OXIME SULFONATE DERIVATIVES

Abstract

Oxime sulfonate compounds of the formula (I), wherein R.sub.1 is O(CO)R.sub.4, COOR.sub.5 or CONR.sub.6R.sub.7; n is 1 or 2; R.sub.2 for example is C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.6cycloalkyl or benzyl; R.sub.3 is for example C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, benzyl, phenyl or naphthyl, which optionally are substituted; R.sub.4 is for example C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, benzyl, phenyl or naphthyl, which optionally are substituted; R.sub.5 is for example C.sub.3-C.sub.20alkyl, C.sub.3-C.sub.14cycloalkyl, C.sub.2-C.sub.8alkenyl, C.sub.1-C.sub.12alkyl which is substituted for example by one or more halogen; or R.sub.5 is phenyl or naphthyl, which are unsubstituted; R.sub.6 and R.sub.7 each independently of one another for example are hydrogen, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.4haloalkyl, phenyl-C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.8alkenyl or C.sub.3-C.sub.6cycloalkyl, phenyl or naphthyl; or R.sub.6 and R.sub.7, together with the N-atom to which they are attached, form a 5- or 6-membered ring; are suitable as thermal radical initiators.

##STR00001##

Claims

1. A compound of formula I ##STR00039## wherein R.sub.1 is O(CO)R.sub.4, COOR.sub.5 or CONR.sub.6R.sub.7, n is 1 or 2; R.sub.2 is C.sub.1-C.sub.8 alkyl, C.sub.2-C.sub.8 alkyl which is interrupted by one or more O, or C.sub.3-C.sub.6 cycloalkyl, which is uninterrupted or is interrupted by one or more O; or R.sub.2 is benzyl, which is unsubstituted or is substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6 alkylsulfanyl or C.sub.1-C.sub.6 alkoxy; R.sub.3 is C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.8 haloalkyl or C.sub.2-C.sub.8 alkenyl; or R.sub.3 is benzyl, phenyl or naphthyl, where the benzyl, phenyl or naphthyl is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 alkoxy, phenyl or COO(C.sub.1-C.sub.6 alkyl); R.sub.4 is C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.8 haloalkyl or C.sub.2-C.sub.8 alkenyl; or R.sub.4 is benzyl, phenyl or naphthyl, where the benzyl, phenyl or naphthyl are unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6 alkylsulfanyl, phenylsulfanyl, C.sub.1-C.sub.6 alkoxy, phenoxy, phenyl or COO(C.sub.1-C.sub.6 alkyl); R.sub.5 is C.sub.3-C.sub.20 alkyl, C.sub.3-C.sub.14 cycloalkyl or C.sub.2-C.sub.8 alkenyl; or R.sub.5 is C.sub.1-C.sub.12 alkyl substituted by one or more halogen, CN, phenylsulfanyl, phenoxy, N(C.sub.1-C.sub.6 alkyl).sub.2, N(phenyl).sub.2, phthalimido, phenyl or phenyl substituted by one or more C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6 alkylsulfanyl phenylsulfanyl, C.sub.1-C.sub.6 alkoxy, phenoxy, N(C.sub.1-C.sub.6 alkyl).sub.2, N(phenyl).sub.2; or R.sub.5 is C.sub.2-C.sub.12 alkyl or C.sub.3-C.sub.6 cycloalkyl, each of which is interrupted by one or more O or S; or R.sub.5 is phenyl or naphthyl, where the phenyl or naphthyl are unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 alkoxy, phenyl or COO(C.sub.1-C.sub.6 alkyl); R.sub.6 and R.sub.7 each independently are hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.4 haloalkyl, phenyl-C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.8 alkenyl or C.sub.3-C.sub.6 cycloalkyl, or R.sub.6 and R.sub.7 are C.sub.2-C.sub.12 alkyl which is interrupted by O, S, N(C.sub.1-C.sub.8 alkyl) or CO, or R.sub.6 and R.sub.7 are C.sub.2-C.sub.4 haloalkyl which is interrupted by O, S, N(C.sub.1-C.sub.8 alkyl) or CO, or R.sub.6 and R.sub.7 each independently are phenyl-C.sub.1-C.sub.4 alkyl which is interrupted by O, S, N(C.sub.1-C.sub.8 alkyl) or CO; or R.sub.6 and R.sub.7 are C.sub.2-C.sub.8 alkenyl which is interrupted by O, S, N(C.sub.1-C.sub.8 alkyl) or CO, or R.sub.6 and R.sub.7 are C.sub.3-C.sub.6 cycloalkyl which is interrupted by O, S, N(C.sub.1-C.sub.8 alkyl) or CO, or R.sub.6 and R.sub.7 each independently are phenyl or naphthyl, where the phenyl or naphthyl is unsubstituted or is substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, CN, NO.sub.2, C.sub.1-C.sub.6 alkylsulfanyl, C.sub.1-C.sub.6 alkoxy, phenyl or COO(C.sub.1-C.sub.6 alkyl); or R.sub.6 and R.sub.7, together with the N-atom to which R.sub.6 and R.sub.7 are attached, form a 5- or 6-membered ring via C.sub.2-C.sub.5alkylene, where the C.sub.2-C.sub.5 alkylene ring is uninterrupted or interrupted by one or more O, S, N(C.sub.1-C.sub.8 alkyl), NH or CO.

2. The compound according to claim 1, wherein R.sub.1 is O(CO)R.sub.4, COOR.sub.5 or CONR.sub.6R.sub.7, n is 1 or 2; R.sub.2 is C.sub.1-C.sub.4 alkyl or benzyl; R.sub.3 is benzyl, phenyl or phenyl substituted by one or more C.sub.1-C.sub.6 alkyl; R.sub.4 is benzyl, phenyl or phenyl substituted by one or more C.sub.1-C.sub.6 alkyl; R.sub.5 is C.sub.3-C.sub.18 alkyl or C.sub.3-C.sub.12 cycloalkyl, or R.sub.5 is C.sub.2-C.sub.12 alkyl which is interrupted by one or more O, or R.sub.5 is C.sub.1-C.sub.6 alkyl substituted by phenylsulfanyl, phenoxy, N(C.sub.1-C.sub.6 alkyl).sub.2, N(phenyl).sub.2, phthalimido, phenyl or phenyl substituted by one or more C.sub.1-C.sub.12 alkyl; R.sub.6 and R.sub.7 each independently are hydrogen, C.sub.1-C.sub.6 alkyl or phenyl, or together with the N-atom to which R.sub.6 and R.sub.7 are attached form a morpholino ring.

3. The compound according to claim 1, wherein R.sub.1 is O(CO)R.sub.4, COOR.sub.5 or CONR.sub.6R.sub.7; n is 1 or 2 R.sub.2 is methyl, ethyl or benzyl R.sub.3 is benzyl, phenyl or phenyl substituted by C.sub.1-C.sub.6 alkyl; R.sub.4 is benzyl, phenyl or phenyl substituted by one or more C.sub.1-C.sub.6 alkyl; R.sub.5 is C.sub.3-C.sub.18 alkyl or C.sub.3-C.sub.12 cycloalkyl, or R.sub.5 is C.sub.2-C.sub.12 alkyl interrupted by one or more O, or R.sub.5 is C.sub.1-C.sub.6 alkyl substituted by phenyl, phenoxy or phthalimido; R.sub.6 and R.sub.7 each independently are hydrogen or phenyl.

4. A polymerizable composition, comprising, (a) a monomeric, oligomeric or polymeric compound comprising at least one ethylenically unsaturated double bond; and (b) at least one compound of the formula I according to claim 1.

5. The polymerizable composition according to claim 4, further comprising at least one photoinitiator (c).

6. The polymerizable composition according to claim 4, further comprising a binder polymer (d).

7. The polymerizable composition according to claim 6, further comprising at least one component (e) selected from the group consisting of (e1) a pigment, (e2) a dye, (e3) a filler, (e4) a dispersant, (e5) a sensitizer, (e6) a thermosetting compound, which is different from the compound of the formula (I) and the binder polymer (d), and a mixture thereof.

8. The polymerizable composition according to claim 7, comprising the as further component (e5), which comprising a compound selected from the group consisting of and its derivatives a derivative thereof, and its derivatives a derivative thereof, and its derivatives a derivative thereof, and its derivatives a derivative thereof.

9. The polymerizable composition according to claim 4, comprising: (a) at least one acrylate monomer, (b) at least one compound of the formula I, (c) at least one photoinitiator, and (d) at least one alkaline developable resin.

10. The polymerizable composition according to claim 4, comprising the component (a) in an amount of from 0.01 to 50% by weight, based on a total weight of the composition.

11. A process for thermally polymerizing a composition containing ethylenically unsaturated double bonds, the processing comprising heating the polymerizable composition according to claim 4.

12. The process according to claim 11, wherein the heating occurs at a temperature of from 80° C. to 260° C.

13. An article, obtained by the process according to claim 12, wherein the article is a color filter, a spacer for LCD, an overcoat layer for color filter and LCD, a sealant for LCD and OLED, an optical film, an anisotropy conducting adhesive for LCD, an insulation/passivation layer for LCD, an organic light-emitting diode display, a touch panel, a flexible display, a bank/pixel definition layer of OLED, an insulation for metal wiring/transparent conductive film for touch panel, a coating for touch panel, a hard coat and optical coat, decorative ink for touch panel, a protective film for touch panel, an etching resist for touch panel, or a structure or a layer in manufacturing a plasma-display panel, an electroluminescence display, an organic light-emitting diode display, a touch panel, a flexible display and LCD, or a solder mask or a dielectric layer in a sequential build-up layer of a printed circuit board.

14. A resist, comprising the polymerizable composition according to claim 4 wherein the resist is suitable for making a color filter, a spacer for LCD, an overcoat layer for color filter and LCD, a sealant for LCD and OLED, an optical film, an anisotropy conducting adhesive for LCD, an insulation/passivation layer for LCD, an organic light-emitting diode display, a touch panel, a flexible display, a bank/pixel definition layer of OLED, an insulation for metal wiring/transparent conductive film for touch panel, a coating for touch panel, a hard coat and optical coat, decorative ink for touch panel, a protective film for touch panel, an etching resist for touch panel, or a resist or a photosensitive composition to generate a structure or a layer in manufacturing a plasma-display panel, an electroluminescence display, an organic light-emitting diode display, a touch panel, a flexible display and LCD, or a solder resist, or a photoresist material for forming a dielectric layer in a sequential build-up layer of a printed circuit board.

15. A coated substrate, which is coated on at least one surface with the polymerizable composition according to claim 4.

16. A color filter, obtained by a process comprising providing red, green and blue picture elements and optionally a black matrix, all comprising a photosensitive resin and a pigment on a transparent substrate and providing a transparent electrode either on a surface of the substrate or on a surface of the color filter, wherein the photosensitive resin comprises a polyfunctional acrylate monomer, an organic polymer binder, a photopolymerization initiator and at least one compound of the formula I according to claim 1.

17. A method for preparing the compound of the formula (I) according to claim 1, the method comprising reacting a free oxime of formula (IA) ##STR00040## wherein R.sub.1 is O(CO)R.sub.4, COOR.sub.5 or CONR.sub.6R.sub.7; n is 1 or 2; and R.sub.2 is C.sub.1-C.sub.8 alkyl, C.sub.2-C.sub.8 alkyl which is interrupted by one or more O, or C.sub.3-C.sub.6 cycloalkyl, which is uninterrupted or is interrupted by one or more O, with a sulfonic acid halide of formula (IB) ##STR00041## wherein R.sub.3 is C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.8 haloalkyl or C.sub.2-C.sub.8 alkenyl; and Hal is a halogen.

Description

PREPARATION EXAMPLES

[0343] Preparation of OS1OS1 is prepared as described in the following scheme.

##STR00017##

(1.1) Preparation of 2-benzoyloxyethylthiol

[0344] 11.8 g of 2-mercaptoethanol and 12.2 g of benzoic acid are combined in 50 mL of xylene. To this solution are added 0.36 g of Ti(O.sup.nBu).sub.4, and the mixture is heated to reflux for 18 hours. The resulting water is removed by Dean-Stark trap during reflux. After cooling down, water and ethyl acetate are added to the reaction mixture. The organic layer is separated from the aq. layer and washed with water twice and then brine, followed by drying over anhydrous MgSO.sub.4. 18.4 g of colorless oil is obtained and used for next reaction without further purification.

(1.2) Preparation of Intermediate I2

[0345] 6.87 g of intermediate I1, which is prepared according to the procedure described in WO2012101245, and 11.4 g of 2-benzoyloxyethylthiol are dissolved in 40 mL of ethyl acetate. To this solution are added 6.38 g of triethyl amine in 10 mL of ethyl acetate dropwise over 20 min. under cooling with an ice bath. After completion of the addition, the reaction mixture is further stirred at room temp. for 1.5 hours. After adding water, the organic layer is separated from the aq. layer and washed with water twice and then brine, followed by drying over anhydrous MgSO.sub.4. After concentration of the organic layer, the resulting pale brown solid is washed with a mixture of t-buthyl methyl ether and hexane, and 8.54 g of white solid is obtained.

(1.3) Preparation of OS1

[0346] 8.36 g of intermediate I2 and 5.94 g of p-toluenesulfonyl chloride are dissolved in 60 mL of ethyl acetate. To this solution are added 3.29 g of triethyl amine in 5 mL of ethyl acetate dropwise over 10 min. under cooling with an ice bath. After completion of the addition, the reaction mixture is further stirred at room temp. for 14 hours. After adding water, the organic layer is separated from the aq. layer and washed with water twice and then brine, followed by drying over anhydrous MgSO.sub.4. After concentration of the organic layer, the resulting solid is recrystallized from a mixture of CH.sub.2Cl.sub.2 and hexane, and 7.88 g of white solid is obtained.

Preparation of OS13

[0347] OS13 is prepared as described in the following scheme.

##STR00018##

(13.1) Preparation of Benzyl 2-mercaptopropanoate

[0348] 2.19 g of 2-mercaptopropanoic acid and 2.28 g of benzyl alcohol are combined in 10 mL of toluene. To this solution are added 3 drops of conc. H.sub.2SO.sub.4, and the mixture is heated to reflux for 100 minutes. The resulting water is removed by Dean-Stark trap during reflux. After cooling down, water and ethyl acetate are added to the reaction mixture. The organic layer is separated from the aq. layer and washed with water twice, NaHCO.sub.3 aq. solution and then brine, followed by drying over anhydrous MgSO.sub.4. 3.95 g of colorless oil is obtained and used for next reaction without further purification.

(13.2) Preparation of Intermediate I3

[0349] The intermediate I3 is prepared by the procedure given for example 1.2 and obtained as pale yellow oil.

(13.3) Preparation of Intermediate OS13

[0350] The title compound is prepared by the procedure given for example 1.3. The title compound is obtained as colorless resin.

[0351] The following novel oxime sulfonate compounds are prepared in a similar manner.

TABLE-US-00001 Oxime sulfonate (OS) Structure .sup.1H NMR in CDCl.sub.3 OS1 [00019] 2.44 (s, 3H), 3.35 (t, 2H), 3.84 (s, 3H), 4.45 (t, 2H), 7.33 (d, 2H), 7.44 (t, 2H), 7.59 (t, 1H), 7.86 (d, 2H), 8.02 (d, 2H) OS2 [00020] 2.45 (s, 3H), 2.56 (s, 3H), 3.35 (t, 2H), 3.81 (s, 3H), 4.42 (t, 2H), 7.20-7.30 (m, 2H), 7.34 (d, 2H), 7.42 (t, 1H), 7.83-7.90 (m, 3H) OS3 [00021] 2.20 (s, 6H), 2.28 (s, 3H), 2.47 (s, 3H), 3.36 (t, 2H), 3.58 (s, 3H), 4.41 (t, 2H), 6.83 (s, 2H), 7.35 (d, 2H), 7.87 (d, 2H) OS4 [00022] 2.44 (s, 3H), 3.22 (t, 2H), 3.58 (s, 2H), 3.87 (s, 3H), 4.21 (t, 2H), 7.22-7.37 (m, 7H), 7.87 (d, 2H) OS5 [00023] 1.14 (d, 3H), 1.73-1.76 (m, 2H), 2.46 (s, 3H), 3.26 (s, 3H), 3.31-3.41 (m, 1H), 3.82 (s, 2H), 3.84 (s, 3H), 4.20 (t, 2H), 7.35 (d, 2H), 7.87 (d, 2H) OS6 [00024] 0.76-1.62 (m, 15H), 2.46 (s, 3H), 3.83 (s, 2H), 3.84 (s, 3H), 4.06-4.13 (m, 2H), 7.35 (d, 2H), 7.87 (d, 2H) OS7 [00025] 1.17 (d, 3H), 1.74-1.84 (m, 2H), 3.31 (s, 2H), 3.36-3.44 (m, 1H), 3.87 (s, 2H), 3.94 (s, 3H), 4.25 (t, 2H), 4.59 (s, 2H), 7.49 (br, 5H) OS8 [00026] 1.13 (d, 3H), 1.70-1.79 (m, 2H), 3.28 (s, 3H), 3.32-3.41 (m, 1H), 4.20 (t, 2H), 7.57 (t, 2H), 7.69 (t, 1H), 7.99 (d, 2H) OS9 [00027] 0.83-1.66 (m, 15H), 2.46 (s, 3H), 3.82 (s, 2H), 4.06-4.14 (m, 2H), 4.29 (q, 2H), 7.34 (d, 2H), 7.87 (d, 2H)  OS10 [00028] 0.88 (t, 3H), 1.26-1.66 (m, 35H), 2.46 (s, 3H), 3.82 (s, 2H), 4.08 (t, 2H), 4.29 (q, 2H), 7.34 (d, 2H), 7.87 (d, 2H)  OS11 [00029] 0.82-1.66 (m, 15H), 2.44 (s, 3H), 3.79 (s, 2H), 3.97-4.07 (m, 2H), 7.33 (d, 2H), 7.37 (br, 5H), 7.85 (d, 2H)  OS12 [00030] 1.16 (d, 3H), 1.74-1.83 (m, 2H), 2.45 (s, 3H), 2.64 (t, 2H), 3.19 (t, 2H), 3.31 (s, 3H), 3.38- 3.42 (m, 1H), 4.20 (t, 2H), 7.35 (d, 2H), 7.85 (d, 2H)  OS13 [00031] 2.44 (s, 3H), 2.69 (t, 2H), 3.20 (t, 2H), 3.85 (s, 3H), 5.13 (s, 2H), 7.30-7.41 (m, 7H), 7.85 (d, 2H)  OS14 [00032] 2.44 (s, 3H), 2.62 (t, 2H), 2.93 (t, 2H), 3.14 (t, 2H), 3.86 (s, 3H), 4.31 (t, 2H), 7.17-7.27 (m, 3H), 7.28-7.36 (m, 4H), 7.85 (d, 2H)  OS15 [00033] 2.45 (s, 3H), 2.70 (t, 2H), 3.19 (t, 2H), 3.86 (s, 3H), 4.17 (dd, 2H), 4.45 (dd, 2H), 6.91 (d, 2H), 6.98 (t, 1H), 7.30 (t, 2H), 7.34 (d, 2H), 7.85 (d, 2H)  OS16 [00034] 2.45 (s, 3H), 2.62 (t, 2H), 3.14 (t, 2H), 3.87 (s, 3H), 3.95 (t, 2H), 4.34 (t, 2H), 7.34 (d, 2H), 7.72-7.78 (m, 2H), 7.82-7.90 (m, 4H)  OS17 [00035] 1.25-1.50 (m, 20H), 1.63-1.76 (m, 2H), 2.45 (s, 3H), 2.61 (t, 2H), 3.17 (t, 2H), 3.88 (s, 3H), 4.98-5.07 (m, 1H), 7.34 (d, 2H), 7.86 (d, 2H)  OS18 [00036] 2.45 (s, 3H), 2.73 (t, 2H), 3.31 (t, 2H), 3.88 (s, 3H), 7.13 (t, 1H), 7.30-7.37 (m, 4H), 7.50 (d, 2H), 7.85 (d, 2H)

APPLICATION EXAMPLES

Preparation of Acrylate Formulation (Clear)

[0352]

TABLE-US-00002 3.8 parts by weight solvent (PGMEA) 2.6 parts by weight alkaline developable binder, 37.8% solution (Ripoxy SPC-2000, provided by Showa Highpolymer) 1.0 parts by weight multifunctional acrylate (DPHA, provided by UCB Chemicals)

Thermal Curing Tests of Acrylate Formulation

Thermogravimetric Analysis of Dry Film Containing Oxime Sulfonate: Test A

[0353] The oxime sulfonate to be tested and additionally Irgacure® 369 (12.5 wt % in solid, provided by BASF) as photoinitiator are added to the above clear resist composition and mixed. The mixture is applied to a glass substrate using a spin coater (1H-DX2, MIKASA). The solvent is removed by heating at 80° C. for 2 min in a convection oven. Exposure is then carried out using a 250 W super high pressure mercury lamp (USHIO, USH-250BY) at a distance of 15 cm. The total exposure dose determined by measuring the light intensity with an optical power meter (ORC UV Light Measure Model UV-M02 with UV-35 detector) is 150 mJ/cm.sup.2. The thickness of the dry film is approximately 2.5 μm. The coating film is flaked and filled the aluminum cell with approximately 5 mg. Thermal weight loss is measured by thermogravimetric analysis (Shimadzu, DTAG-60/60H). The rate of temperature increase is 10° C./minutes and the flaked film in the aluminum cell is baked at 230° C. for 30 minutes. The lower weight loss is required to reduce contamination of a baking equipment or a substrate in use.

[0354] The results of the tests are given in table 1.

Thermal Curing Tests of Acrylate Formulation after Photocuring: Test B

[0355] The oxime sulfonate to be tested and additionally Irgacure® 369 (12.5 wt % in solid) as photoinitiator are added to the above clear resist composition and mixed. The mixture is applied to a Si Wafer using a spin coater (1H-DX2, MIKASA). The solvent is removed by heating at 80° C. for 2 min in a convection oven. Exposure is then carried out using a 250 W super high pressure mercury lamp (USHIO, USH-250BY) at a distance of 15 cm. The total exposure dose determined by measuring light intensity with an optical power meter (ORC UV Light Measure Model UV-M02 with UV-35 detector) is 150 mJ/cm.sup.2. The thickness of the dry film is approximately 2.5 μm. The coating is further baked at 180° C. for 30 min. The conversion of the acrylic group in baking is determined by measuring IR absorption at 810 cm.sup.−1, with a FT-IR spectrometer (FT-720, HORIBA) before and after baking. The results of the tests are given in table 1.

TABLE-US-00003 TABLE 1 Concentration of OS Oxime (wt % in Percentage sulfonate solid contents Molecular of weight Conversion of (OS) of composition) weight loss/% acrylate/% OS1 5 437.5 7.9 69.5 OS2 5 451.5 7.6 70.1 OS3 5 479.6 7.9 70.2 OS4 5 451.5 7.3 68.3 OS5 5 433.5 7.7 67.8 OS6 5 459.9 7.1 69.2 OS8 5 419.5 7.4 70.0 OS9 5 473.6 7.3 66.3  OS10 5 613.9 7.6 66.0  OS11 5 535.7 8.2 67.9  OS12 5 447.5 7.7 68.3  OS13 5 451.5 6.9 69.7  OS14 5 465.6 6.9 70.1  OS15 5 481.6 7.2 68.9  OS16 5 534.6 8.2 70.1  OS17 5 527.7 5.9 67.8  OS18 5 436.5 7.4 69.9 No OS 0 0 7.7 64.6 Comparison 5 497.7 10.4  62.8 Example 1 Comparison 5 377.4 8.8 69.8 Example 2 Comparison example 1 [00037]Comparison example 2 [00038]