NON-PIGMENTED DISPERSANT COMPOSITION

Abstract

The invention relates to a non-pigmented composition comprising a) 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, repeating unit 1 and the second block comprises repeating units 2, repeating unit 2 wherein Z represents O or NH, R.sup.1 represents H or CH.sub.3, R.sup.2 represents a group selected from hydrocarbyl groups and ether group-containing groups, R.sup.3 represents an organic group having 2 to 4 carbon atoms, R.sup.4 and R.sup.5 independently represent an organic group, wherein R.sup.4 and R.sup.5 are optionally linked to each other to form a cyclic structure, and b) a polymer comprising at least one acidic group, and having a number average molecular weight of 300 g/mol or higher.

##STR00001##

Claims

1. A non-pigmented composition comprising: 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 independently represent an organic group, wherein R.sup.4 and R.sup.5 are optionally linked to each other to form a cyclic structure, and a polymer comprising at least one acidic group, and having a number average molecular weight of 300 g/mol or higher, wherein repeating unit 2 of the block co-polymer is at least partially present as salt of the polymer comprising the at least one acidic group, and wherein the composition is essentially free of pigments, dyes, and inorganic filler materials.

2. The composition according to claim 1, wherein the at least one acidic group comprises at least one of a carboxylic acid group, an acidic group containing phosphorus, and a sulfonic acid group.

3. The composition according to claim 1, wherein the polymer comprising the at least one acidic group has an average functionality in the range of 0.9 to 1.2 acidic groups per molecule.

4. The composition according to claim 1, wherein the molar ratio of repeating unit 2 of the block co-polymer and the at least one acidic group of the polymer is in the range of 1.00:0.20 to 1.00:1.25.

5. The composition according to claim 1, wherein the polymer comprising the at least one acidic group further comprises one or more of an ether group and an ester group.

6. The composition according to claim 1, wherein the block co-polymer further comprises at least one third block.

7. The composition according to claim 6, wherein in the block co-polymer the at least one second block comprising repeating unit 2 is located between the at least one first block and the at least one third block.

8. The composition according to claim 7, wherein the at least one first block and the at least one third block have the same type of repeating unit 1.

9. The composition according to claim 7, wherein the at least one first block and the at least one third block have different types of repeating unit 1.

10. The composition according to claim 6, wherein in the block co-polymer the at least one third block comprises a different type of repeating unit 1 than the at least one first block, and wherein the at least one third block is located between at least one first block and the at least one second block.

11. (canceled)

12. (canceled)

13. A process of preparing a colored composition, the process comprising: providing a composition according to claim 1, adding one or more color imparting pigments or dyes to the composition, and dispersing the one or more pigments or dyes in the composition to form a colored composition.

14. The process according to claim 13, wherein the colored composition is an inkjet ink composition.

15. (canceled)

16. The process according to claim 13, wherein the colored composition comprises a color filter composition.

17. The process according to claim 13, wherein the colored composition comprises a coating composition for transportation vehicles.

Description

EXAMPLES

Raw Materials Used

[0081] MMA: Methyl methacrylate (Evonik) [0082] BMA: n-Butyl methacrylate (Evonik) [0083] BzMA: Benzyl methacrylate (Evonik) [0084] EHMA: 2-Ethylhexyl methacrylate (Evonik) [0085] IBOMA: Isobornyl methacrylate (Evonik) [0086] BDGMA: Butyldiglycol methacrylate (Evonik) [0087] MPEG-1000MA: Methoxy polyglycol (number of ethyleneoxide unit: 23) methacrylate (Shin-Nakamura Chemical) [0088] DMAEMA: N,N-Dimethylaminoethyl methacrylate (Evonik) [0089] MMTP: 1-Methoxy-1-(trimethylsiloxy)-2-methylpropene (Sigma-Aldrich) [0090] Catalyst: Tetrabutylammonium 3-chlorobenzoate, 50% strength in acetonitrile, see U.S. Pat. No. 4,588,795 [0091] AMBN: 2,2′-Azodi(2-methylbutyronitrile) (Akzo Nobel) [0092] PMA: 1-Methoxy-2-propyl acetate (DOW Chemicals) [0093] PM: 1-Methoxy-2-propylalcohol (DOW Chemicals) [0094] BzCl: Benzyl chloride (Sigma-Aldrich) [0095] Grilonit RV 1814: Alkyl (number of carbon: 13-15) glycidyl ether (EMS-GRILTECH) [0096] CGE: o-Cresylglycidylether (Sigma-Aldrich) [0097] Benzoic acid: (Sigma-Aldrich), theoretical molecular weight=122.12 [0098] Lutensol AO11: C13-C15 Alkoxylated polyethyleneglycol (number of ethyleneoxide unit: 11) (BASF) [0099] MPEG-350: Methoxy polyethylene glycol (number of ethyleneoxide unit: 8) [0100] ε-Caprolactone: (Sigma-Aldrich) [0101] δ-Valerolactone: (Sigma-Aldrich) [0102] PPA: Polyphosphoric acid (Sigma-Aldrich) [0103] Succinic anhydride: (Sigma-Aldrich) [0104] Maleic anhydride: (Sigma-Aldrich) [0105] KOH: Potassium hydroxide (Sigma-Aldrich) [0106] DBSA: Dodecylbenzenesulfonic acid (Sigma-Aldrich) [0107] Phosmer M: (2-Methacryloyloxy)ethyl phosphate (Uni-Chemical), theoretical molecular weight=210.12 [0108] Dibutylamine (Sigma-Aldrich)

General Methods

[0109] 1-Methoxy-2-propyl acetate and all monomers were stored over 3 A molecular sieve for 48 hours before use.

Gel Permeation Chromatography (GPC)

[0110] Number-average Mn and weight-average Mw 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 mm×7.8 mm ID/column, a particle size of 5 μm, 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)

[0111] The sample (2.0±0.2 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

[0112] 1.5 to 3.0 g of a sample was precisely weighed out into a 80 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]=(561×0.1×f×V)/(W×S)

(wherein f: factor of titration agent, V: titration amount at titration endpoint [mL], W: weighed amount of sample [g], S: solid matter concentration of sample [wt %])

Measurement of the Acid Value

[0113] 1.5 to 3.0 g of a sample was precisely weighed out into a 80 mL beaker and is dissolved with 50 mL of ethanol. Using an automatic titration device provided with a pH electrode, this solution was neutralization-titrated with a 0.1 mol/L ethanolic KOH 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.

Acid value [mg KOH/g]=(561×0.1×f×V)/(W×S)

[0114] (wherein f: factor of titration agent, V: titration amount at titration endpoint [mL], W: weighed amount of sample [g], S: solid matter concentration of sample [wt %])

Preparation of Polymers

Synthesis of Diblock Copolymer DB-1

[0115] 58.9 g of dried 1-methoxy-2-propyl acetate (PMA) was placed into a water-free reaction vessel. 36.3 g of monomer mixture 1 was added dropwise over 60 minutes. Immediately after the start of the metering, the respective amount of initiator and catalyst 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, 3.6 g of monomer 2 was added dropwise over 30 minutes. The subsequent reaction time after the end of the metering of monomer 2 was 60 minutes. Afterwards 1.1 g of 1-methoxy-2-propanol (PM) was added in order to stop the reaction. Analytical results of diblock copolymer DB-1 are described in Table 1.

Synthesis of Diblock Copolymer DB-2-DB-6

[0116] Diblock copolymer DB-2-DB-6 were synthesized using the same procedure as used for block copolymer DB-1, except using different monomer mixture 1 and monomer mixture 2 (Details are described in Table 1).

Synthesis of Random Copolymer RC-1

[0117] 41.0 g of PMA was placed into a reaction vessel and the reactor vessel was heated up to 120° C. Then, 40.0 g of monomer mixture 1 and 13.5 g of initiator solution (3.5 g of AMBN was dissolved in 10.0 g of PMA) were separately added dropwise to the reaction vessel over 3 hours. After the addition of monomer mixture 1 and initiator solution was finished, the reactor vessel was kept at 120° C. for 1 hour under stirring. After that, 5.5 g of initiator solution (0.5 g of AMBN was dissolved in 5.0 g of PMA) was added into the reactor vessel, and the he subsequent reaction time after adding the initiator solution was 60 minutes.

[0118] Analytical results of random copolymer RC-1 are described in Table 1.

Synthesis of Triblock Copolymer TB-1

[0119] 36.8 g of dried PMA was placed into a water-free reaction vessel. 24.1 g of monomer mixture 1 was added dropwise for 30 minutes. Immediately after the start of the metering, the respective amount of initiator and catalyst 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, 11.8 g of monomer 2 was added dropwise for 30 minutes. After the end of the metering of monomer mixture 2, 24.1 g of monomer 3 was added dropwise for 30 minutes. The subsequent reaction time after the end of the metering of monomer 3 was 60 minutes. Afterwards 1.6 g of PM was added in order to stop the reaction.

[0120] Analytical results of triblock copolymer TB-1 are described in Table 2.

Synthesis of Triblock Copolymer TB-2

[0121] Triblock copolymer TB-2 was synthesized using the same procedure as used for triblock copolymer TB-1, except using different dosages and/or compositions of monomer mixture 1, monomer mixture 2 and monomer mixture 3 (Details are described in Table 2).

Synthesis of Quaternized Diblock Copolymer QB-1

[0122] 58.4 g of diblock copolymer DB-6, 7.6 g of PMA, 29.0 g of PM and 5.0 g of benzyl chloride were placed into a reaction vessel, and the reactor vessel was heated up to 120° C. The quaternization reaction was carried out at 120° C. for 4 hours. An overview of quaternized diblock copolymers is provided in Table 3.

Synthesis of Quaternized Diblock Copolymer QB-2

[0123] 54.2 g of diblock copolymer DB-6, 37.4 g of PMA and 2.5 g of benzoic acid were placed into a reaction vessel, and the reactor vessel was heated up to 120° C. Then, 5.9 g of Grilonit RV 1814 was added to the reaction vessel. The quaternization reaction was carried out at 120° C. for 4 hours.

Synthesis of Quaternized Diblock Copolymer QB-3

[0124] Quaternized diblock copolymer QB-3 was synthesized using the same procedure as used for quaternized diblock copolymer QB-2, except using a different quaternization agent, different dosages of quaternization agent and PMA (Details are described in Table 3).

Synthesis of Quaternized Random Copolymer QR-1

[0125] Quaternized random copolymer QR-1 was synthesized using the same procedure as used for quaternized diblock copolymer QB-1.

Synthesis of Acidic Polymer AP-1

[0126] 0.3 g of potassium hydroxide, 77.5 of methoxypolyethyleneglycol (number of polyethylene oxide unit=13) and succinic anhydride were placed into a reaction vessel, and the reaction vessel was heated up to 80° C. Synthesis of acidic polymer AP-1 was carried out at 80° C. for 1 hour. An overview of acidic polymers is provided in Table 4.

Synthesis of Acidic Polymer AP-2

[0127] 86.0 g of Lutensol AO11 was placed into a reaction vessel, and the reaction vessel was heated up to 50° C. Then, 14.0 g of polyphosphoric acid (PPA) was added to the reaction vessel dropwise, and the reactor vessel was heated up to 80° C. Synthesis of acidic polymer AP-2 was carried out at 80° C. for 1 hour.

Synthesis of Acidic Polymer AP-3-AP-4

[0128] Acidic polymer AP-3 and AP-4 were synthesized using the same procedure as used for acidic polymer AP-1, except using different dosages and/or compositions of catalysts, alcohols, caprolactones and acidic parts (Details are described in Table 4).

Synthesis of Acidic Polymer AP-5

[0129] 0.10 g of dodecylbenzenesulfonic acid (DBSA), 44.9 g of MPEG-350, 28.2 g of E-caprolactone and 16.5 g of 6-valerolactone were placed into a reaction vessel, and the reaction vessel was heated up to 80° C. The reaction was carried out at 80° C. for 1 hour. After that, 10.3 g of PPA were placed to the reaction vessel. Synthesis of acidic polymer AP-5 was carried out at 80° C. for 1 hour.

Synthesis of Neutralization Product S-1

[0130] 89.2 g of aminic diblock copolymer DB-1, 4.3 g of acidic polymer AP-1 and 6.5 g of PMA were placed into a reaction vessel, and the reaction vessel was heated up to 80° C. Neutralization reaction was carried out at 80° C. for 1 hour. An overview of neutralization products is provided in Table 5.

Synthesis of Neutralization Product S-2, S-5-S-16

[0131] Neutralization product S-2-S-16 were synthesized using the same procedure as used for neutralization product S-1, except using different aminic block copolymer and acidic polymer, different molar ratio of amine to acid and different dosage of PMA (Details are described in Table 5).

Synthesis of Neutralization Product S-3, S-4 and NS-1

[0132] Neutralization product S-3, S-4 and NS-11 were synthesized using the same procedure as used for neutralization product S-1, except using different aminic block copolymer and acidic polymer, different molar ratio of amine to acid and different dosage of PMA (Details are described in Table 5). After neutralization process, a distillation of PMA from the reactor was carried out at 150° C. under reduced pressure. After that, 60 g of ionized water was added to the reactor to dissolve neutralization product in water. Analytical results of neutralization product S-3, S-4 and NS-1 are described in Table 5.

Synthesis of Alkali-Soluble Resin R1:

[0133] 300 g of PMA was 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 PMA (DIN EN ISO 3251:2008-06 at 150° C. for 20 min).

TABLE-US-00001 TABLE 1 Recipes of diblock copolymer DB-1 - DB-6 and random copolymer RC-1 Initiator/ Monomer mixture 1 Catalyst [weight-%] Monomer mixture 2 Product [weight- MPEG- [weight-%] name %] MMA BMA EHMA BzMA IBOMA BDGMA 1000MA DMAEMA DMAEMA MMA BzMA DB-1 1.10/0.04 21.8 3.6 7.3 3.7 3.6 DB-2 1.10/0.04 17.3 4.3 18.4 DB-3 1.10/0.04 17.2 3.4 10.3 5.0 0.3 0.3 DB-4 1.10/0.04 16.0 16.0 8.0 DB-5 1.58/0.06 19.3 4.8 24.1 11.8 DB-6 1.58/0.06 16.0 8.0 8.0 4.0 4.0 20.0 RC-1* 4.00/— 16.0 8.0 8.0 4.0 4.0 20.0 Amine Value of Solids Polymers M.sub.n M.sub.w/M.sub.n content Product name [mg KOH g.sup.−1] [g/mol] [g/mol] [weight-%] DB-1 30 6912 1.17 40 DB-2 160 6524 1.16 40 DB-3 47 6903 1.15 40 DB-4 70 8539 1.24 40 DB-5 70 6630 1.18 60 DB-6 120 6438 1.15 60 RC-1* 120 3874 2.12 40 Comparative Examples are marked in all TABLEs by *

TABLE-US-00002 TABLE 2 Recipes of triblock copolymer TB-1-TB-4 Initiator/ Monomer mixture 1 Monomer mixture 2 Product Catalyst [weight-%] [weight-%] name [weight-%] MMA BMA BDGMA DMAEMA MMA BMA BDGMA TB-1 1.58/0.06 9.7 2.4 12.0 11.8 TB-2 1.58/0.06 19.3 4.8 11.8 Amine Monomer mixture 3 Value of Solids Product [weight-%] Polymers M.sub.n M.sub.w/M.sub.n content name DMAEMA MMA BMA BDGMA [mg KOH g.sup.−1] [g/mol] [g/mol] [weight-%] TB-1 9.7 2.4 12.0 70 6432 1.26 60 TB-2 24.1 70 6275 1.28 60

TABLE-US-00003 TABLE 3 Recipes of quaternized diblock copolymer QB-1-QB-3 and quaternized random copolymer QR-1 Quaternization agent Intermediate [weight-%] polymer Grilonit RV CGE/ Solvent Quaternization Solids Product Amount 1814/ Benzoic [weight-%] degree content name Name [weight-%] BzCl acid PMA PM [mol-%] [weight-%] QB-1 DB-6 58.4 5.0 7.6 29.0 30 40 QB-2 DB-6 54.2 5.9/2.5 37.4 30 40 QB-3 DB-6 57.8 3.6/2.7 35.9 30 40 QR-1* RC-1 58.4 5.0 7.6 29.0 30 40 indicates data missing or illegible when filed

TABLE-US-00004 TABLE 4 Recipes of acidic polymer AP-1-AP-5 Alcohol Caprolactone Acidic part Molecular Acid Catalyst [weight-%] [weight-%] [weight-%] Solids weight Value of Product [weight-%] Lutensol MPEG- ε-Capro δ-Valero Succinic Maleic content (theoretical) Polymers name KOH DBSA AO11 350 lactone lactone anhydride anhydride PPA [weight-%] [g/mol] [mg KOH g.sup.−1] AP-1 0.30 77.5 22.2 100 450 124 AP-2 86.0 14.0 100 772 186 AP-3 0.30 77.9 21.8 100 448 125 AP-4 0.30 0.10 43.7 27.4 16.1 12.4 100 780 70 AP-5 0.10 44.9 28.2 16.5 10.3 95 875 129

TABLE-US-00005 TABLE 5 Recipes of neutralization product S-1 - S-16, and non-neutralized product NS-1 Amine Acid Aminic block copolymer Acidic component Solvent Neutralization Solids Value of Value of Product Amount Amount [weight-%] degree content Polymers Polymers name Name [weight-%] Name [weight-%] PMA Water [mol-%] [weight-%] [mg KOH g.sup.−1] [mg KOH g.sup.−1] S-1 DB-1 89.2 AP-1 4.3 6.5 50 40 11 5 S-2 DB-2 22.1 AP-5 22.1 33.2 100 40 71 71 S-3 DB-4 72.7 AP-2 10.9 60.0 100 40 20 20 S-4 DB-4 64.8 AP-5 14.1 60.0 100 40 18 18 S-5 DB-3 66.5 AP-4 13.4 20.1 75 40 13 9 S-6 DB-5 43.2 AP-5 14.1 42.7 100 40 45 45 S-7 TB-1 43.2 AP-5 14.1 42.7 100 40 45 4510 S-8 TB-2 43.2 AP-5 14.1 42.7 100 40 45 45 S-9 QB-1 83.4 AP-2 6.6 10.0 50 40 25 12 S-10 QB-2 87.5 AP-5 5.0 7.5 25 40 34 17 S-11 QB-3 78.7 AP-5 8.5 12.8 50 40 33 21 S-12* RC-1 51.0 AP-3 19.6 29.4 100 40 24 24 S-13* QR-1 77.0 AP-1 9.2 13.8 50 40 23 11 S-14* DB-6 59.7 Phosmer M 16.1 24.2 100 40 43 43 S-15* DB-3 71.8 Benzoic acid 11.3 16.9 100 40 52 52 S-16* QB-1 87.8 Phosmer M 4.9 7.3 50 40 26 13 NS-1* DB-4 100.0 60.0 40 70

Preparation of Pigmented Compositions

Production of Red, Green and Blue Dispersions Used for Color Filter Application

[0134] PG-58: Fastogen Green A110 (DIC) [0135] PR-254: Irgaphor Red BT-CF (BASF) [0136] PB-15:6: Fastogen Blue EP-193 (DIC) [0137] LP N 6919: BYK-LP N 6919, diblock copolymer, non volatile=60%, amine value=72 mg-KOH/g (BYK-Chemie) [0138] DIS-111: DISPERBYK-111, acidic polymer, acid value=129 mg-KOH/g (BYK-Chemie)

[0139] General procedure for producing dispersion R-1 used for color filter application:

[0140] 4.3 g of alkali-soluble resin R1 and 9.4 g of the dispersant S-2, shown in table 5, were placed into a 140 ml glass bottle. After that, 28.8 g of PMA was added to the glass bottle to dissolve the alkali-soluble resin R1 and the dispersant. Then, 7.5 g of PR-254 and 150 g of zirconia beads (diameter: 0.4-0.6 mm) were added into the glass bottle. The dispersion process was performed in a LAU-Disperser DAS 200 over a period of 5 hours at 30° C. After 5 hours, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0141] General procedure for producing dispersions R-2, G-1-G-10 and B-1-B-3 used for color filter application

[0142] Dispersions R-2, G-1-G-10 and B-1-B-3 were prepared according to the procedure for dispersion R-1 (Details are described in Table 6).

TABLE-US-00006 TABLE 6 Recipes of red, green and blue dispersions used for color filter application Dispersant [weight-%] Alkali- Pigment Aminic polymer soluble Solvent Amount Product resin R1 PMA Dispersion Name [weight-%] name Amount DIS-111 [weight-%] [weight-%] R-1 PR-254 7.5 S-2 9.4 4.3 28.8 R-2* PR-254 7.5 LP N 6919 5.9 3.5 4.3 28.8 G-1 PG-58 7.5 S-6 9.4 4.3 28.8 G-2 PG-58 7.5 S-7 9.4 4.3 28.8 G-3 PG-58 7.5 S-8 9.4 4.3 28.8 G-4* PG-58 7.5 S-12* 9.4 4.3 28.8 G-5* PG-58 7.5 S-14* 9.4 4.3 28.8 G-6* PG-58 7.5 S-15* 9.4 4.3 28.8 G-7* PG-58 7.5 S-16* 9.4 4.3 28.8 G-8* PG-58 7.5 LP N6919 5.9 3.5 4.3 28.8 G-9* PG-58 7.5 DB-5 9.4 4.3 28.8 G-10* PG-58 7.5 DB-5 3.8 6.4 32.3 B-1 PB-15:6 7.5 S-11 9.4 4.3 28.8 B-2 PB-15:6 7.5 S-13 9.4 4.3 28.8 B-3* PB-15:6 7.5 S-13* 9.4 4.3 28.8

Production of Resist Ink

[0143] BYK-330: Silicone-type additive (BYK-Chemie)

[0144] Aronix M305: Pentaerythritol triacrylate (TOA GOSEI)

[0145] Omnirad 369: Former name: Irgacure 369, 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone (IGM Resins B.V.)

[0146] The recipe of the resist inks are described as follows;

TABLE-US-00007 Dispersion  50.0 g 2% solution of BYK-330 in PMA  1.0 g Alkali-soluble resin R-1  14.2 g Aronix M305  2.0 g Omnirad 369  1.0 g PMA  31.8 g Total 100.0 g

Application Test Results

[0147] Viscosity of red, green and blue dispersions

[0148] Viscosity of red, green and blue dispersions were measured by using BROOKFIELD VISCOMETER DV-II+ (BROOKFIELD, upper limitation of viscosity: 1000 mPa.Math.s).

[0149] Particle size of red, green and blue dispersions: Particle size (median diameter: D50) of red, green and blue dispersion were measured by using Particle Size Analyzer ELSZ-1000 (Otsuka Electronics).

Developing Property

[0150] Red, Green and Blue resist inks were coated to glass plate by using bar coater No. 4 (9.16 μm of thickness at wetting-film), and the coating films were dried at 80° C. for 3 minutes. The dried coating films were gradually dipped to 0.05% KOH aqueous solution (interval: 10-60 seconds).

[0151] After washing them by water, the coating films were wiped by using KimWipes (Kimberly Clark Corporation product), and marked appearance of coating film described as follows;

[0152] 1 (Excellent): The coating film was completely eliminated after wiping

[0153] 2 (Very good): The coating film was partially eliminated after wiping

[0154] 3 (Good): The coating film was not eliminated, but the surface of the coating film was mostly removed after wiping

[0155] 4 (Poor): The coating film was not eliminated, but the surface of the coating film was partially removed after wiping

[0156] 5 (Miserable): The appearance of the coating film didn't change after wiping

Re-Solubility in PMA

[0157] Red, Green and Blue resist inks were coated to glass plate by using bar coater No. 4 (9.16 μm of thickness at wetting-film), and the coating films were dried at 80° C. for 3 minutes. One droplet of PMA was put on the coating film, and wiped immediately by using KimWipes. The appearance of the coating film after wiping was marked as follows;

[0158] 1 (Excellent): The coating film in the trace of PMA droplet was completely eliminated after wiping

[0159] 2 (Very good): The coating film in the trace of PMA droplet was partially eliminated after wiping

[0160] 3 (Good): The coating film in the trace of PMA was not eliminated, but the surface of the coating film was mostly removed after wiping

[0161] 4 (Poor): The coating film was in the trace of PMA not eliminated, but the surface of the coating film was partially removed after wiping

[0162] 5 (Miserable): The appearance of the coating film didn't change after wiping

Example 1-6: Viscosity and Particle Size of Red (R), Green (G) and Blue (B) Dispersions, and Developing Property and Re-Solubility in PMA of Red (R), Green (G) and Blue (B) Resist Inks

[0163] Viscosity (mPa.Math.s at 20° C., rotation: 60 rpm) and particle size (D50) of red, green and blue dispersions as well as developing property and re-solubility in PMA of red, green and blue resist inks are described in Table 7.

TABLE-US-00008 TABLE 7 Viscosity and particle size of red, green and blue dispersions, and developing property and re-solubility in PMA of red, green and blue resist inks Viscosity (mPa .Math. s) of dis- persion (60 rpm) Storage Property of resist ink Ex- at 40° C. Particle Re- am- Dis- Ini- for 5 size Developing solubility ples persion tial days (D50)/nm property in PMA 1 R-1 6.4 6.6 72 1 1 2 G-1 5.1 5.6 63 3 1 3 G-2 3.8 4.4 57 2 1 4 G-3 3.8 4.3 65 1 1 5 B-1 5.0 5.1 60 1 1 6 B-2 4.8 4.8 62 1 1

[0164] Comparison example C-1 to C-9: Viscosity and particle size of red (R), green (G) and blue (B) dispersions, and developing property and re-solubility in PMA of red, green and blue resist inks;

[0165] Viscosity (mPa.Math.s at 20° C., rotation: 60 rpm) and particle size (D50) of red, green and blue dispersions are described in Table 8, and developing property and re-solubility in PMA of red, green and blue resist inks are described in Table 8.

TABLE-US-00009 TABLE 8 Viscosity and particle size of red, green and blue dispersions, and developing property and re-solubility in PMA of red, green and blue resist inks Viscosity (mPa .Math. s) of dispersion (60 rpm) Property of Storage resist ink at 40° C. Particle Re- Comparison for 5 size Developing solubility examples Dispersion Initial days (D50)/nm property in PMA C-1 R-2* 6.4 9.6 80 3 3 C-2 G-4* >100 Gelation 342 C-3 G-5* 5.3 5.8 68 4 3 C-4 G-6* 5.6 7.0 70 4 3 C-5 G-7* 6.0 7.8 90 5 2 C-6 G-8* 5.6 6.8 60 3 3 C-7 G-9* 8.7 7.6 60 5 4 C-8 G-10* 5.5 47.3 72 5 2 C-9 B-3* >100 Gelation 267

[0166] According to the results in Table 7 and 8, red, green and blue dispersions including neutralized product between aminic diblock copolymer or aminic triblock copolymer and acidic polymer show excellent dispersibility and storage stability (Example 1-6). Moreover, red, green and blue resist inks including the dispersions also show excellent developing property and re-solubility in PMA. However, red and green dispersions including BYK-LP N 6919 and DISPERBYK-111 which added during the grinding process (Comparison example C-1 and C-6) show lower storage stability, and their resist inks also show poor developing property and re-solubility in PMA.

[0167] Green and blue dispersions including aminic random copolymer and acidic polymer (Comparison example C-2 and C-9) show poor dispersibility.

[0168] Green dispersions including aminic block copolymer and low molecular weight of acidic component (Comparison example C-3 to C-5) show poor storage stability, and their resist inks show poor developing property and re-solubility in PMA.

Production of Carbon Black Dispersions Used for Solvent-Based Dark Black Coating

[0169] Raven U3: Raven 5000 Ultra 3 (Birla Carbon)

[0170] Butyl acetate (Sigma-Aldrich)

[0171] General procedure for producing solvent-based carbon black dispersion Bk-1:

[0172] 9.7 g of a dispersant was placed into a 140 ml glass bottle. After that, 36.0 g of butyl acetate was added to the glass bottle to dissolve the dispersant. Then, 4.3 g of Raven 5000 Ultra 3 (Raven U3) and 150 g of zirconia beads (diameter: 0.4-0.6 mm) were added into the glass bottle. Dispersion process was performed in a LAU-Disperser DAS 200 over a period of 10 hours at 30° C. After 10 hours, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0173] General procedure for producing carbon black solvent-based dispersion Bk-2-Bk-5:

[0174] Solvent-based dispersions Bk-2-Bk-5 were according to the procedure dispersion Bk-1 (Details are described in Table 9).

TABLE-US-00010 TABLE 9 Recipes of solvent-based carbon black dispersions Bk-1-Bk-5 Pigment Dispersant Solvent Amount Product Amount Butyl acetate Dispersion Name [weight-%] name [weight-%] [weight-%] Bk-1 Raven U3 4.3 S-1 9.7 36.0 Bk-2 Raven U3 4.3 S-5 9.7 36.0 Bk-3 Raven U3 4.3  S-11 9.7 36.0 Bk-4 Raven U3 4.3  S-12 9.7 36.0 Bk-5* Raven U3 4.3 DB-5 6.5 39.2

Example 7-10: Viscosity and Particle Size of Solvent-Based Carbon Black Dispersions Bk-1-Bk-4

[0175] Viscosity (mPa.Math.s at 20° C., rotation: 60 rpm) and particle size (D50) of solvent-based carbon black dispersions Bk-1-Bk-4 are described in Table 10.

TABLE-US-00011 TABLE 10 Viscosity and particle size of solvent-based carbon black dispersions Bk-1-Bk-4 Viscosity (mPa .Math. s) of dispersion (60 rpm) Storage Particle at 40° C. size for 5 (D50)/ Examples Dispersion Initial days nm 7 Bk-1 59 57 102 8 Bk-2 46 54 93 9 Bk-3 19 19 83 10 Bk-4 21 20 80

Comparison Example 10: Viscosity and Particle Size of Solvent-Based Carbon Black Dispersions Bk-5

[0176] Viscosity (mPa.Math.s at 20° C., rotation: 60 rpm) and particle size (D50) of solvent-based carbon black dispersions Bk-5 are described in Table 11.

TABLE-US-00012 TABLE 11 Viscosity and particle size of solvent-based carbon black dispersions Bk-5 Viscosity (mPa .Math. s) of dispersion (60 rpm) Particle Comparison Storage at 40° C. size (D50)/ example Dispersion Initial for 5 days nm C-10 Bk-5 >100 Gelation 189

[0177] According to the results in Table 10 and 11, neutralized product between aminic block copolymer and acidic polymer showed lower viscosity, improved storage stability and lower particles size when used as dispersant for solvent-based carbon black dispersion suitable for coatings for transportation vehicles. On the other hand, non-neutralized aminic block copolymer showed poor dispersibility.

Production of Waterborne Dispersions Used for Inkjet Application

[0178] Yellow 3GL-TP: (Clariant)

[0179] Inkjet Yellow 4GC: Pigment Yellow 155 (Clariant)

[0180] Riaplas Red 2BL-TP: (Clariant)

[0181] Inkjet Magenta E7B VP3958: (Clariant)

[0182] General procedure for producing waterborne dispersion Y-1:

[0183] 10.0 g of dispersant S-3 was placed into a 140 ml glass bottle. After that, 10.0 g of deionized water was added to the glass bottle and mixing homogeneously. Then, 10.0 g of Yellow 3GL-TP and 150 g of zirconia beads (diameter: 0.4-0.6 mm) were added into the glass bottle.

[0184] Dispersion process was performed in a LAU-Disperser DAS 200 over a period of 16 hours at 30° C. After 16 hours, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0185] General procedure for producing waterborne dispersions Y-2-Y-3, Re-1 and M-1-M-2

[0186] Waterborne dispersions were prepared using the same procedure as used for waterborne dispersion Y-1, except using different dispersants and different dosages (Details are described in Table 12).

TABLE-US-00013 TABLE 12 Recipes of waterborne dispersions Y-1-Y-3, Re-1, M-1 and M-2 Dispersant Pigment [weight-%] Deionized Dis- Amount Product water persion Name [weight-%] name Amount [weight-%] Y-1 Yellow 3GL-TP 10.0 S-3 10.0 30.0 Y-2* Yellow 3GL-TP 10.0 NS-1 10.0 30.0 Y-3 Inkjet Yellow 4GC 10.0 S-4 5.0 35.0 Re-1 Riaplas Red 2BL-TP 10.0 S-3 5.0 35.0 M-1 Inkjet Magenta 10.0 S-4 12.5 27.5 E7B VP3958 M-2* Inkjet Magenta 10.0 NS-1 12.5 27.5 E7B VP3958

Example 11-14: Viscosity and Particle Size of Waterborne Dispersions Y-1, Y-3, Re-1 and M-1

[0187] Viscosity (mPa.Math.s at 20° C., rotation: 60 rpm) and particle size (D50) of waterborne dispersions Y-1, Y-3, Re-1 and M-1 are described in Table 13.

TABLE-US-00014 TABLE 13 Viscosity and particle size of waterborne dispersions Y-1, Y-3, Re-1 and M-1 Viscosity (mPa .Math. s) of dispersion (60 rpm) Storage Particle at 70° C. size for 7 (D50)/ Examples Dispersion Initial days nm 11 Y-1 4.2 3.7 82 12 Y-3 5.0 4.7 84 13 Re-1 3.7 5.1 90 14 M-1 14.1 11.9 78

Comparison Example 11-12: Viscosity and Particle Size of Waterborne Dispersions Y-2 and M-2

[0188] Viscosity (mPa.Math.s at 20° C., rotation: 60 rpm) and particle size (D50) of waterborne dispersions Y-2 and M-2 are described in Table 14.

TABLE-US-00015 TABLE 14 Viscosity and particle size of waterborne dispersions Y-2 and M-2 Viscosity (mPa .Math. s) of dispersion (60 rpm) Particle Storage size at 70° C. Comparison for 7 (D50)/ examples Dispersion Initial days nm C-11* Y-2 5.2 11.3 91 C-12* M-2 14.0 Gelation 82

[0189] According to the results in Table 13 and 14, neutralized product between aminic block copolymer and acidic polymer showed good results as dispersant for waterborne dispersion used for inkjet application. In particular, the inventive examples exhibited an improved storage stability compared to non-neutralized aminic block copolymer.