NITROCELLULOSE BASED DISPERSANT

Abstract

The invention relates to a polysaccharide-g-polyether dispersant represented as a compound of Formula 1 or a mixture of compounds of Formula (I) and Formula (II) wherein, T is the backbone polymer and is a residue of a modified cellulose or chitosan, with a molecular weight of 500-1000,000 g/mol; A and B are each, independently, —O— or —NH—; R is linear or branched —(C1-C50alkylene)-, arylene, cyclo-C5-C8-alkylene, isophoronediyl, or linear or branched —(C2-C10alkylene)- which is interrupted by phenylene or cyclohexanediyl; P is the residue of a polyether and/or polyester chain with molecular weight between 100 and 10,000 g/mol, n is a number of 1-5000.

Description

This invention relates to a modified cellulose based dispersant characterized by a “graft onto” approach, which can be used in ink applications.

Dispersants for nitrocellulose (NC) ink system become more and more important because of their profitable effects on the final ink performance, especially on the reduction of viscosity of millbase, which means a higher pigment loading.

Japanese Application JP 58083001 refers to a modified nitrocellulose obtained by reacting an active hydrogen compound with a specified diisocyanate compound and then mixing the resulting reaction product with a nitrocellulose solution. The chemical structure of the nitrocellulose compound obtained is a kind of a blend compound of polyurethane and NC resin. The polyurethane is formed based on diol and diisocyanate, and then the resultant was mixed with NC resin to obtain the blend compound. This blend compound can be used as adhesive in coating a polyester film, and binders for magnetic recording tapes.

M. Barikani et al describe in Carbohydrate Polymers 68 (2007) 773-780 the preparation of starch modified polyurethanes by reacting starch with an urethane prepolymer. The prepolymer was prepared by introducing diisocyanate on both ends of polycaprolactone. The grafting was performed by addition of the prepolymer to starch.

Starch g-polyether materials have almost no dispersion effect.

There is a need to provide a dispersant having improved rheological performance, chromatic strength and transparency in final ink films.

It has now been found that a modified cellulose based dispersant which is characterized by a “graft onto” approach performs lower viscosity of pigment millbase, higher gloss, higher density, and better transparency of final ink films.

Thus, the invention relate to a dispersant represented as compounds of Formula 1 or a mixture of compounds of Formula 1 and Formula 2

wherein,

• T is the backbone polymer and is a residue of a modified cellulose or chitosan, with a molecular weight of 500-1000,000 g/mol;
• A and B are each, independently, —O— or —NH—;
• R is linear or branched —(C₁-C₅₀alkylene)-, arylene, cyclo-C₅-C₈-alkylene, isophoronediyl, or linear or branched —(C₂-C₁₀alkylene)- which is interrupted by phenylene or cyclohexanediyl;
• P is the residue of a polyether and/or polyester chain with molecular weight between 100 and 10,000 g/mol,
• n is a number of 1-5000.n is preferably a number of 1-2000, more preferably 10-1000.

DEFINITIONS

The term “modified cellulose” refers to cellulose acetate, cellulose propionate, cellulose nitrate (nitrocellulose), methylcellulose, ethylcellulose, hydroxy ethylcellulose, carboxymethylcellulose, benzylcellulose and the like.

The term “chitosan” refers to deacetylated chitin or (poly)N-glucosamine linked in a beta-1,4 position.

Most preferred is the use of nitrocellulose.

The group R is the linker of the isocyanate groups. Preferred alkylene linkers are C₁-C₂₀ alkylene linkers, more preferred C₁-C₁₀alkylene, mostly preferred C₁-C₆alkylene.

Examples of diisocyanates having an alkylene linker are:

2-methylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate. Especially preferred is hexamethylene diisocyanate.

In another embodiment the linker is selected from an arylene such as toluene, 4,4 methylene diphenylene, naphthalene, tetramethyl-m-xylylene. The arylene group may be substituted by methyl.

Examples of diisocyanates having an arylene linker are:

Especially preferred is toluene diisocyanate.

Examples of diisocyanates having a substituted arylene linker are: 3,3′-dimethyl-biphenyl-4,4′-diisocyanate

In another embodiment the linker is selected from cycloC₅-C₈alkylene, preferably cyclohexylene such as 4,4 methylene dicyclohexylene, cyclohexanediyl, methylcyclohexanediyl, trimethylcyclohexanediyl methylene.

Examples of diisocyanates having a cycloalkylene linker are:

In another embodiment the alkylene linker is interrupted by phenylene or cyclohexanediyl.

Examples of diisocyanates having a linker which is interrupted by phenylene or cyclohexanediyl are:

Isophorone diisocyanate is;

The isocyanates are commercially available.

R is preferably toluenediyl, 4,4 methylene diphenylene, tetramethyl-m-xylylene, hexamethylene, isophoronyl, 4,4 methylene dicyclohexylene.

The term polyether includes linear and branched polyether and containing at least one hydroxyl group (mono-hydroxyl polyether), amine group (mono-amine polyether), imine group (mono imine polyether).

Mono amine polyether are amino terminated polyalkylene glycols, particularly amino terminated polypropylene glycols, polyethylene glycols or copolymers of propylene glycol and ethylene glycol. Commercially available amines are sold under the trade name JEFFAMINE by Huntsman.

Preferred are mono-hydroxyl polyether such as polyethylene glycol mono ether, polypropylene glycol mono ether and mixtures thereof. Non limiting examples are polyethylene glycol methyl ether (MPEG) and polypropylene glycol monobutyl ether.

The term polyester includes linear and branched polyester containing at least one hydroxyl group (mono-hydroxyl polyester). The mono hydroxyl polyester are derived from an aliphatic hydroxy carboxylic acid or a related ester, such as, for example, lactic acid, glycolic acid, or a related lactone such as, for example, ε-caprolactone, δ-glutarolactone, δ-valerolactone, γ-butyrolactone and mixtures, thereof. Preferred are polyester of lactones such as ε-caprolactone or δ-valerolactone.

Preparation:

The preparation of compounds of Formula 1 or of mixtures of the compounds of Formula 1 and Formula 2 is based on the “graft onto” manufacturing process, characterized by grafting the side chains onto the backbone polymer (T) via graft agent at the present of catalyst, which means the side chain is modified with graft agent first at temperature t₁ and then grafted onto backbone polymer at temperature t₂.

The polymer backbone is a residue of a modified cellulose or chitosan as defined above, with a molecular weight of 500-1000,000 g/mol; preferably nitrocellulose

The side chains are polyether and/or polyester side chains and can be selected from monohydroxyl polyether, mono-hydroxyl polyester, mono-amine or imine polyether, etc, with the molecular weight between 100 and 10,000 g/mol.

The graft agent is a polyisocyanate as described above and is preferably selected from toluene diisocyanate, 4,4 methylene diphenylene diisocyanate, tetramethyl-m-xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4 methylene dicyclohexylene diisocyanate and the like.

The catalyst can be selected from triethylene diamine, triethylamine, dibutyl tin dilaurate etc.

Thus, the process to prepare a compound of the Formula 1 or a mixture of compounds of the Formula 1 and 2 according to claim 1 comprises the steps of

a) reacting the polyisocyanate NCO—R—NCO wherein R is as defined in claim 1 with a polyether and/or polyester at temperature t₁ which ranges from 0° C. to 100° C. in the presence of a catalyst,b) grafting the obtained modified polyether and/or modified polyester onto the modified cellulose or chitosan backbone at temperature t₂ which ranges from 40° C. to 150° C.

In the two-pot method, step a) is followed by adding the resultant of step a) into another pot containing the modified cellulose or chitosan backbone.

In the one-pot method, step a) is followed by adding the modified cellulose or chitosan backbone into the pot of step a).

A process is thus disclosed to prepare a compound of the Formula 1 or a mixture of compounds of the Formula 1 and 2 as described above wherein the modified polyether and/or modified polyester obtained in step a) is isolated and added to the modified cellulose or chitosan backbone (two-pot method) or wherein the modified cellulose or chitosan backbone is added to the modified polyether and/or modified polyester obtained in step a) (one-pot method).

The molar ratio of graft agent to side chains ranges from 1:1 to 1:2.

The weight ratio of backbone polymer to modified side chains ranges from 5:1 to 1:10.

Dosage of catalyst ranges from 0.05% to 1%.

The molecular weight of the modified cellulose or chitosan backbone is 500-1000,000 g/mol, preferably 1000-500,000 g/mol.

The molecular weight of the polyether and/or polyester side is weight between 100 and 10,000 g/mol, preferably 300-5,000 g/mol.

Use:

The inventive dispersant is used for organic pigment dispersions, especially in nitrocellulose-alcohol (NC-A), nitrocellulose-ester (NC-E) and Nitrocellulose-alcohol/ester (NC-NE) systems, applied in general coating, ink applications or flexo applications as well as food contact applications.

Accessibility of the Starting Materials

Abbreviations of chemicals and their suppliers
ABBREVIATION	CHEMICAL NAME	SUPPLIER
MPEG	poly(ethylene glycol) methyl ether	Clariant
	with different molecular weight
BPPG	poly(propylene glycol) monobutyl
	ether with different molecular weight
Jeffamine	Jeffamine ® M-series	Huntsman
	monofunctional amine based on
	poly(ethylene-block-propylene
	glycol)
Surfonamine	Surfonamine ® ML and MNPA
	monofunctional amine based on
	poly(propylene glycol)
NC	nitrocellulose	Hagedorn,
EA	ethanol	Wolff
IPA	isopropanol
ESO	epoxidized soybean oil
DBP	dibutyl phthalate
ATBC	acetyl tributyl citrate
DOA	dioctyl adipate
CAB	cellulose acetate-butyrate	Eastman
CTS	chitosan	Shanghai,
		Nicechem
HPMC	Hydroxypropyl Methyl Cellulose	Aldrich
HEC	2-hydroxyethyl cellulose
TDI	toluene diisocyanate
IPDI	isophorone diisocyanate
HDI	hexamethylene diisocyanate
DBTL	dibutyl tin dilaurate
EtoAc	ethyl acetate
MEK	methyl ethyl ketone

EXAMPLES

Two-Pot Method

Intermediates

Intermediate 1

The wetting agent was removed from 100 g nitrocellulose (NC) resin (Walsroder NC-E330 IPA 33%) by vacuum at 70° C., then a 25% wt NC solution was prepared by dissolving the above resultant in 200 g EtOAc with 0.4 g DBTL addition. This is Intermediate 1.

Intermediate 2

100 g NC resin (Walsroder NC-E330 ESO 20%) with 0.5 g DBTL addition was dissolved in 220 g EtOAc to obtain a 25% wt NC solution, Intermediate 2.

Intermediate 3-9

Intermediate 3-9 were all prepared in a similar manner as Intermediate 1 except that the type of NC resin was varied as detailed in Table 1 below.

TABLE 1
Intermediate NC resin
3            Walsroder NC-E330 EA 33%
4            Walsroder NC-E375 IPA 33%
5            Walsroder NC-E375 EA 33%
6            Walsroder NC-A300 IPA 33%
7            Walsroder NC-A400 EA 33%
8            Walsroder NC-AM330 IPA 33%
9            BNC NC-E15 IPA 33% (France, BNC)

Intermediate 10-22

Intermediate 10-22 were all prepared in a similar manner as Intermediate 2 except that the type of NC resin was varied as detailed in Table 2 below.

TABLE 2
Intermediate NC resin
10           Walsroder NC-E330 DBP 20%
11           Walsroder NC-E330 ATBC 20%
12           Walsroder NC-E330 DOA 20%
13           Walsroder NC-E375 ESO 20%
14           Walsroder NC-E375 DBP 20%
15           Walsroder NC-E375 ATBC 20%
16           Walsroder NC-E375 DOA 20%
17           Walsroder NC-A300 ESO 20%
18           Walsroder NC-A400 ESO 20%
19           Walsroder NC-A300 DBP 20%
20           Walsroder NC-A400 DBP 20%
21           Walsroder NC-AM330 ESO 20%
22           BNC-NC-E15 ESO 20% (Fr, BNC)

Intermediate 23

50 g CAB resin (CAB-531-1) with 0.3 g DBTL addition was dissolved in 150 g MEK to obtain a 25% wt solution. This is Intermediate 23.

Intermediate 24-26

Intermediate 24-26 were all prepared in a similar manner as Intermediate 23 except that the polysaccharide resin was varied as detailed in Table 3 below.

TABLE 3
Intermediate polysaccharide resin
24           CTS
25           HPMC
26           HEC

Intermediate 27

The mixture of 50.0 g MPEG500 (molecular weight of 500 g/mol), 17.2 g TDI, 0.2 g DBTL, and 68 g EtOAc were stirred under nitrogen at room temperature (RT) for 1 h and at 40° C. for further 3 h. Intermediate 27 was obtained as a 50% wt solution.

Intermediate 28-45

Intermediate 28-45 were all prepared in a similar manner as Intermediate 27 except that the type and amounts of monofunctional polyether, diisocyanate monomer, amount of EtOAc, and the reaction condition were varied as detailed in Table 4 below. Quantitative EtOAc is added to the reaction formulation to obtain a solution with solid contain of 50% wt. The dosage of DBTL is set as 0.15% wt.

TABLE 4
	Monofunctional	Diisocyanate	Reaction
Intermediate	polyether	monomer	condition
28	MPEG1000	TDI	RT 1 h
	50 g	8.6 g	40° C. 3 h
29	MPEG2000	TDI	RT 1 h
	100 g	8.6 g	40° C. 3 h
30	BPPG350	TDI	RT 1 h
	35 g	17.2 g	40° C. 3 h
31	BPPG1000	TDI	RT 1 h
	50 g	8.6 g	40° C. 3 h
32	BPPG2500	TDI	RT 1 h
	62.5 g	4.3 g	40° C. 3 h
33	Jaffamine M-600	TDI	RT 2 h
	60 g	17.2 g	40° C. 2 h
34	Jaffamine M-1000	TDI	RT 2 h
	50 g	8.6 g	40° C. 2 h
35	Jaffamine M-2005	TDI	RT 2 h
	50 g	4.3 g	40° C. 2 h
36	Jaffamine M-2070	TDI	RT 2 h
	50 g	4.3 g	40° C. 2 h
37	Surfonamine ML-300	TDI	RT 2 h
	30 g	17.2 g	40° C. 2 h
38	Surfonamine MNPA-1000	TDI	RT 2 h
	50 g	8.6 g	40° C. 2 h
39	MPEG1000	IPDI	RT 1 h
	50 g	11.1 g	60° C. 3 h
40	BPPG1000	IPDI	RT 1 h
	50 g	11.1 g	60° C. 3 h
41	Jaffamine M-1000	IPDI	RT 2 h
	50 g	11.1 g	60° C. 2 h
42	Jaffamine M-2005	IPDI	RT 2 h
	50 g	5.6 g	60° C. 2 h
43	Surfonamine MNPA-1000	IPDI	RT 2 h
	50 g	11.1 g	60° C. 2 h
44	BPPG1000	HDI	RT 1 h
	50 g	8.4 g	60° C. 3 h
45	Surfonamine MNPA-1000	HDI	RT 2 h
	50 g	8.4 g	60° C. 2 h

Intermediate 46

The mixture of 13.5 g 1-octadecanol, 36.5 g ε-caprolactone and 0.3 g DBTL were stirred under nitrogen at 170° C. for 6 h, then 60 g EtOAc was added and the resultant was cooled down to RT. 8.6 g TDI was added into the above resultant and stirred under nitrogen at RT for 1 h and at 40° C. for further 3 h. Intermediate 46 was obtained as a 50% wt solution.

Intermediate 47

The mixture of 13.5 g 1-octadecanol, 36.5 g ε-caprolactone and 0.3 g DBTL were stirred under nitrogen at 170° C. for 6 h, then 62 g EtOAc was added and the resultant was cooled down to RT. 11.1 g IPDI was added into the above resultant and stirred under nitrogen at RT for 1 h and at 60° C. for further 3 h. Intermediate 47 was obtained as a 50% wt solution.

Intermediate 48

The mixture of 13.5 g 1-octadecanol, 86.5 g ε-caprolactone and 0.6 g DBTL were stirred under nitrogen at 170° C. for 6 h, then 110 g EtOAc was added and the resultant was cooled down to RT. 11.1 g IPDI was added into the above resultant and stirred under nitrogen at RT for 1 h and at 60° C. for further 3 h. Intermediate 48 was obtained as a 50% wt solution.

Dispersants

Dispersant 1

Backbone polymer (Intermediate 1) 40.0 g was stirred under nitrogen at 60° C. firstly, and then side chains (Intermediate 27) 13.4 g was dropped into the above resultant slowly. The mixture was cooked at 60° C. for 8 h and 80° C. for further 2 h. Then quantitative EtOAc was removed under vacuum to obtain a yellowish viscous solution (solid contain of 50% wt). This is Dispersant 1.

Dispersant 2-68

Dispersant 2-68 were all prepared in a similar manner as Dispersant 1 except that the type and amounts of side chains, backbone polymer, and the reaction condition were varied as detailed in Table 5 below.

TABLE 5
		Backbone	Reaction
Dispersant	Side chain	polymer	condition
2	Intermediate 28	Intermediate 1	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
3	Intermediate 29	Intermediate 1	60° C. 8 h
	43.4 g	40.0 g	80° C. 2 h
4	Intermediate 30	Intermediate 1	60° C. 8 h
	10.4 g	40.0 g	80° C. 2 h
5	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
6	Intermediate 32	Intermediate 1	60° C. 8 h
	53.4 g	40.0 g	80° C. 2 h
7	Intermediate 33	Intermediate 1	60° C. 8 h
	15.4 g	40.0 g	80° C. 2 h
8	Intermediate 34	Intermediate 1	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
9	Intermediate 35	Intermediate 1	60° C. 8 h
	43.4 g	40.0 g	80° C. 2 h
10	Intermediate 36	Intermediate 1	60° C. 8 h
	43.4 g	40.0 g	80° C. 2 h
11	Intermediate 37	Intermediate 1	60° C. 8 h
	9.4 g	40.0 g	80° C. 2 h
12	Intermediate 38	Intermediate 1	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
13	Intermediate 39	Intermediate 1	80° C. 12 h
	24.4 g	40.0 g
14	Intermediate 40	Intermediate 1	80° C. 12 h
	24.4 g	40.0 g
15	Intermediate 41	Intermediate 1	80° C. 12 h
	24.4 g	40.0 g
16	Intermediate 42	Intermediate 1	80° C. 12 h
	44.4 g	40.0 g
17	Intermediate 43	Intermediate 1	80° C. 12 h
	24.4 g	40.0 g
18	Intermediate 44	Intermediate 1	80° C. 12 h
	23.4 g	40.0 g
19	Intermediate 45	Intermediate 1	80° C. 12 h
	23.4 g	40.0 g
20	Intermediate 46	Intermediate 1	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
21	Intermediate 47	Intermediate 1	80° C. 12 h
	24.4 g	40.0 g
22	Intermediate 48	Intermediate 1	80° C. 12 h
	44.4 g	40.0 g
23	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
24	Intermediate 31	Intermediate 3	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
25	Intermediate 31	Intermediate 4	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
26	Intermediate 31	Intermediate 5	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
27	Intermediate 31	Intermediate 6	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
28	Intermediate 31	Intermediate 7	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
29	Intermediate 31	Intermediate 8	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
30	Intermediate 31	Intermediate 9	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
31	Intermediate 31	Intermediate 10	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
32	Intermediate 31	Intermediate 11	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
33	Intermediate 31	Intermediate 12	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
34	Intermediate 31	Intermediate 13	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
35	Intermediate 31	Intermediate 14	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
36	Intermediate 31	Intermediate 15	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
37	Intermediate 31	Intermediate 16	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
38	Intermediate 31	Intermediate 17	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
39	Intermediate 31	Intermediate 18	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
40	Intermediate 31	Intermediate 19	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
41	Intermediate 31	Intermediate 20	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
42	Intermediate 31	Intermediate 21	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
43	Intermediate 31	Intermediate 22	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
44	Intermediate 31	Intermediate 23	60° C. 8 h
	23.4 g	80.0 g	80° C. 8 h
45	Intermediate 31	Intermediate 24	60° C. 6 h
	23.4 g	32.0 g	80° C. 2 h
46	Intermediate 31	Intermediate 25	60° C. 8 h
	23.4 g	32.0 g	80° C. 8 h
47	Intermediate 31	Intermediate 26	60° C. 8 h
	23.4 g	32.0 g	80° C. 8 h
48	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	10.0 g	80° C. 2 h
49	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	20.0 g	80° C. 2 h
50	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	60.0 g	80° C. 2 h
51	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	80.0 g	80° C. 2 h
52	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	10.0 g	80° C. 2 h
53	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	20.0 g	80° C. 2 h
54	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	60.0 g	80° C. 2 h
55	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	80.0 g	80° C. 2 h
56	Intermediate 38	Intermediate 1	60° C. 8 h
	23.4 g	20.0 g	80° C. 2 h
57	Intermediate 38	Intermediate 2	60° C. 8 h
	23.4 g	20.0 g	80° C. 2 h
58	Intermediate 40	Intermediate 1	80° C. 12 h
	24.3 g	20.0 g
59	Intermediate 40	Intermediate 2	80° C. 12 h
	24.4 g	20.0 g
60	Intermediate 38	Intermediate 5	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
61	Intermediate 40	Intermediate 5	80° C. 12 h
	24.4 g	40.0 g
62	Intermediate 38	Intermediate 14	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
63	Intermediate 40	Intermediate 14	80° C. 12 h
	24.4 g	40.0 g
64	Intermediate 40	Intermediate 14	80° C. 12 h
	24.4 g	20.0 g
65	Intermediate 40	Intermediate 14	80° C. 12 h
	24.4 g	10.0 g
66	Intermediate 38	Intermediate 5	60° C. 8 h
	23.4 g	10.0 g	80° C. 2 h
67	Intermediate 38	Intermediate 5	60° C. 8 h
	23.4 g	20.0 g	80° C. 2 h
68	Intermediate 38	Intermediate 5	60° C. 8 h
	23.4 g	80.0 g	80° C. 2 h

One-Pot Method

Dispersant 69

The mixture of 50.0 g MPEG500 (molecular weight of 500 g/mol), 17.2 g TDI, 0.2 g DBTL, and 68 g EtOAc were stirred under nitrogen at room temperature (RT) for 1 h and at 40° C. for further 3 h. Then, backbone polymer (Intermediate 1) 400.0 g was added into above resultant and stirred under nitrogen at 60° C. for 8 h and 80° C. for further 2 h. Quantitative EtOAc was removed under vacuum to obtain a yellowish viscous solution (solid contain of 50% wt). This is Dispersant 69.

Dispersant 70-78

Dispersant 70-78 were all prepared in a similar manner as Dispersant 69 except that the type and amounts of side chains, backbone polymer, and the reaction condition were varied as detailed in Table 6 below.

TABLE 6
		Backbone	Reaction
Dispersant	Side chain	polymer	condition
70	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
71	Intermediate 40	Intermediate 1	80° C. 12 h
	24.4 g	40.0 g
72	Intermediate 44	Intermediate 1	80° C. 12 h
	23.4 g	40.0 g
73	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	40.0 g	80° C. 2 h
74	Intermediate 31	Intermediate 1	60° C. 8 h
	23.4 g	60.0 g	80° C. 2 h
75	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	20.0 g	80° C. 2 h
76	Intermediate 31	Intermediate 2	60° C. 8 h
	23.4 g	60.0 g	80° C. 2 h
77	Intermediate 40	Intermediate 1	80° C. 12 h
	24.3 g	20.0 g
78	Intermediate 40	Intermediate 2	80° C. 12 h
	24.4 g	20.0 g

Performance Screening

In order to test the dispersion effect of the obtained dispersants, millbase was prepared according to the Formulation 1. The millbase was dispersed in Scandex Shaker for 2.0 h with the help of glass beads, and then filtered and stored at RT overnight. Final ink for testing was based on a NC-A system (Formulation 2). The final ink was prepared via mix with Scandex Shaker for 10 min, and applied on black-white paper with a 12 μm film thickness.

Formulation 1. Preparation of Millbase

	dispersant dosage
	ingredients (unit in gram)	0%	2.5%
1)	NC medium**	30.9	29.86
2)	Dispersant (50%)	0	1.04
3)	EA	48.1
4)	Pigments	21
5)	3.0 mm glass beads	200
	Total (g)	300
Pigments	IRGALITE Yellow BXL, BXFL	Supplied from Ciba
	IRGALITE Rubine 4BGL, 4BXL
	IRGALITE Blue GLVO, GLO
	Permanent Yellow PGRL05, 06	Supplied from Clariant
**NC	NC resin A300 EA 33% (Wolff)	34.5% wt
medium	EA	50.6% wt
	EtOAc	10.0% wt
	Dioctyl phathalate	4.9% wt

Formulation 2. Final Ink System

1)	NC medium	29.4% wt
2)	Millbase	47.6% wt
3)	EA	18.4% wt
4)	Ethoxypropanol	4.6% wt

The performance of Dispersant 1-68 was tested according to Formulation 1 and 2. In general, some dispersants were taken as the representative dispersants, such as 5, 12, 14, 17, 23, 24, 29, 31-33, 42, 70, 73, and so on. The rheological behavior of the millbase was measured by Thermo-Haake RheoStress 600 equipment (Table 7). It was observed that the millbase flow well and their viscosities were comparable or lower than the blank formulation (dispersant dosage of 0%).

TABLE 7
Rheological data of Millbase
	IRGALITE	Permanent	IRGALITE	IRGALITE
	Yellow	Yellow	Rubine	Blue
	BXL	BXFL	PGRL05	PGRL06	4BGL	4BXL	GLVO	GLO
Blank formulation	5500	4000	2850	5550	2200	1600	2400	16700
Comparative	12500	9050	6500	9950	4500	3450	7550	35400
Example A
Dispersant 5	5300	2600	2800	5400	1300	900	3200	15900
Dispersant 12	5250	2500	2850	5300	1400	800	3000	16000
Dispersant 14	5350	2550	2900	5350	1200	750	3100	15950
Dispersant 17	5300	2650	2950	5450	1100	900	3050	16500
Dispersant 23	5200	2500	2850	5350	1000	850	3250	16000
Dispersant 29	5250	2450	2800	5400	1200	800	3100	16050
Dispersant 32	5300	2550	2900	5450	1150	900	3250	16100
Dispersant 42	5250	2450	2850	5350	1100	850	3050	16000
Dispersant 73	5200	2550	2850	5350	1050	850	3250	15900
η (mPas)
γ = 1.0 (1/s)
Comparative sample A was synthesized according to CN1128274.

The results show that comparative sample A performs worse dispersion effect (viscosity, gloss and opacity) than the blank formulation and than other dispersants, such as Dispersant 5, 14, 32 etc.

Tested in NC-A system, the performance of the dispersants was generally very good with satisfactory results, e.g. high gloss (Table 8), low opacity (Table 9), and high density, etc, compared with blank formulation.

TABLE 8
Gloss (60°) of final ink in NC-A system
	IRGALITE	Permanent	IRGALITE	IRGALITE
	Yellow	Yellow	Rubine	Blue
	BXL	BXFL	PGRL05	PGRL06	4BGL	4BXL	GLVO	GLO
Blank formulation	50.3	63.2	52.1	50.0	70.6	85.5	54.8	17.9
Comparative	48.4	54.3	49.5	47.3	65.4	81.1	50.3	14.7
Example A
Dispersant 5	59.3	67.3	56.4	52.7	94.5	88.6	61.5	19.7
Dispersant 12	57.8	66.0	55.7	54.2	90.7	90.3	60.6	20.2
Dispersant 17	60.2	67.7	56.1	55.6	97.4	93.4	59.5	18.5
Dispersant 23	58.5	65.2	55.4	54.8	89.8	91.5	58.9	17.4
Dispersant 32	56.9	68.3	54.7	51.6	92.4	89.4	60.3	19.2
Dispersant 42	57.7	66.4	57.4	54.6	93.7	90.8	61.7	21.3
Dispersant 73	58.7	65.2	55.6	54.8	89.8	91.3	58.9	17.0

TABLE 9
Opacity of final ink in NC-A system
	IRGALITE	Permanent	IRGALITE	IRGALITE
	Yellow	Yellow	Rubine	Blue
	BXL	BXFL	PGRL05	PGRL06	4BGL	4BXL	GLVO	GLO
Blank formulation	4.7	5.9	5.1	4.3	18.6	18.1	6.3	18.9
Comparative	5.2	7.0	5.9	4.8	20.3	21.6	7.8	22.6
Example A
Dispersant 5	3.3	5.4	4.1	3.7	14.4	17.2	4.8	18.0
Dispersant 12	3.1	5.0	3.7	3.4	15.1	16.4	5.3	17.4
Dispersant 17	3.2	5.7	4.2	3.8	13.8	17.3	4.3	18.1
Dispersant 23	3.5	4.9	3.9	3.1	14.9	15.6	5.0	15.8
Dispersant 32	3.7	5.1	4.0	3.5	13.9	14.7	5.2	16.5
Dispersant 42	3.3	5.2	3.8	3.3	15.3	13.9	4.0	15.8
Dispersant 73	3.4	4.9	3.8	3.2	14.9	15.8	5.1	16.0

Claims

1. Dispersant represented as a compound of Formula 1 or a mixture of compounds of Formula 1 and Formula 2

2. Dispersant according to claim 1, wherein T is cellulose nitrate (nitrocellulose).

3. Dispersant according to claim 1 wherein R is selected from toluenediyl, 4,4 methylene diphenylene, tetramethyl-m-xylylene, hexamethylenene, isophoronyl and 4,4 methylene dicyclohexylene.

4. Dispersant according to claim 1, wherein P is a mono-hydroxyl polyether.

5. A process to prepare a compound of the Formula 1 or a mixture of compounds of the Formula 1 and 2

6. A process to prepare a compound of the Formula 1 or a mixture of compounds of the Formula 1 and 2 according to claim 5 wherein the modified polyether and/or modified polyester obtained in step a) is isolated and added to the cellulose acetate, cellulose propionate, cellulose nitrate (nitrocellulose), methylcellulose, ethylcellulose, hydroxy ethylcellulose, carboxymethylcellulose, benzylcellulose or chitosan backbone or wherein the cellulose acetate, cellulose propionate, cellulose nitrate (nitrocellulose), methylcellulose, ethylcellulose, hydroxy ethylcellulose, carboxymethylcellulose, benzylcellulose or chitosan backbone is added to the modified polyether and/or modified polyester obtained in step a).

7. A process according to claim 5, wherein the molar ratio of polyisocyanate to the polyether and/or polyester ranges from 1:1 to 1:2 and the weight ratio of backbone polymer to the modified polyether and/or modified polyester ranges from 5:1 to 1:10.

8. An organic pigment dispersion comprising as dispersant the compound of Formula 1 or of the mixture of compounds of the Formula 1 and 2 according to claim 1.

9. (canceled)

10. An organic pigment dispersion according to claim 8 in nitrocellulose-alcohol (NC-A), nitrocellulose-ester (NC-E) or Nitrocellulose-alcohol/ester (NC-NE).

11. A coating or ink comprising the organic pigment dispersion according to claim 8.

12. A coating or ink comprising the organic pigment dispersion according to claim 10.