Amine functional compound

Abstract

An amine functional compound comprising i. least one segment consisting of at least one ether unit E and at least one ester unit, wherein the ether units and ester units are connected by an ether link or by an ester link, and wherein the sum of the number of ether units and ester units is at least three, and wherein the ether units and ester units are arranged in random order, and ii. at least one amine group ii. selected from a tertiary amine group, a salt of a tertiary amine group and a quaternary ammonium group, wherein the at least one segment is covalently linked to a polymerization starter moiety comprising the at least one amine group ii.

Claims

1. An ink or coating composition comprising pigment particles and an amine functional compound comprising i. at least one segment comprising at least one ether unit and at least one ester unit, wherein the at least one ether unit and the at least one ester unit are connected by an ether link or by an ester link, and wherein the sum of the number of the at least one ether unit and the at least one ester unit is at least three, and wherein the at least one ether unit and the at least one ester unit are arranged in random order, and ii. at least one amine group ii. selected from a tertiary amine group, a salt of a tertiary amine group and a quaternary ammonium group, wherein the at least one segment is covalently linked to a polymerization starter moiety comprising the at least one amine group ii.

2. The composition according to claim 1, wherein the polymerization starter moiety is directly linked to said at least one segment via one or more selected from an ether group, an ester group, a secondary amide group, a tertiary amide group, a secondary amine group and a tertiary amine group.

3. The composition according to claim 1, wherein the polymerization starter moiety comprises a polyethylenimine.

4. The composition according to claim 1, wherein the at least one ether unit includes a unit of formula (IV) —[CR.sup.30.sub.2].sub.n—O—, wherein n is an integer of 2 or 3, and R.sup.30 independently of each other represent organic groups having 1 to 25 carbon atoms or hydrogen.

5. The composition according to claim 1, wherein the at least one segment has a molar ratio between the at least one ether unit and the at least one ester unit in the range 19:1 to 1:1.

6. A composition comprising pigment particles and an amine functional compound, the amine functional compound being included in an amount ranging from 1 to 50 wt. % based on the weight of the pigment, the amine functional compound comprising i. at least one segment comprising at least one ether unit and at least one ester unit, wherein the at least one ether unit and the at least one ester unit are connected by an ether link or by an ester link, and wherein the sum of the number of the at least one ether unit and the at least one ester unit is at least three, and wherein the at least one ether unit and the at least one ester unit are arranged in random order, ii. at least one amine group ii. selected from a tertiary amine group, a salt of a tertiary amine group and a quaternary ammonium group, wherein the at least one segment is covalently linked to a polymerization starter moiety comprising the at least one amine group ii.

7. The composition according to claim 6, wherein the polymerization starter moiety is directly linked to said at least one segment via one or more selected from an ether group, an ester group, a secondary amide group, a tertiary amide group, a secondary amine group and a tertiary amine group.

8. The composition according to claim 6, wherein the polymerization starter moiety comprises a polyethylenimine.

9. The composition according to claim 6, wherein the at least one ether unit includes a unit of formula (IV) —[CR.sup.30.sub.2].sub.n—O—, wherein n is an integer of 2 or 3, and R.sup.30 independently of each other represent organic groups having 1 to 25 carbon atoms or hydrogen.

10. The composition according to claim 6, wherein the at least one segment has a molar ratio between the at least one ether unit and the at least one ester unit in the range 19:1 to 1:1.

Description

EXAMPLES

(1) General Remarks

(2) In the case of substances without molecular uniformity the stated molecular weights—below as already in the foregoing description—represent average values of the numerical mean. The molecular weights or number-average molecular weights M.sub.n, are determined, when titratable hydroxyl or amino groups are present, by end-group determination via the determination of the OH number or amine number, respectively. In the case of compounds to which an end-group determination cannot be applied, the number-average molecular weight is determined by means of gel permeation chromatography against a polystyrene standard. Unless otherwise remarked percentages are percentages by weight.

(3) Measurement of Non-Volatile Components

(4) The sample (2.0±0.1 g of the tested substance) was weighed in a previously dried aluminum crucible and dried in furnace for 20 minutes at 150° C., cooled in a desiccator and then reweighed. The residue corresponds to the solids content in the sample (ISO 3251).

(5) Measurement of Acid Numbers

(6) The acid number is the KOH quantity in mg that is required for neutralizing 1 g of substance under the defined conditions. The acid numbers were determined by a neutralization reaction with a 0.1 N KOH in Ethanol according to DIN EN ISO 2114.

(7) ##STR00002##
Measurement of Hydroxyl Numbers

(8) The alcoholic hydroxyl groups were reacted by acetylation with an excess of acetic anhydride. The excess acetic anhydride was cracked into acetic acid by adding water and titrated back using ethanolic KOH. The hydroxyl number was understood to be the KOH quantity in mg, which is equivalent to the acetic acid quantity bound when acetylating 1 g of substance (according to DIN ISO 4629)

(9) Measurement of Amine Numbers

(10) Perchloric acid (HClO.sub.4) in acetic acid has proved to be a suitable titration agent for organic bases containing nitrogen as well as primary, secondary and tertiary amine groups. Acid solvents such as acetic acid have stood the test in determining weak organic bases (good dissolving properties, proton-donating acid solvent). Additions of inert solvents such as cyclohexane, dioxane, chlorobenzene, acetone and methyl ethyl ketone can improve the titration of very weak bases (according to DIN 16945).
R—NH.sub.2+HClO.sub.4.fwdarw.R—NH.sub.3.sup.++ClO.sub.4.sup.−
NMR Measurements

(11) The NMR measurements were carried out on a Bruker DPX 300 at 300 MHZ (.sup.1H) or 75 MHZ (.sup.13C). Solvents used were deuterated chloroform (CDCl.sub.3) and deuterated dimethyl sulfoxide (DMSO-d.sub.6).

Preparation of the Intermediate Products: First Step

Examples According to the Invention

Preparation Method 1

(12) A clean dry four-necked flask (500 mL) equipped with reflux condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with a mixture of the lactone and the epoxide and heated up to 80° C. Then a polymerization starter was slowly added into this mixture. After complete addition the mixture was heated up to 140° C. and stirred for 2 h. Then the reaction mixture was cooled down to 40° C., the catalysts were added and the temperature was increased up to 140° C. The incorporation of epoxide and the lactone monomers was determined by the means of NMR.

(13) TABLE-US-00001 TABLE 1 Intermediate products prepared according to the method 1 Polymerization Example starter wt. % lactone wt. % epoxide wt. % catalyst wt. % A1 PEI300 3.72 CAPA 55.88 2-EHGE 39.45 AlCl.sub.3/DBN 0.80/0.15 A2 PEI300 1.23 CAPA 53.60 2-EHGE 44.22 AlCl.sub.3/DBN 0.80/0.15 A3 PEI300 8.12 VAL 61.88 2-EHGE 29.05 AlCl.sub.3/DBN 0.80/0.15 A4 PEI300 3.91 VAL 67.13 2-EHGE 28.01 AlCl.sub.3/DBN 0.80/0.15 A5 PEI300 4.41 CAPA 67.10 CGE 27.54 AlCl.sub.3/DBN 0.80/0.15 A6 PEI300 6.51 CAPA 56.63 C12-C14- 35.91 AlCl.sub.3/DBN 0.80/0.15 AlkylGE A7 PEI300 3.02 CAPA 46.01 C12-C14- 50.02 AlCl.sub.3/DBN 0.80/0.15 AlkylGE A8 PEI 1300 7.46 CAPA 64.88 2-EHGE 26.71 AlCl.sub.3/DBN 0.80/0.15 A9 PEI 1300 4.33 CAPA 47.02 C12-C14- 47.70 AlCl.sub.3/DBN 0.80/0.15 AlkylGE A10 PEI 1300 6.61 CAPA 71.80 CGE 20.64 AlCl.sub.3/DBN 0.80/0.15 A11 PEI 2000 4.67 CAPA 60.93 2-EHGE 33.45 AlCl.sub.3/DBN 0.80/0.15 A12 PEI 2000 5.70 CAPA 61.94 C12-C14- 31.42 AlCl.sub.3/DBN 0.80/0.15 AlkylGE A13 PEI 2000 9.30 CAPA 60.68 CGE 29.07 AlCl.sub.3/DBN 0.80/0.15 A14 PEI 2000 3.67 CAPA 55.91 2-EHGE 39.47 AlCl.sub.3/DBN 0.80/0.15 PEI (number) = polyethylenimine (molecular weight), VAL = delta-Valerolactone, CAPA = ε-Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, CGE = o-cresyl glycidyl ether, C12-C14-AlkylGE = C12-C14 alkyl glycidyl ether, DBN = 1,5-Diazabicyclo(4.3.0)non-5-ene, AlCl.sub.3 = aluminum trichloride.

Preparation of Comparative Intermediate Products: First Step

Preparation Method 2

(14) A clean dry four-necked flask (500 mL) equipped with reflux condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with the epoxide and heated up to 80° C. Then a polymerization starter was slowly added into this mixture. After complete addition the temperature was increased up to 140° C. and the mixture was stirred for 2 h. Then the reaction mixture was cooled down to 40° C., the catalysts were added and the temperature was increased up to 140° C. The reaction mixture was stirred at this temperature until the epoxide was completely reacted (controlled by the means of NMR). Then the lactone was slowly added at 140° C. The incorporation of epoxide and the lactone monomers was determined by the means of NMR.

(15) TABLE-US-00002 TABLE 2 Intermediate products prepared according to the method 2 polymerization Example starter wt. % lactone wt. % epoxide wt. % catalyst wt. % B1* PEI300 3.72 CAPA 55.88 2-EHGE 39.45 AlCl.sub.3/DBN 0.80/0.15 B2* PEI300 1.23 CAPA 53.60 2-EHGE 44.22 AlCl.sub.3/DBN 0.80/0.15 PEI (number) = polyethylenimine (molecular weight), CAPA = ε-Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, DBN = 1,5-Diazabicyclo(4.3.0)non-5-ene, AlCl.sub.3 = aluminum trichloride

Preparation of the products: second step

(16) Comparative samples are marked with (*).

Preparation Method 3

(17) A clean dry four-necked flask (500 mL) equipped with reflux condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with the intermediate product and tall oil fatty acid and heated up to 50° C. The reaction mixture was stirred at that temperature for 2 h.

(18) After that, the acid value and the amine value are determined.

(19) TABLE-US-00003 TABLE 3 Intermediate products prepared according to the method 3 Intermediate Post sol- Active Example products wt. % modification wt. % vent substance L1* B1* 97.71 TÖF 2.29 — 100 L2 A1 98.20 TÖF 1.80 — 100 L3* B2* 99.16 TÖF 0.84 — 100 L4 A2 99.39 TÖF 0.61 — 100 TÖF = tall oil fatty acid

Application Examples

(20) Samples marked with (*) are comparative examples.

Application Example 1

(21) Samples marked with (*) are comparative examples.

Working Method 1

(22) During the application test additive L2 was compared with L1* and additive L4 with L3*.

(23) Raw Material Used for the Application Tests

(24) Ebecryl 4381: UV/EB Curable Resins-unsaturated polyester resin diluted in 30% dipropylene glycol diacrylate (DPGDA), purchased from Allnex

(25) Laromer DPGDA: Dipropylene glycol diacrylate, purchased from BASF Irgacure 1173: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one used in reactive and radiation curing adhesives, purchased from IGM

(26) ACEMATT HK 440: Untreated silica-based matting agent, purchased from Evonik

(27) BYK-088: Defoamer for solvent-borne systems, purchased from BYK Chemie GmbH

(28) BYK-306: Silicone-containing surface additive for ambient-curing plastic systems and solvent-borne coating systems, purchased from BYK Chemie GmbH

(29) BYK-350: An acrylic leveling additive for solvent-borne and solvent-free systems, purchased from BYK Chemie GmbH

Preparation of UV Matt Base

(30) In order to achieve a high quality UV matt base, a sufficient wetting and dispersing of the matting agent is important. The following properties indicate the effect of the additives used: gloss reduction (preferable low gloss), surface appearance (preferable smooth and fine) and coating viscosity (preferable low/flowable).

(31) The detailed composition of the formulation is presented in the table 4.

(32) TABLE-US-00004 TABLE 4 Composition of the formulation Position Raw Materials Composition [wt %] 1 Ebecryl 4381 30.2 2 Laromer DPGDA 46.5 3 Irgacure 1173 5.0 4 BYK-088 0.4 5 BYK-306 0.2 6 BYK-350 0.2 7 Laromer DPGDA 1.0 8 W&D-Additive 1.5 9 ACEMATT HK 440 15 total 100.0

(33) First raw materials listed in the position 1-3 were mixed shortly by dissolver (1865 rpm) for the preparation of the UV matt base. Then the additives listed in the positions 4-7 were added to this mixture and stirred for another 3 minutes at 1865 rpm. Subsequently the W&D additive (position 8) was added to the mixture under stirring. Finally, a matting agent (position 9) was added and the whole mixture was stirred for 10 minutes at 1865 rpm.

(34) The final coatings were applied on black PMMA (poly methyl methacrylate) panels and cured using mercury UV lamp from IST Metz GmbH (speed 5 m/min, 100% intensity).

(35) The results of the application tests are presented below.

(36) Results

(37) In the tested coating system the additives L2 and L4 lead to better viscosity reduction compared to corresponding samples L1* and L3* and enable the formulation of higher loaded coatings (coatings which contain 15-20 wt % of matting agent). The low viscosity supports application with a roller coater and improves leveling and orientation of the matting agents in the final coating. Appearance and haptic of coatings prepared with L2 and L4 are very smooth and fine and offer the sensation of high-quality surfaces, as shown in Table 6.

(38) TABLE-US-00005 TABLE 5 Results of the viscosity measurement L2 and L4 lead to lower coating viscosity compared to the comparative samples L1* and L3*. sample L1* L2 L3* L4 Viscosity Viscosity Viscosity Viscosity Shear rate 1/s mPa s mPa s mPa s mPa s 1 83 50 46 38 10 10 5 14 5

(39) TABLE-US-00006 TABLE 6 Coating surface appearance L2 and L4 lead to a significant better surface appearance compared to L1* and L3*. Surface appearance L1* rough, coarse L2 smooth, fine L3* rough, coarse L4 smooth, fine