from C1-C22-alkyl (meth)acrylates.

7. The polymer of claim 1, wherein (C) comprises one or more monomers selected from vinylpolyalkylene glycols and polymerizable surfactants.

8. The polymer of claim 7, wherein (C) comprises one or more monomers selected from EO/PO 1,4-butanediol vinyl ether (EO/PO 30 mol), allylpolyalkylene glycol ether (EO 30 mol), allylpolyalkylene glycol ether (EO 20 mol, PO 20 mol), vinylpolyalkylene glycol ether (EO 20 mol), allyl alcohol alkoxylates, polyalkyleneglycol allyl butyl ether (EO 25 mol, PO 8 mol).

9. The polymer of claim 1, wherein (D) comprises one or more monomers selected from polyol (meth)acrylates comprising at least two (meth)acrylate groups, and mixed esters of polyols with at least one of acrylic acid and methacrylic acid.

10. The polymer of claim 1, wherein the polymer comprises from 10% to 75% by weight of (A), from 10% to 90% by weight of (B), from 0.5% to 40% by weight of (C), and up to 1% by weight of (D).

11. The polymer of claim 1, wherein a weight ratio (A):(B) is from 1:2 to 2:1.

12. The polymer of claim 1, wherein (B) comprises ethyl acrylate.

13. A thickened preparation, wherein the preparation comprises one or more polymers according to claim 1.

14. The preparation of claim 13, wherein the preparation comprises from 2% to 3% by weight of the one or more polymers.

15. The preparation of claim 13, wherein the preparation is one or more of a health product, a cleaning product, a household product, a shower gel, a paint, an ink, a dispersant, an antisettling agent, a concrete or cement additive, a coating composition, a medicinal product, a cosmetic product, and a dermatological product.

16. The preparation of claim 13, wherein the preparation has a tan of from 0.05 to 0.6.

17. The preparation of claim 13, wherein at a pH of <6.2 the preparation has a turbidity value of NTU <20.

18. A polymer which is obtained by free-radical emulsion polymerization of monomers comprising (A) from 35% to 49% by weight of one or more monomers selected from vinyl monomers comprising carboxyl groups and alkali, alkaline earth, ammonium, and alkylammonium salts thereof, (B) from 47% to 60% by weight of one or more monomers selected from C1-C22-alkyl (meth)acrylates, (C) from 2% to 6% by weight of one or more monomers selected from vinylpolyalkylene glycols and polymerizable surfactants, (D) from 0.1% to 0.35% by weight of one or more monomers selected from polyol (meth)acrylates comprising at least two (meth)acrylate groups, and mixed esters of polyols with at least one of acrylic acid and methacrylic acid, and (E) optionally, a protective colloid, wherein no associative monomers are present, the polymerization being controlled such that at least at times a gel effect arises, achieved by monomer addition (dosing time) taking place over not more than 30 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The preparationsif they are gel-like preparations with yield pointare advantageously designed such that they have a yield point of 0.5-20 Pa, preferably 1-6 Pa.

(2) The yield point is considered to be the critical shear stress of the flow curve. It can be ascertained according to the invention as follows:

(3) The flow curve is measured on a shear-stress-controlled rheometer at 25 C.1 C. with 20 mm plate/plate geometry with a gap between 0.8 mm and 1.2 mm, with charging being carried out in a structure-preserving manner. A suitable constant shear stress gradient is pregiven and, before the test, a corresponding structure recovery time is observed and the critical shear stress at the maximum of the flow curve is given.

(4) Advantageously, the preparations are designed such that they have a tan of 0.05-0.6, preferably 0.1-0.5.

(5) According to the invention, tan is understood as meaning the quotient of the loss modulus and the storage modulus. The tan is ascertained as follows:

(6) Loss and storage moduli are measured by a dynamic frequency test on a shear-stress-controlled rheometer at 40 C.1 C. with 20 mm plate/plate geometry with a gap between 0.8 mm and 1.2 mm, charging being carried out in a structure-preserving manner. The frequency test is carried out according to the prior art with an appropriate structure recovery time before the test, and the tan in the frequency range between 0.05 rad/s and 3.0 rad/s is quoted, preferably between 0.08 rad/s and 1.0 rad/s.

(7) The preparations are advantageously designed such that, at pH<6.2, they have a turbidity value of NTU (Nephelometric Turbidity Unit)<20. The turbidity value is measured using a turbidity measuring device, with distilled water having a value of NTU=0 serving as standard.

(8) It is also in accordance with the invention if not water, but other polar liquids are thickened by polymers according to the invention. In particular, alcohols, glycols, polyols, amines and organic acids such as for example acrylic acid can be thickened.

(9) The use of polymers according to the invention as emulsifier is also in accordance with the invention. In this way, creams and lotions can be provided.

(10) The polymers are also suitable as dispersants and antisettling agents.

EXAMPLES

(11) Synthesis of the Copolymers

(12) The examples below aim to illustrate the present invention without limiting it. The preparation of the examples takes place in accordance with the method described below, the type and amounts of the monomers, chain-transfer agents and protective colloids each used as starting components being summarized in Table 2. Parts and percentages refer to the weight.

Example 1

(13) TABLE-US-00001 Monomer phase Methacrylic acid 37.000 parts Ethyl acrylate 51.800 parts Octadecyl acrylate 5.000 parts Emulsogen R307 6.000 parts Trimethylolpropane triacrylate 0.300 parts Water phase Water 33.060 parts Sodium lauryl sulfate 0.984 parts Reaction vessel Water 173.146 parts Sodium lauryl sulfate 0.300 parts Initiator phase A Water 1.911 parts Ammonium persulfate 0.069 parts Initiator phase B Water 2.909 parts Ammonium persulfate 0.021 parts

(14) The reaction vessel, which is equipped with stirrer, reflux condenser, nitrogen feed, dosing device and internal thermometer, is charged with 173.146 parts of water and 0.300 parts of sodium lauryl sulfate. The mixture is heated to 82 C. with stifling and under a nitrogen atmosphere.

(15) The monomer mixture is prepared in a second stirred vessel which is equipped with stirrer and nitrogen feed. For this purpose, the monomer phase with 37.000 parts methacrylic acid, 51.800 parts ethyl acrylate, 5.000 parts octadecyl acrylate, 6.000 parts Emulsogen R307 and 0.300 parts trimethylpropane triacrylate is introduced, and into this is mixed the water phase with 33.060 parts water and 0.984 parts sodium lauryl sulfate with stirring and under a nitrogen atmosphere.

(16) As soon as a temperature of 82 C. is reached in the reaction vessel, an initiator phase A, consisting of 0.069 parts ammonium persulfate and 1.911 parts of water, is added and the monomer mixture is metered in uniformly at 85-88 C. over the course of 30 minutes. Then, an initiator phase B, consisting of 0.021 parts ammonium persulfate and 2.909 parts water, is added and then the reaction mixture is post-polymerized for a further 4 hours at 90 C. before being cooled to <40 C.

Examples 2-52

(17) The examples below (Table 1) are prepared analogously to Example 1. In most examples, sodium lauryl sulfate was used as emulsifier. In a departure from this, Examples 5 and 11 were prepared from a combination of sodium lauryl sulfate and ethoxylated isotridecyl alcohol (Genapol X1005, Clariant), and Example 10 was prepared with isotridecyl alcohol (Genapol X1005, Clariant).

Abbreviations

(18) MAA Methacrylic acid

(19) EA Ethyl acrylate

(20) LA Lauryl acrylate

(21) ODA Octadecyl acrylate

(22) S20W Bisomer S20W (Cognis)

(23) Methoxypolyethylene glycol methacrylate (EO 45 mol)
M5010 Maxemul 5010 (Croda) C.sub.12H.sub.23HCCH(C.sub.2H.sub.4O.sub.25CH.sub.3
R307Emulsogen R307 (Clariant) EO/PO 30 1,4-butanediol vinyl ether (EO/PO 30 mol)
RAL307 Emulsogen RAL307 (Clariant) Allylpolyalkylene glycol ether (EO 30 mol)
R208Emulsogen R208 (Clariant) 1,4-Butanediol vinyl ether (EO/PO 25 mol)
A11/1800 Polyglycol A11/1800 (Clariant) Allylpolyalkylene glycol ether (EO 20 mol, PO 20 mol)
R500Polyglycol R500 (Clariant) Vinylpolyalkylene glycol ether (EO 9 mol)
R1100 Polyglycol R1100 (Clariant) Vinylpolyalkylene glycol ether (EO 20 mol)
R2000 Polyglycol R2000 (Clariant) Vinylpolyalkylene glycol ether (EO 40 mol)
AM 20/20 Polyglycol AM 20/20 (Clariant) Polyalkylene glycol allyl methyl ether (EO 20 mol, PO 20 mol)
AB 1500 Polyglycol AB1500 (Clariant) Polypropylene glycol allyl butyl ether (PO 25 mol)
AB/25-8 Polyglycol AB/25-8 (Clariant) Polyalkylene glycol allyl butyl ether (EO 25 mol, PO 8 mol)
A31/1600 Polyglycol A31/1600 (Clariant) Polyalkylene glycol allyl ether (EO 25 mol, PO 8 mol)
A 10 R Pluriol A10R (BASF) Allyl alcohol alkoxylates
A 111 RPluriol A111R (BASF) Allyl alcohol alkoxylates
SPE RALUMER SPE (Raschig) Dimethyl[2-[(2-methyl-1-oxoallyl)oxy]ethyl](3-sulfopropyl)ammonium hydroxide
SPM RALUMER SPM (Raschig) Potassium 3-sulfopropylmethacrylate
SPP RALUMER SPP (Raschig) Dimethyl[3-[(2-methyl-1-oxoallyl)amino]propyl]-3-sulfopropylammonium hydroxide
HMP Bisomer HMP (Cognis) Monoester of maleic acid and C16-18 fatty alcohol
KH-10 Hitenol KH-10 (Dai-Ichi Kogyo Seiyaku) Ammonium polyoxyalkylene-1-(allyloxymethyl)alkyl ether sulfate

(24) ##STR00001##
BC-10 Hitenol BC-10 (Dai-Ichi Kogyo Seiyaku) Ammonium nonylphenol polyoxyethylene alkyl ether sulfate

(25) ##STR00002##
BEM Behenyl ethylene glycol-1100 methacrylate
TMPTA Trimethylolpropane triacrylate
TMPTMA Trimethylolpropane trimethacrylate
IMP Isooctyl 3-mercaptopropionate
AMHEC Tylose AM H40 YP2 (SE Tylose) Allyl-modified hydroxyethylcellulose

(26) TABLE-US-00002 TABLE 1 Examples 1-52 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 MAA 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 37 EA 51. 53. 53. 53. 51. 53. 53. 53. 53. 53. 53. 47. 53. 53. 53. 53. 51. 51. 51.6 53. 53. 51. 53. 52. 54. 33. 56. ODA 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 LA 2 2 S20W 2 2 2 M5010 2 2 2 2 2 2 2 2 R307 6 2 2 2 2 4 2 2 2 10 2 2 2 2 6 6 6 2 2 RAL307 6 2 R208 24 A11/18 5.4 R500 R1100 2.9 R2000 AM AB AB/25-8 A31/16 A 10 R 1.7 A 111 R SPE 2 SPM 2 SPP 2 HMP 2 KH-10 2 BC-10 2 BEM TMPTA 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.5 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 TMPTM 0.3 IMP 0.15 AMHEC 0.0

(27) TABLE-US-00003 TABLE 2 Results for polymer emulsions Example pH value Particle size* in nm 1 2.48 108 2 2.47 103 3 n.d. n.d. 4 n.d. n.d. 5 n.d. n.d. 6 n.d. n.d. 7 n.d. n.d. 8 n.d. n.d. 9 n.d. n.d. 10 n.d. n.d. 11 n.d. n.d. 12 n.d. n.d. 14 2.57 102 14 2.62 129 15 3.13 95 16 2.14 186 17 2.53 88 18 2.52 107 19 2.51 101 20 2.53 79 21 2.54 79 22 2.50 96 23 2.52 89 24 2.55 87 25 2.47 111 26 2.67 165 27 2.76 89 28 2.50 87 29 2.56 103 30 2.58 87 31 2.57 95 32 2.48 79 33 2.30 104 34 2.37 96 35 2.46 85 36 2.36 85 37 2.46 113 38 2.39 89 39 2.37 96 40 2.38 94 41 2.65 85 42 2.32 103 43 2.42 91 44 2.39 90 45 2.36 87 46 2.42 101 47 2.34 84 48 2.40 106 49 2.40 123 50 2.69 100 51 2.46 99 52 2.50 124 *The particle size in the polymer emulsion is determined using dynamic light scattering (DLS) in a dilute aqueous sample of the emulsion at 25 C. 1 C.

Example 53

(28) The preparation below is intended to illustrate the present invention without limiting it. Unless stated otherwise, all quantitative data, fractions and percentages are based on the weight and the total amount or on the total weight of the preparation.

(29) The polymer according to the invention is diluted with some of the water phase and added to the surfactant phase with stirring. The other formulation constituents apart from NaOH and the suspended bodies are then added with stirring. After the pH has been adjusted, the suspended bodies are stirred into the finished gel base with as little shear as possible.

(30) TABLE-US-00004 TABLE 3 Preparation shower gel Sodium laureth sulfate 6.50 Cocoamidopropylbetaine 4.60 Sodium cocoyl glutamate 0.50 Polymer 2.25 PEG-40 hydrogenated castor oil 0.80 PEG-7 glyceryl cocoate 1.75 Pigments q.s. NaOH q.s. Perfume q.s. Water ad 100

(31) TABLE-US-00005 TABLE 4 Results for preparation shower gel Example tan Viscosity in mPas pH of shower gel 1 0.30 3544 6.19 2 0.29 2600 6.21 3* 0.89 2605 6.15 4* 8.58 1977 6.18 5* 1.89 2014 6.15 6* 0.59 2234 6.20 7* 1.56 1967 6.18 8* 5.03 1548 6.19 9* 1.54 2043 6.18 10* n.d. n.d. n.d. 11* n.d. n.d. n.d. 12* 8.14 1465 6.11 13 0.32 2404 6.18 14 4.54 2055 6.25 15 0.70 1964 6.18 16 0.27 2423 6.15 17 3.57 3356 6.18 18 0.31 2092 6.20 19 1.12 1998 6.18 20 1.92 2754 6.17 21 4.42 2090 6.23 22 0.37 3118 6.23 23 0.35 3089 6.22 24 0.17 3409 6.20 25 0.19 4100 6.22 26 4.42 3592 5.86 27 0.15 2967 6.17 28 0.14 3301 6.15 29 2.58 2442 6.18 30 2.54 1941 6.21 31 0.52 2233 6.15 32 1.83 2752 6.15 33 0.79 2953 6.20 34 0.83 2208 6.21 35 0.24 3501 6.20 36 0.34 2833 6.38 37 0.23 3432 5.91 38 0.20 3262 6.18 38 0.26 3580 6.11 40 0.16 4120 6.25 41 0.39 3317 6.19 42 0.17 3230 6.15 43 0.25 3690 6.15 44 0.22 4167 6.28 45 5.97 3196 5.97 46 0.60 2385 6.14 47 0.26 4349 6.17 48 0.22 4073 6.29 49 0.42 3313 6.09 50 0.37 3827 5.87 51 0.83 3580 5.93 52 0.14 7344 6.07 *The examples were prepared without perfume in the shower gel.

(32) The viscosity of the preparations is measured on a rheometer at 25 C.1 C. with 40 mm cone/plate geometry (1 cone angle) with a gap of 0.03 mm, charging being carried out in a structure-preserving manner. A suitable constant shear rate time ramp is pregiven and a corresponding structure recovery time is observed before the test. The viscosity is given for a shear rate of 10 s.sup.1.

Example 54

(33) It has surprisingly been found that the morphology of the polymers produced by a rapid dosing of the monomer mixture is advantageous within the context of the present invention. Table 4 shows the various properties of two polymers when the dosing time is varied. The dosing time is preferably 40 minutes and particularly preferably 30 minutes.

(34) TABLE-US-00006 TABLE 5 Dosing time and results Polymer Dosing time tan Viscosity in mPas Example 35 30 minutes 0.24 3501 Example 35 40 minutes 0.21 4114 Example 35 50 minutes 0.49 4056 Example 35 60 minutes 1.45 3585 Example 24 30 minutes 0.17 3409 Example 24 50 minutes 24.26 1805

Example 55

(35) The polymers according to the invention must have adequate storage stability. For this purpose, a shower gel according to Example 53 was produced again after one year from Examples 1, 22, 24, 25 and 28. It is found that the polymers according to the invention are also advantageous after prolonged storage at room temperature.

(36) TABLE-US-00007 TABLE 6 Results of storage stability after 24 h after storage Viscosity Viscosity Polymer tan in mPas Time tan in mPas Example 1 0.30 3544 15 months 0.24 4285 Example 22 0.37 3118 13 months 0.29 4247 Example 24 0.17 3409 13 months 0.20 4083 Example 25 0.19 4100 13 months 0.22 4823 Example 28 0.14 3301 10 months 0.20 3754

Example 56

(37) Compared to other polymers, the polymers according to the invention overcome deficiencies in the prior art compared to other polymers.

(38) In order to illustrate this, a shower gel according to Example 53 was prepared in each case from Examples 24, 37 and Carbopol AQUA SF-1 (Lubrizol).

(39) TABLE-US-00008 TABLE 7 Results compared to AQUA SF-1 Example 24 Example 37 Carbopol AQUA SF-1 tan 0.17 0.23 0.42 Viscosity in mPas 3409 3432 3834 Yield point in Pa 3.6 3.4 3.3 pH 6.20 5.91 6.45 Turbidity in NTU 8 9 18 (58 at pH 6.20)

(40) At a lower pH than AQUA SF-1, the polymers according to the invention have a better tan and a lower turbidity. Turbidity values of <10 are comparable with spring water. Upon adjusting a preparation containing AQUA SF-1 to a lower pH value, e.g.: 6.20, the preparation is distinctly perceptibly turbid (NTU=58).