BLOCK CO-POLYMER

Abstract

The invention relates to a block-co-polymer comprising at least one first block and at least one second block which is different from the first block, wherein the first block comprises repeating units 1, and the second block comprises repeating units 2, wherein Z represents O or NH, R.sub.1 represents H or CH.sub.3, R.sub.2 represents a group selected from hydrocarbyl groups and ether group-containing groups, R.sub.3 represents an organic group having 2 to 4 carbon atoms, R.sub.4 and R.sub.5 independently represent an organic group, wherein R.sub.4 and R.sub.5 are optionally linked to each other to form a cyclic structure, and wherein the first block comprises wherein the first block comprises at least two different types of repeating units comprising ether groups.

##STR00001##

Claims

1. A block co-polymer comprising at least one first block and at least one second block which is different from the first block, wherein the first block comprises repeating unit 1, ##STR00007## and the second block comprises repeating unit 2, ##STR00008## wherein Z represents O or NH, R.sup.1 represents H or CH.sub.3, R.sup.2 represents a hydrocarbyl group or an ether group-containing group, R.sup.3 represents an organic group having 2 to 4 carbon atoms, R.sup.4 and R.sup.5 each independently represent an organic group or wherein R.sup.4 and R.sup.5 are linked to each other to form a cyclic organic structure, and wherein the first block comprises at least two different repeating units comprising ether groups.

2. The block co-polymer according to claim 1, wherein the second block further comprises repeating unit 3 ##STR00009## wherein R.sup.6 represents an organic group and Xrepresents an anion.

3. The block co-polymer according to claim 1, wherein the first block comprises at least six different types of repeating unit 1.

4. The block co-polymer according to claim 1, wherein the first block comprises between 3 and 50 mol-% of repeating units comprising ether groups.

5. The block co-polymer according to claim 1, wherein the first block consists of polymerized units of a) methyl methacrylate in an amount of 20 to 60% by weight, b) butyl methacrylate in an amount of 10 to 30% by weight, c) 2-ethyl-hexyl methacrylate in an amount of 10 to 30% by weight, d) one or more methacrylates having an aromatic or aliphatic ring in an amount of 3 to 20% by weight, and e) two or more methacrylates having ether groups in an amount of 3 to 20% by weight, wherein the % by weight of a) to e) add up to 100%.

6. The block co-polymer according to claim 1, wherein the block co-polymer has a polydispersity in the range of 1.03 to 1.80.

7. The block co-polymer according to claim 1, wherein the block co-polymer has a number average molecular weight M.sub.n in the range of 2000 to 20000 g/mol.

8. The block co-polymer according to claim 1, wherein the first block comprises repeating units derived from one or more of ethyl triglycol methacrylate, methyl triglycol methacrylate, and butyl diglycol methacrylate.

9. The block co-polymer according to claim 1, wherein the weight ratio of the first block and the second block is in the range of 90:10 to 25:75.

10. The block co-polymer according to claim 1, wherein the block co-polymer comprises a third block, which is different from the first and the second block.

11. The block co-polymer according to claim 10, wherein the third block is located between the first block and the second block.

12. The block co-polymer according to claim 1, wherein the block co-polymer consists of the first block and the second block.

13. A composition comprising: (A) at least one wetting and/or dispersing agent, (B) at least one colorant, and (C) at least one organic solvent, wherein the wetting and/or dispersing agent comprises the block co-polymer according to claim 1.

14. The composition according to claim 13, wherein the colorant includes one or more of a pigment and a dye.

15. The composition according to claim 13, wherein the composition further comprises at least one alkali-soluble resin.

16. The composition according to claim 13, further comprising a component having at least one ethylenically unsaturated polymerizable group.

17. A process for preparing a color filter, the process comprising applying the composition according to claim 13 to a substrate and curing selected areas of the composition by exposure to actinic radiation.

18. (canceled)

19. The block co-polymer according to claim 1, wherein R.sup.4 and R.sup.5 are linked to each other to form a cyclic organic structure.

20. A color filter comprising a cured material, the cured material obtained by curing a composition with the actinic radiation, the composition comprising: an organic solvent, a colorant, and a block co-polymer comprising a first block and a second block, the second block being different from the first block, the first block comprising repeating unit 1, and the second block comprising repeating unit 2, ##STR00010## wherein Z represents O or NH, R.sup.1represents H or CH.sub.3, R.sup.2 represents a hydrocarbyl group or an ether group-containing group, R.sup.3 represents an organic group having 2 to 4 carbon atoms, R.sup.4 and R.sup.5 each independently represent an organic group or wherein R.sup.4 and R.sup.5 are linked to each other to form a cyclic organic structure, and wherein the first block comprises at least two different repeating units comprising ether groups.

21. An apparatus comprising a liquid crystal display including the color filter according to claim 20.

22. An apparatus comprising a liquid crystal screen including the color filter according to claim 20.

23. An apparatus comprising a color resolution device including the color filter according to claim 20.

24. An apparatus comprising a sensor including the color filter according to claim 20.

Description

EXAMPLES

Raw Materials:

[0097] MMA: methyl methacrylate (manufacturer: Evonik)

[0098] BMA: n-butyl methacrylate (manufacturer: Evonik) [0099] CHMA: cyclohexyl methacrylate (manufacturer: Evonik) [0100] BzMA: benzyl methacrylate (manufacturer: Evonik) [0101] EHMA: 2-ethylhexyl methacrylate (manufacturer: Evonik) [0102] iBOMA: iso bornyl methacrylate (manufacturer: Evonik) [0103] MTGMA: methyltriglycol methacrylate (purchased from Sigma-Aldrich) [0104] BDGMA: butyldiglycol methacrylate (purchased from Sigma-Aldrich) [0105] ETGMA: ethyltriglycol methacrylate (manufacturer: Evonik) [0106] DMAEMA: N,N-dimethylaminoethyl methacrylate (manufacturer: Evonik) [0107] Initiator: 1-methoxy-1-(trimethylsiloxy)-2-methylpropene (purchased from Sigma-Aldrich) [0108] Catalyst: tetrabutylammonium 3-chlorobenzoate, 50% strength in acetonitrile, see U.S. Pat. No. 4,588,795 [0109] AMBN: 2,2-azo-di(2-methylbutyronitrile) (manufacturer: Akzo Nobel) [0110] PMA: 1-methoxy-2-propyl acetate (manufacturer: DOW Chemical) [0111] PM: 2-methoxypropanol (manufacturer: DOW Chemical)

[0112] 1-Methoxy-2-propyl acetate and all monomers are stored over 3 molecular sieve for 48 hours before use.

Gel Permeation Chromatography (GPC)

[0113] Number-average M.sub.n and weight-average M.sub.w molecular weights and the molecular weight distribution were determined according to DIN 55672-1:2007-08 at 40 C. using a high-pressure liquid chromatography pump (WATERS 600 HPLC pump) and a refractive index detector (Waters 410). As separating columns, a combination was used of 3 Styragel columns from WATERS with a size of 300 mm7.8 mm ID/column, a particle size of 5 m, and pore sizes HR4, HR2 and HR1. The eluent used was tetrahydrofuran with 1% by volume of dibutylamine, with an elution rate of 1 mL/min. The conventional calibration was carried out using polystyrene standards.

Measurement of Non-Volatile Content (Solids Content)

[0114] The sample (2.00.2 g of the tested substance) was weighed accurately into a previously dried aluminum dish and dried for 20 minutes at 150 C. in the varnish drying cabinet, cooled in a desiccator and then reweighed. The residue corresponds to the solids content in the sample (ISO 3251).

Measurement of the Amine Value

[0115] 0.5 to 1.5 g of a dispersant was precisely weighed out into a 100 mL beaker and is dissolved with 50 mL of acetic acid. Using an automatic titration device provided with a pH electrode, this solution was neutralization-titrated with a 0.1 mol/L HCLO.sub.4 acetic acid solution. A flexion point of a titration pH curve was used as a titration endpoint, and an amine value was obtained by the following equation.

Amine value [mg KOH/g]=(561V)/(WS)

(wherein W: weighed amount of dispersant sample [g], V: titration amount at titration endpoint [mL], S: solid matter concentration of dispersant sample [wt.-%])
General Procedure for Preparing Block Co-Polymers 1-9 (see Table 1) 75 g of 1-methoxy-2-propyl acetate were placed into a water-free reaction vessel.

[0116] Monomer mixture 1 was metered at a rate of 1.2 g/min. Immediately after the start of the metering, the respective amount of initiator and 10 wt.-% of the catalyst, in respect to the amount of initiator, were introduced into the reaction vessel. Throughout the reaction, the reaction temperature was kept at 20 C. After the end of the metering of monomer mixture 1, monomer 2 was metered in at a rate of 1.3 g/min. The subsequent reaction time after the end of the metering of monomer 2 was 60 minutes. Afterwards 3.3 g of 2-methoxypropanol were added in order to stop the reaction.

Procedure for Preparing Block Co-Polymer 10 by (see Table 1)

[0117] 75 g of 1-methoxy-2-propyl acetate were placed into a water-free reaction vessel. 59.1 g of monomer mixture 1 was metered in at a rate of 1.2 g/min. Immediately after the start of the metering, the respective amount of initiator and 10 wt.-% of the catalyst, in respect to the amount of initiator, were introduced into the reaction vessel. Throughout the reaction, the temperature was kept at 20 C. After finalization of the dosage of 59.1 g of monomer mixture 1 additional 19.3 g of monomer mixture 1 was metered in within 14 minutes with a continuously reduced metering rate of 1.2 g/min to 0.5 g/min. Parallel 16.2 g of monomer 2 were metered in with a continuously increased metering rate of 0.5 g/min to 1.3 g/min. The residual amount of monomer 2 was metered in at a rate of 1.3 g/min after finalization of the parallel metering of monomer mixture 1 and monomer 2. The subsequent reaction time after the end of the metering of monomer 2 was 60 minutes. Afterwards 3.3 g of 2-methoxypropanol were added in order to stop the reaction.

Procedure for Preparing Block Co-Polymer 11 (see Table 1)

[0118] 75 g of 1-methoxy-2-propyl acetate were placed into a water-free reaction vessel. 70.9 g of monomer mixture 1 was metered in at a rate of 1.2 g/min. Immediately after the start of the metering, the respective amount of initiator and 10 wt.-% of the catalyst, in respect to the amount of initiator, were introduced into the reaction vessel. Throughout the reaction, the temperature was kept at 20 C. After finalization of the dosage of 70.9 g of monomer mixture 1 additional 7.5 g of monomer mixture 1 was metered in at a rate of 0.6 g/min parallel to 16.2 g of monomer 2 which was metered in at a rate of 1.3 g/min. The residual amount of monomer 2 was metered in at a rate of 1.3 g/min after finalization of the parallel metering of monomer mixture 1 and monomer 2. The subsequent reaction time after the end of the metering of the monomer 2 was 60 minutes. Afterwards 3.3 g of 2-methoxypropanol were added in order to stop the reaction.

Procedure for Preparing Block Co-Polymer 12 (see Table 1)

[0119] 75 g of 1-methoxy-2-propyl acetate were placed into a water-free reaction vessel. 59.1 g of monomer mixture 1 was metered in at a rate of 1.2 g/min. Immediately after the start of the metering, the respective amount of initiator and 10% wt.-% of the catalyst, in respect to the amount of initiator, were introduced into the reaction vessel. Throughout the reaction, the temperature was kept at 20 C. A combination of 19.3 g of monomer mixture 1 and 16.2 g of monomer 2 was metered in at a rate of 1.2 g/min. After the end of the metering, 23.6 g of monomer 2 was metered in at a rate of 1.3 g/min. The subsequent reaction time after the end of the metering of monomer 2 was 60 minutes. Afterwards 3.3 g of 2-methoxypropanol were added in order to stop the reaction.

TABLE-US-00001 TABLE 1 Raw material quantities in gram for preparing block co-polymers 1 to 12 and analytical data thereof Poly- Initiator/ Monomer Mixture 1 mers Catalyst MMA BMA EHMA CHMA BzMA iBOMA MTGMA 1 * 3.3/0.33 39.2 31.3 2* 3.3/0.33 31.3 19.6 19.6 3* 3.3/0.33 23.5 15.7 15.7 15.7 4* 3.3/0.33 15.7 3.9 15.7 15.7 5 3.3/0.33 31.3 15.7 15.7 7.8 3.9 6 3.3/0.33 31.3 15.7 15.7 7.8 2.4 7 3.3/0.33 31.3 15.7 15.7 7.8 5.5 8 3.3/0.33 28.9 14.5 14.5 7.2 3.9 9 3.3/0.33 28.7 14.4 14.4 2.8 7.2 3.5 3.7 10 3.3/0.33 31.3 15.7 15.7 7.8 3.9 11 3.3/0.33 31.3 15.7 15.7 7.8 3.9 12 3.3/0.33 31.3 15.7 15.7 7.8 3.9 Monomer Amine Solids Poly- Mixture 1 Monomer 2 Value of M.sub.w/ content mers ETGMA BDGMA DMAEMA Polymers M.sub.n M.sub.n in % 1 * 7.8 39.8 118 7191 1.21 60 2* 7.8 39.8 118 7404 1.26 60 3* 7.8 39.8 118 7654 1.25 60 4* 27.4 39.8 118 7320 1.24 60 5 3.9 39.8 118 7126 1.19 60 6 5.5 39.8 118 7022 1.27 60 7 2.4 39.8 118 7464 1.19 60 8 5.5 3.9 39.8 118 7477 1.26 60 9 3.7 39.8 118 7117 1.23 60 10 3.9 39.8 118 7588 1.19 60 11 3.9 39.8 118 7530 1.27 60 12 3.9 39.8 118 7045 1.17 60 Comparative examples are marked with *
Preparation of alkali-soluble resin R1:

[0120] 300 g of 1-methoxy-2-propyl acetate were placed into a reaction vessel. 137 g of BzMA, 34 g of methacrylic acid and 1.65 g of AMBN were metered in at a temperature of 120 C. over 180 minutes. The subsequent reaction time after the end of the metering was 120 minutes. The solids content was then adjusted to 35 wt.-% with 1-methoxy-2-propyl acetate (DIN EN ISO 3251:2008-06 at 150 C. for 20 min).

[0121] Preparation of the pigment dispersions

[0122] Pigments:

TABLE-US-00002 PG 58 Fastogen Green A110 (manufacturer: DIC) PY 150 Chromophtal Yellow D1085J (manufacturer: BASF)
PG 58/PY 150 pigment dispersion

TABLE-US-00003 Alkali-soluble resin R1 7.14 g 1-Methoxy-2-propyl acetate 29.11 g n-Butanol 2.50 g Block Co-polymer 3.75 g PG 58 4.30 g PY 150 3.20 g

[0123] The alkali-soluble resin R1, 1-methoxy-2-propyl acetate, n-butanol, the block co-polymer as per table 1, 4.3 g Pigment Green 58, and 3.20 g Pigment Yellow 150 were put together in a 100 mL glass bottle. 100 g of zirconium beads (diameter 0.4-0.6 mm) were added. Dispersion process was performed in a LAU-Disperser DAS 200 over a period of 5 hours at 40 C. After 16 hours, the concentrate was filtered into a 50 mL glass bottle to remove the zirconium beads. The pigment dispersions also represent examples of the compositions according to the invention.

Measurement of the viscosity of the dispersions:

[0124] The pigment dispersions' viscosity was measured after grinding and filtering by means of an Anton-Paar Rheometer using the CP50-1 measurement system at 25 C. according to DIN 53019-1:2008-09. After one week, storage at 40 C. the viscosity was measured again.

[0125] Viscosity 1: the viscosity after grinding and filtering

[0126] Viscosity 2: the viscosity after storage for 7 days at 40 C.

TABLE-US-00004 TABLE 2 Results of the viscosity measurements: Viscosity 1 Viscosity 2 W&D additive [mPa*s] [mPa*s] 1* 120 thick 2* thick 29.8 3* 118 30.1 4* 230 22.6 5 43.1 11.2 6 43.5 11.0 7 35.5 11.1 8 28.6 10.0 9 28.7 10.3 10 18.3 11.2 11 30.2 13.9 12 44.7 12.4 Comparative examples are marked with*

[0127] In Table 2, the indication thick means that the composition had almost solidified and that viscosity was too high to be measured. From Table 2 it can be inferred that the compositions containing the polymers according to the invention as dispersing agents have a significantly lower viscosity than the comparative compositions. The viscosity of the compositions of the invention is also more stable after storage at 40 C. than the comparative compositions.