WO2002030913A1

WO2002030913A1 - Aqueous dispersion fluidising agents

Info

Publication number: WO2002030913A1
Application number: PCT/GB2001/003592
Authority: WO
Inventors: Dean Thetford; Patrick John Sunderland
Original assignee: Avecia Limited
Priority date: 2000-10-12
Filing date: 2001-08-10
Publication date: 2002-04-18
Also published as: AU2001276560A1; GB0025263D0

Abstract

A compound of formula (1) and its use as fluidising agents for dispersions of particulate solids in a polar liquid, such as water, wherein R?1, R2 and R3¿ are each, independently, aryl, heteroaryl or alkyl, all of which may be optionally substituted, or polyoxyalkylene chain; X?1, X2 and X3¿ are each, independently, a direct link, -O-, -S- or a group -NR4- wherein R4 is hydrogen or C¿1-6?-alkyl, provided that at least one of R?1, R2 and R3¿ carries an anionic group, including salts thereof. Preferably R1-X1- is the residue of either 5-aminosalicylic acid and R2-X2 is the residue of either 5-aminosalicylic acid or sulphanilic acid.

Description

APPLICANTS

AVECIA LIMITED

TITLE

AQUEOUS DISPERSION FLUIDISING AGENTS

Aqueous Dispersion Fluidising Agents

The present invention relates to triazinyl anionic fluidising agents for aqueous based paints and inks and dispersions, millbases, paints and inks, including inks for non-contact printing. The fluidising agents are especially effective in aiding the dispersion of carbon black and quinacridone pigments. Some of the triazinyl anionic compounds are effective dispersants in their own right.

According to the invention there is provided a compound of formula 1.

Formula 1

wherein

R\ R² and R³ are each independently, aryl, heteroaryl, alkyl or cycloalkyl, all of which may be optionally substituted, or a polyoxyalkylene chain; X¹, X² and X³ are each, independently, a direct bond, -O-, -S- or a group -NR⁴- wherein R⁴ is hydrogen or C^-alky!, provided that at least one of R¹, R² and R³ carries an anionic group. The compoupd of formula 1 is hereinafter referred to as The Fluidising Agent.

Preferably, each of X¹, X² and X³ is -NR⁴-, which may be the same or different and especially -NH-.

When R¹, R² and R³is aryl it is preferably naphthyl and especially phenyl. When R¹, R² and R³ is alkyl, it is preferably C,_₃₀ -alkyl, more preferably C.,-₂₀ -alkyl and especially C,.^ -alkyl which may be linear or branched.

When R¹, R² and R³is cycloalkyl, it is preferably cyclohexyl. When R¹, R ² and R ³ is substituted, the substituent is preferably halogen such as chlorine and bromine, C,.₆ -alkoxy, cyano, hydroxy and a poly-C₂-₆- alkyleneoxy chain. The polyoxyalkylene chain is preferably obtainable from ethyleneoxide and/or propyleneoxide.

The polyoxyalkylene chain represented by R¹, R ² and R ³ is preferably poly (C₂.₆ alkyleneoxy) and especially those derived from ethyleneoxide and/or propyleneoxide. These polyoxyalkylene chains may be random or preferably block copolymers. The anionic group is preferably a phosphonic, phosphoric, sulphonic or carboxylic acid group which may be present as a free acid or in the form a salt with an alkali metal, alkaline earth metal, amine or quaternary ammonium cation.

Examples of alkali metals are lithium, potassium and especially sodium, including mixtures thereof. Examples of alkali earth metals are magnesium, calcium and barium, including mixtures thereof. Preferably, the compound of formula 1 is in the form of its sodium salt.

Preferred compounds of formula 1 contain two or more anionic groups and especially carboxylic acid groups. In a particularly preferred class of compounds of formula 1 , the group R¹-X¹- is the same as R²-X²-.

Particularly useful fluidising agents are those wherein R¹-X¹- and R²-X²- are both residues of 5-aminosalicylic acid. Other useful fluidising agents are those wherein R¹-X¹- is the residue of 5-aminosalicylic acid and R²-X²- is the residue of sulphanilic acid and those wherein R³-X³- is the residue of a polyalkyleneoxy alkylamine.

The compounds of formula 1 may be prepared by any method known to the art and are readily prepared by reacting a hydroxy compound, mercaptan or primary or secondary amine with cyanuric fluoride or especially cyanuric chloride in a mixture of water and a polar organic solvent such as acetone. The successive and controlled replacement of the halogen atoms in cyanuric fluoride or chloride is readily performed by temperature and adjustment of pH. Thus, the first halogen atom may be replaced at 0 to 10°C and a pH of between 3 and 5, the second halogen may be replaced at 30 to 50°C and a pH between 6 and 8 and the third halogen may be replaced at 60°C to 100°C and a pH value between 9 and 11. Examples of suitable amines are 4-aminophenol, 3-aminobenzoic acid, 4-and 5- amino salicylic acid, sulphanilic acid, metanilic acid, taurine, N-methyltaurine, n- butylamine, n-hexylamine, 2-ethylhexylamine, n-octylamine, aliphatic animal and vegetable amines which include mixtures of saturated and unsaturated amines such as tallowamine (mainly C₁₆.₁₈ fatty chains) and hydrogenated derivatives thereof and polyalkyleneoxy alkylamines of formula 2.

R⁵O - (C₂H₄ O)_π (CH, -CH O) CH₂ CH - NHR⁷

C I H₃ ^p R I.⁶

Formula 2 wherein

R⁵ is hydrogen or C,^ -alkyl; R⁶ is hydrogen or C,.₆-alkyl; R⁷ is hydrogen or C^-alkyl; n is 0 to 200; and p is 0 to 200; provided that n and p are not both zero.

When R⁵, R⁶ and R^τ is alkyl, it may be linear or branched.

When R⁵ is alkyl, it is preferably C^o-alkyl, more preferably C^-alkyl, even more preferably C.,-₆-alkyl and especially methyl.

R⁶ is preferably hydrogen or methyl

It is also preferred that n>p.

Preferably, n+p is not less than 4, more preferably not less than 6 and especially not less than 10. It is also preferred that n+p is not greater than 200, more preferably not greater than 100 and especially not greater than 80.

The ratio of n to p may vary over wide limits such as from 100:1 to 1 :100, more preferably from 50:1 to 1 :50, even more preferably from 20:1 to 1 :20 and especially from 10:1 to 1 :10.

Examples of amines of formula 2 wherein R⁵ is methyl, R⁶ is methyl and R⁷ is hydrogen are the so-called Jeffamines available from Huntsman Corporation. Specific examples are Jeffamine M-1000 (n=19, p=3), Jeffamine M-600 (n=1 , p=9), Jeffamine M- 2070 (n-32, p=10), Jeffamine M-2005 (n=β, p=39) and Jeffamine M-3003 (n=49, p=8).

When X¹, X² or X³ is -O-, the compound of formula 1 is obtainable by replacing one or more halogen atoms of cyanuric fluoride or chloride with a monohydric alcohol, a phenol or a polyalkoxy mono-alkyl or aryl ether. Examples of such monoalkyl ethers are polyethyleneglycol mono methyl ethers with weight average molecular weights of 550,

750 and 2000 (available from Fluka).

As disclosed hereinbefore, the compounds of formula 1 are particularly useful as fluidising agents for dispersing a particulate solid such as a pigment in a polar liquid, especially water.

Thus, according to a further aspect of the invention there is provided the use of a compound of formula 1 as a fluidising agent.

There is also provided a composition comprising a dispersant, the Fluidising Agent, a particulate solid and a polar liquid medium. The dispersant is preferably anionic and especially non-ionic. Preferred anionic dispersants are sulpholigninates and formaldahyde condensates of naphthol sulphonic acids. Preferred nonionic dispersants are alkylphenol, naphthol, C₁₀.₂₆ -aliphatic alcohol and styrenated phenol condensates with alkyleneoxide, especially ethylene oxide condensates. Specific examples of nonionic dispersants are octylphenol, nonylphenol, 2-naphthol, C₁₃.₁₅ -aliphatic alcohol and tristyrenated phenol with 10 to 20 ethylene oxide repeat units.

Since the dispersant and the Fluidising Agent may be added to the particulate solid at the same time there is also provided a composition comprising a dispersant and the Fluidising Agent. The particulate solid may be any inorganic or organic solid which is substantially insoluble in the polar medium and which it is desired to stabilise in finely divided form therein.

Examples of suitable particulate solids are pigments; extenders and fillers for paints and plastics materials; dyes, especially disperse dyes; optical brightening agents and textile auxiliaries for aqueous dyebaths; dirt; particulate ceramic materials; magnetic materials and magnetic recording media; fire retardants such as those used in plastic materials; biocides and agrochemicals and pharmaceutical compounds that are applied in aqueous dispersions or emulsions. A preferred particulate solid is a pigment from any of the recognised classes of pigments described, for example, in the Third Edition of the Colour Index (1971) and subsequent revisions of, and supplements thereto, under the chapter headed "Pigments". Examples of inorganic pigments are titanium dioxide, zinc oxide, Prussian blue, cadmium sulphide, iron oxides, vermilion, ultramarine and the chrome pigments, including chromates, molybdates and mixed chromates and sulphates of lead, zinc, barium, calcium and mixtures and modifications thereof which are commercially available as greenish-yellow to red pigments under the names primrose, lemon, middle, orange, scarlet and red chromes. Examples of organic pigments are those from the azo, disazo, condensed azo, thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone, isodibenzanthrone, triphendioxazine, quinacridone and phthalocyanine_, series, especially copper phthalocyanine and its nuclear halogenated derivatives, and also lakes of acid, basic and mordant dyes. Carbon black, although strictly inorganic, behaves more like an organic pigment in its dispersing properties. Preferred organic pigments are phthalocyanines, especially copper phthalocyaniries, monoazos, disazos, indanthrones, anthranthrones, quinacridones and carbon blacks.

Other preferred solids are: extenders and fillers such as talc, kaolin, silica, barytes and chalk; particulate ceramic materials such as alumina, silica, zirconia, titania, silicon nitride, boron nitride, silicon carbide, boron carbide, mixed silicon-aluminium nitrides and metal titanates; particulate magnetic materials such as the magnetic oxides of transition metals, especially iron and chromium, e.g. gamma-Fe₂O₃, Fe₃O₄, and cobalt-doped iron oxides, calcium oxide, ferrites, especially barium fer tes; and metal particles, especially metallic iron, nickel, cobalt and alloys thereof; agrochemicals such as the fungicides flutriafen, carbendazim, chlorothalonil and mancozeb and fire retardants such as aluminium trihydrate and magnesium hydroxide. It is especially preferred that the pigment is carbon black or a quinacridone.

The polar liquid medium is preferably water or a mixture of water and a polar organic liquid.

Examples of suitable polar organic liquids are amines, ethers, especially lower alkyl ethers, organic acids, esters, ketones, glycols, alcohols and amides. The term "polar" in relation to the organic liquid means an organic liquid or resin capable of forming moderate to strong bonds as described in the article entitled "A Three

Dimensional Approach to Solubility" by Crowley et al in Journal of Paint Technology, Vol

38, 1966, page 265. Such organic liquids generally have a hydrogen bonding number of 5 or more as defined in this article.

Numerous specific examples of such moderately strongly hydrogen bonding liquids are given in the book entitled "Compatibility and Solubility" by lbert Mellan (published in 1968 by Noyes Development Corporation) in Table 2.14 on pages 39-40 and these liquids all fall within the scope of the term polar organic liquid as used herein. Preferred polar organic liquids are dialkyl ketones, alkyl esters of alkane carboxylic acids and alkanols, especially such liquids containing up to, and including, a total of 6 carbon atoms. As examples of the preferred and especially preferred liquids there may be mentioned dialkyl and cycloalkyl ketones, such as acetone, methyl ethyl ketone, diethyl ketone, di-isopropyl ketone, methyl isobutyl ketone, di-isobutyl ketone, methyl isoamyl ketone, methyl n-amyl ketone and cyclohexanone; alkyl esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxy propylacetate and ethyl butyrate; glycols and glycol esters and ethers, such as ethylene glycol, 2-ethoxyethanol, 3-methoxypropylpropanol, 3-ethoxypropylpropanol, 2- butoxyethyl acetate, 3-methoxypropyl acetate, 3-ethoxypropyl acetate and 2-ethoxyethyl acetate; alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol and dialkyl and cyclic ethers such as diethyl ether and tetrahydrofuran.

Examples of suitable polar resins, as the medium for the dispersion form of the present invention, are film-forming resins such as are suitable for the preparation of inks, paints and chips for use in various applications such as paints and inks. Examples of such resins include polyamides, such as Versamid™ and Wolfamid™, and cellulose ethers, such as ethyl cellulose and ethyl hydroxyethyl cellulose. Examples of paint resins include short oil alkyd/melamine-formaldehyde, polyester/melamine-formaldehyde, thermosetting acrylic/melamine-formaldehyde, long oil alkyd and multi-media resins such as acrylic and urea/aldehyde. Preferably, the amount of polar organic liquid in the polar liquid medium is not greater than 10%, more preferably not greater than 5% and especially not greater than 2% based on the total amount of liquid medium.

It is, however, especially preferred that the liquid medium is water.

The composition preferably contains from 5 to 70%, by weight, particulate solid based on the total weight of the composition and from 1 to 50% by weight fluidising agent and from 3 to 50% by weight dispersant, both latter amounts being based on the total amount of particulate solid. It is especially preferred that the amount of particulate solid is from 25 to 60% based on the total amount of the composition and the amount of fluidising agent is from 5 to 15% and the amount of dispersant is from 10 to 30%, respectively, based on the amount of particulate solid.

When the composition is a dispersion, it may be made by any means known to the art. Thus, the particle size of the particulate solid may be reduced by attrition processes such as grinding or milling preferably in the presence of dispersant, fluidising agent and polar liquid medium. The fluidising agent may, however, be added at any stage, including addition to the final dispersion. It is preferred to add the fluidising agent prior to the attrition process. Preferably, the particle size of the particulate solid is reduced to less than 10μ, more preferably to less than 3μ and especially to less than 1μ. The attrition process is normally carried out at 20 to 25°C.

The fluidising agent may also be used in the preparation of millbases where the composition additionally comprises a film-forming binder resin and the attrition process is preferably carried out in the presence of the binder resin. Typically, the millbase contains from 20 to 70% by weight, pigment based on the total mount of millbase. Preferably, the millbase contains not less than 30% and especially not less than 50% pigment. The amount of film-forming binder resin may vary over wide limits but is preferably not less than 10% and especially not less than 20% of the continuous/liquid phase of the millbase. Preferably, the amount of film forming resin is not greater than 50% and especially not greater than 40% by weight of the continuous/liquid phase of the millbase. The amount of dispersant and fluidising agent in the millbase is preferably the same as that disclosed for the dispersion.

The dispersion and millbase may contain other adjuncts which are commonly added to paints and printing inks such as humectants, fillers, cross-linkers and preservatives. The dispersion may also contain viscosity modifiers and other adducts which are commonly used in non-impact printing processes, especially in the case of Drop-on-Demand printers wherein the ink droplet is ejected from an orifice by a thermal or piezoelectric means.

The fluidising agent may also be conveniently intermixed with a particulate solid for ease of use in amounts which produce the dispersions and millbases described herein before. The intermixing may be carried out by any means known to the art including dry attrition processes such as milling or grinding or by milling in the presence of a liquid medium and subsequently removing the liquid.

As a further aspect of the invention there is provided a paint or printing ink comprising a pigment, dispersant, film-forming resin, the Fluidising Agent and polar liquid medium.

The invention is further illustrated by the following non-limiting examples wherein all references are to parts by weight unless specified to the contrary. - Examples

Preparation of Fluidising Agents

Example 1

a)

Cyanuric chloride (20 parts, 0.108M ex Aldrich) was dissolved in acetone (200 ml) and added to a stirred mixture of ice (150 parts) and water (150 parts). A solution of 5-aminosalicylic acid (16.6 parts, 0.108M, ex Acros) in water (150 parts) at pH 8 was added dropwise over 20 minutes with stirring at 0 to 5°C. After stirring for 30 minutes, a second solution of 5-aminosalicylic acid (16.6 parts) in water (150 parts) at pH 8 was added over 20 minutes with stirring at 30-35°C. The pH was adjusted to pH 8 and the reactants stirred for 16 hours at 30-35°C. Finally, the pH was reduced to pH 4 whereupon the product separated as a pale pink solid. This was filtered, washed with water and freeze-dried (51.24 parts). This is Intermediate 1.

Sulphanilic acid (4.15 parts, 0.024 M ex Fluka) and Intermediate 1 (10 parts,

0.024M) were dissolved in acetone (80 ml) and water (150 parts) and the reactants stirred at 100°C at pH 9.5 for 18 hours. After cooling, the pH was adjusted to pH 6 and the product precipitated as the sodium salt by addition of sodium chloride, filtered and freeze- dried (7.03 parts). This is Fluidising Agent 1. Examples 2 to 13

A series of analogues was prepared by repeating Example 1(b) above by replacing the sulphanilic acid by the amine listed under column Y in Table 1 below.

Table 1

Footnote to Table 1

2-naphthylamine-6-sulphonic acid is available as Brδnner Acid Jeffamine M-1000 is MeO EO (19) PO(3) amine Jeffamine M-600 is MeO EO (1) PO(9) amine Jeffamine M-2070 is MeO EO (32) PO(10) amine Jeffamine M-2005 is MeO EO (6) PO(39) amine Jeffamine M-3003 is MeO EO (49) PO(8) amine Hydrogenated tallowamine is available as Armeen HT Examples 14 to 27

Example 1 (a) was repeated except replacing the second addition of 5-amino salicylic acid with the equivalent amount of sulphanic acid to obtain Intermediate 2 (Z is chlorine). Intermediate 2 was used in the process of Example 1 (b) to obtain the fluidising agents listed in Table 2 below.

Table 2

Footnote to Table 2

Methoxy PEG is polyethyleneglycol mono methylether with a weight average molecular weight as indicated (ex Fluka). 10

Example 28 to 53 Fluidising Agents with Carbon Black

The Fluidising Agent (0.1 parts) and nonionic dispersant (0.25 parts β-naphthol with 10 ethyleneoxide repeat units) were dissolved in water (7.65 parts). This solution was placed in a sealable vial with carbon black pigment (2.0 parts, Carbon Black S160 ex Degussa) together with 3mm diameter glass beads (17 parts) and milled for 17 hours by shaking on a horizontal shaker. The resultant dispersions were then assessed by hand shaking and using an arbitrary scale of A to E (very fluid to very viscous). The results are given in Table 3 below.

These results show that the Fluidising Agents exhibit a very marked improvement on the viscosity of the dispersions compared with that obtained using a nonionic dispersant alone.

11

Table 3

Footnote to Table 3

Control contains no fluidising agent but 0.10 parts water to maintain the weight of the dispersion. 12

Examples 54 to 79 Fluidising Agents as dispersants for Carbon Black

The efficacy of the Fluidising Agents to disperse carbon black pigments in water was determined by repeating Examples 28 to 53 except using pigment (2.0 parts), Fluidising Agent (0.25 parts) and water (7.75 parts). The results are given in Table 4 below. These data show that the Fluidising Agents are generally superior dispersants for carbon black in water compared with β-naphthol with 10 ethyleneoxide repeat units.

Table 4

Footnote to Table 4

Control contains β-naphthol with 10 ethyleneoxide units as dispersant. 13

Examples 80 to 105 Fluidising Agents with Quinacridone Pigments

Examples 28 to 53 were repeated except using red quinacridone pigment (3.0 parts Monolite Rubine 3B ex ICI Pic), Fluidising Agent (0.15 parts), nonionic dispersant (0.3 parts β-naphthol with 10 ethyleneoxide repeat units) and water (6.55 parts). The results are given in Table 5 below. These data show that the inclusion of the fluidising agent enhances the aqueous dispersion of quinacridone pigment.

Table 5

Footnote to Table 5 Control contains no fluidising agent but 0.15 parts water to maintain the volume. 14

Examples 106 to 131 Fluidising Agents with Copper Phthalocyanine Pigment.

Examples 28 to 53 were repeated except using copper phthalocyanine pigment (4.0 parts Monastral Blue BG ex Avecia Ltd), Fluidising Agent (0.08 parts), nonionic dispersant (0.15 parts β-naphthol with 10 ethyleneoxide units) and water (5.77 parts). The results are given in Table 6 below and show that the Fluidising Agents are less effective synergists for dispersing copper phythalocyanine pigment in water.

Table 6

Footnote to Table 6

Control contains no fluidising agent but 0.08 parts water to maintain the volume. 15

Examples 132 to 136

Examples 28 to 53 were repeated except using 0.2 parts Fluidising Agent, 0.4 parts nonionic dispersant and 7.4 parts water in place of the amounts shown in these examples. The dispersant used was nonlyphenol having 20 ethyleneoxy repeat units (Synperonic NP 20 ex ICI). The results are shown Table 7 below.

Table 7

Footnote to Table 7

Control contains no fluidising agent but 0.4 parts water to maintain volume.

Examples 137 to 140

Examples 132 to 136 were repeated except replacing the dispersant with the same amount of tristyrenated phenol having 16 ethylene oxy repeat units (Ethylan BCD 42 ex Akcros). The results are given in Table 8 below.

Table 8

Control contains no fluidising agent but 0.4 parts water to maintain volume.

Claims

16Claims

1. A compound of formula 1.

Formula 1

wherein

R\ R² and R³ are each, independently, aryl, heteroaryl, alkyl, all of which may be optionally substituted, or a polyoxyalkylene chain;

X¹, X² and X³ are each independently, a direct link, -O-, -S- or a group -NR⁴ wherein R⁴ is hydrogen or C,.₆-alkyl, provided that at least one of R¹, R²and R³ carries an anionic group, including salts thereof.

2. A compound as claimed in claim 1 wherein R¹, R² and R³ are each phenyl.

3. A compound as claimed in either claim 1 or claim 2 wherein X¹, X² and X³ is -NH-.

4. A compound as claimed in any one of claim 1 to 3 wherein R -X¹- and R²-X²- are both the residue of 5-aminosalicylic acid.

5. A compound as claimed in any one of claims 1 to 3 wherein R¹-X¹- is the residue of 5- aminosalicylic acid and R²-X²- is the residue of sulphanilic acid.

6. A compound as claimed in any one of claims 1 to 5 wherein -X³-R³ is the residue of an amine of formula 2.

R⁵O - (C₂H₄ O)_n (CH₂ -CH O) CH₂ CH - NHR⁷

CH₃ R⁶

Formula 2

wherein

R⁵is hydrogen or C.,-₃₀ -alkyl; R⁶ is hydrogen or C.,-₆-alkyI; R⁷ is hydrogen or C.,-₆-alkyl; n is 0 to 200; and p is 0 to 200; provided that n and p are not both zero. 17

7. A compound as claimed in claim 6 wherein R⁵ and R⁶ are both methyl.

8. The use of compound as claimed in any one of claims 1 to 7 as a fluidising agent for dispersing a particulate solid in a polar liquid.

9. A composition comprising a dispersant, a particulate solid, a polar liquid medium and a fluidising agent which is a compound as claimed in any one of claims 1 to 7.

10. A composition as claimed in claim 9 which additionally comprises a film-forming binder resin.

11. A composition as claimed in claim 9 wherein the dispersant is non-ionic.

12. A composition as claimed in claim 10 wherein the dispersant is an alkylphenol, naphthol, C₁₀.₂₆ -aliphatic alcohol or styrenated phenol condensate with alkylene oxide.

13. A composition as claimed in claim 12 wherein the dispersant is 2-naphthol with from 10 to 20 ethyleneoxide repeat units.

14. A composition comprising a particulate solid and a fluidising agent which is a compound as claimed in any one of claims 1 to 7.

15. A paint or ink which comprises a dispersant, a particulate solid, a polar liquid medium, a film-forming binder resin and a fluidising agent which is a compound as claimed in any one of claims 1 to 7.

16. A paint or ink as claimed in claim 15 wherein the particulate solid is carbon black pigment.

17. A paint or ink as claimed in either claim 15 or claim 16 wherein the polar liquid is ' water.

18. A composition comprising a dispersant and a fluidising agent which is a compound as claimed in any one of claims 1 to 7.