KR100421600B1 - Pigment Compositions - Google Patents

Abstract

The present invention relates to a composition comprising copper phthalocyanine having a crystal size of 0.01 to 0.2 μm and containing 0-4 chlorine atoms, and an ion complex formed from copper phthalocyanine sulfonic acid and a quaternary amine represented by the following formula (1): to provide:

^{_{N + (R 1 R 2 R}} 3 R 4) X -

In the formula, R ₁ is a C ₁ -C ₆ alkyl group; R ₂ is a C ₁ -C ₁₈ alkyl group; R ₃ is the same as R ₂ or is a hydroxyethyl or ethoxylated ethyl group having up to 5 ethyleneoxy units; R ₄ is a hydroxyethyl or ethoxylated ethyl group having up to 5 ethyleneoxy units; X is a halogen atom.

Description

Pigment Compositions

The present invention relates to a pigment composition containing chlorinated copper phthalocyanine having 0-4 chlorine atoms.

The present invention relates to a composition comprising copper phthalocyanine having a crystal size of 0.01 to 0.2 μm and containing 0-4 chlorine atoms, and an ion complex formed from copper phthalocyanine sulfonic acid and a quaternary amine represented by the following formula (1): It aims to provide.

<Formula 1>

^{_{N + (R 1 R 2 R}} 3 R 4) X -

In the formula, R ₁ is a C ₁ -C ₆ alkyl group; R ₂ is a C ₁ -C ₁₈ alkyl group; R ₃ is the same as R ₂ or is a hydroxyethyl or ethoxylated ethyl group having up to 5 ethyleneoxy units; R ₄ is a hydroxyethyl or ethoxylated ethyl group having up to 5 ethyleneoxy units; X is a halogen atom.

Copper phthalocyanine contains 0-4 chlorine atoms that can be covalently bonded, with copper trichlorine phthalocyanine being preferred.

Copper phthalocyanine preferably has a crystal size of 0.03 to 0.08 μm.

The R ₁ group in Formula 1 may be methyl, ethyl, propyl, butyl, aryl or hexyl, but methyl is preferred.

The R ₂ group may be the same as the R ₁ group, but higher alkyl groups containing 12-18 carbon atoms are preferred, such as cocoalkyl, tallowalkyl, stearyl or oleyl.

The R ₃ group may be the same as the R ₂ group, but preferably the same as the R ₄ group. The R ₃ and R ₄ groups may be hydroxy terminal ethoxylated ethyl groups having 1 to 5 ethylene oxy units, but hydroxyethyl is preferred.

X as halogen may be fluorine, chlorine, bromine or iodine, but chlorine is preferred.

Copper phthalocyanine sulfonic acid preferably has a degree of substitution of 0.8 to 1.5, preferably about 1.

The composition may contain, as its aluminum salt, up to 10% by weight of resin, preferably about 5% by weight.

Suitable resins include all rosin acids and derivatives thereof.

The composition can be prepared by treating copper phthalocyanine with a crystal size of 0.01 to 0.2 microns with an ionic complex.

Ionic complexes may be prepared separately and then added to copper phthalocyanine, or prepared in situ, whereby the copper phthalocyanine may be treated with copper phthalocyanine sulfonic acid at alkaline pH in an aqueous slurry and then added to the quaternary amine of formula (1). .

When aluminum resinate is present it is usually added at the end of the preparation phase of the composition.

Copper phthalocyanine can be prepared by performing conventional methods such as acid pasting with a salt or a ball milling method, and then treating the pigment, which is an aqueous slurry, at elevated temperature using an organic solvent in which at least a part is insoluble in water. Solvent treatment gives the correct particle size.

The organic solvent may be a water immiscible ester such as lower alkyl esters of aromatic carboxylic acids such as alkyl benzoates, preferably methyl benzoate. The water immiscible solvent is preferably in the form of an emulsion, ie in the form of a 50% emulsion in water, since otherwise it can be reduced by 20 to 40 times with less solvent than required.

If at least some of the water-soluble solvents are used as alcohols, ie propanol, butanol or n-pentanol, they may be further salted using a base such as sodium hydroxide. Phase transfer catalysts such as benzyl tributyl ammonium chloride are preferably used to promote interaction with the pigment. Water miscible polyglycols, preferably polyethylene glycol, may also be used as the solvent.

The amount of solvent used is only 30% by weight or less, preferably 5 to 20% by weight, based on the weight of the pigment.

The pigment may be treated with the solvent for 1 to 20 hours at 70 to 95 ° C., preferably for 4 to 8 hours at 90 to 95 ° C.

When the ester is used as the solvent, it can be removed by hydrolysis with an aqueous base, ie sodium hydroxide or potassium hydroxide. The treated pigment is then treated using an ionic complex.

A preferred method of preparing the product of the invention comprises the steps of preparing copper phthalocyanine and acid pasting, treating the resulting pigment with 5-20% by weight of an aqueous emulsion of methyl benzoate at 90-95 ° C. for 4-8 hours. Hydrolysing with sodium hydroxide to remove methyl benzoate, adding 5-10% by weight of copper phthalocyanine sulfonic acid at alkaline pH in an aqueous slurry, followed by addition of a quaternary amine of formula 1 and subsequently the product Treating with aluminum resinate.

The invention is illustrated by the following examples.

<Example 1>

100 g of copper trichloride phthalocyanine blue preliminary material was dissolved in 14 parts by weight of 98% sulfuric acid at 80-85 ° C. After stirring for 2 hours, 'paste' was added to the water under high flow and high turbulence conditions. Pigment products having a median crystal size of about 0.05 μm and distributed within a narrow range were isolated as filter cakes.

100 g of the pigment was purified with excess sodium hydroxide at 90 ° C. and then treated with 5%% solids in water and 10% (pigment weight) of methyl benzoate as an aqueous slurry at pH 7-7.5, this slurry Was mixed by high shear dispersion. The ester was added in the form of a stable emulsion in water. The resulting slurry was kept at 90-94 ° C. for 8 hours. The ester was then hydrolyzed by the addition of sodium hydroxide in the reaction system.

The product was again separated as a filterate.

100 g of the treated material was dispersed in water to prepare a slurry having 5-7% solids.

8 g of CuPcSO ₃ H was dispersed in the slurry at pH 11-11.5.

5% Ethoquad 0/12 (9-octadecene-1-aluminum, N, N-bis (2-hydroxyethyl) -N-methyl, chloride) as an aqueous solution, followed by 7% Arquad as an aqueous solution (Arquad) 2C (Di-coco, dimethyl (ammonium chloride), was stirred through the slurry. 5% tall oil rosin soap solution was mixed into the slurry, followed by filtration of the molar equivalents of aluminum chloride to the resin by filtration. Was added last before separation, washing and drying.

The resulting pigments show good color density, gloss, transparency and millbase rheology as well as neutral green fliptones in solvent borne automotive paints. The product is also very dispersible in waterborne automotive paints.

<Example 2>

The procedure of Example 1 was repeated except that the methyl benzoate emulsion step was substituted as follows.

To this slurry was added 30% n-pentanol and 3% water soluble phase transfer catalyst (benzyltributylammonium chloride) at pH> 10.0. The resulting slurry was refluxed for 6 hours to evaporate the solvent. The product was finished in the reaction system as in Example 1.

<Example 3>

100 g of copper trichloride phthalocyanine blue pretreatment was treated with 98% sulfuric acid as in Example 1.

The filtercake was slurried in water, the pH was adjusted to 7.0-7.5 with sodium hydroxide and 10% (pigment weight) methyl benzoate was added in the form of a stable emulsion in water. After heating at 90 ° C. for 4 hours, methyl benzoate was hydrolyzed by addition of sodium hydroxide.

After the end of hydrolysis, 8 g of CuPcSO ₃ H was dispersed in the slurry and the pH was adjusted to 11-11.5. 5% Ethoquad 0/12 as an aqueous solution, then 7% Arquad 2C as an aqueous solution was added to the slurry and stirred.

The 5% tall oil resin soap solution was mixed with the slurry and the pH was adjusted to 10.5-11.5 by finally adding a molar equivalent adduct of aluminum chloride to the resin. Filter and wash with hot water (60 ° C.) then dry the product.

<Example 4>

13 g of CuPcSO ₃ H was dispersed in water at 60 ° C. The pH was raised to 11-11.5 using sodium hydroxide and 12 g of Ethoquad C12 (Coco, N, N, bis (2-hydroxyethyl) N-methylammonium chloride) was added as an aqueous solution. After stirring for 2 hours, the product was filtered and washed and separated as filter cake of ionic complexes.

100 g of copper trichloride phthalocyanine blue pretreatment was treated with 98% sulfuric acid as in Example 1.

The resulting filtercake was slurried in water, the pH was adjusted to 7.0-7.5 with sodium hydroxide, and then 10% (pigment weight) of methyl benzoate was added in the form of a stable emulsion in water. After heating at 90 ° C. for 4 hours, methyl benzoate was hydrolyzed by addition of sodium hydroxide.

After the end of the hydrolysis, 15 g (dry weight) of the ion complex filter cake was mixed into the slurry, a 5% tall oil rosin soap solution was mixed with the slurry, and finally a molar equivalent addition of aluminum chloride to the resin was added, The process was completed as in Example 3.

Example 5

44 g of copper phthalocyanine before purification with a chlorine content of 4.5% was ball milled with 122 g of calcium chloride for 7 hours. The resulting material was then slurried in an aqueous solution containing 5% hydrochloric acid and stirred for 1 hour. The slurry was then filtered and washed to remove salts and the product was separated as filter cake. The particle size ranged from 0.05-0.1 μm.

40 g of the pigment were slurried in water and the pH was adjusted to 7.0-7.5. 10% (pigment weight) of methyl benzoate was added in the form of a stable emulsion in water. After heating at 90 ° C. for 4 hours, methyl benzoate was hydrolyzed by addition of sodium hydroxide.

After the hydrolysis was completed, 3.6 g of CuPcSO ₃ H was dispersed in the slurry and the pH was adjusted to 11-11.5. A 9% Noramox S5, 5% tall oil rosin soap solution was mixed into the slurry, and finally a molar equivalent addition of aluminum chloride to the resin was added to finish the process as in Example 3.

The products of the present invention have excellent compatibility with aqueous and solvent based automotive paint systems. This provides excellent millbase rheology and interesting green down flops at low tonal angles in metallic paint.

Claims (15)

A composition consisting of copper phthalocyanine with a crystal size of 0.01 to 0.2 μm and containing 0-4 chlorine atoms, and an ionic complex formed from copper phthalocyanine sulfonic acid and a quaternary amine of formula (I): <Formula 1> ^{_{N + (R 1 R 2 R}} 3 R 4) X - In the formula, R ₁ is a C ₁ -C ₆ alkyl group; R ₂ is a C ₁ -C ₁₈ alkyl group; R ₃ is the same as R ₂ or is a hydroxyethyl or ethoxylated ethyl group having up to 5 ethyleneoxy units; R ₄ is a hydroxyethyl or ethoxylated ethyl group having up to 5 ethyleneoxy units; X is a halogen atom. The composition of claim 1 wherein the copper phthalocyanine is copper trichlorine phthalocyanine. The composition of claim 1 or 2, wherein the crystal size is in the range of 0.03 to 0.08 μm. The composition of claim 1 or 2, wherein R ₁ is a methyl group, R ₂ is a higher alkyl group having 12 to 18 carbon atoms, and R ₃ and R ₄ are both hydroxyethyl. The composition of claim 1 or 2, wherein X is chlorine. The composition of claim 1 or 2, wherein the copper phthalocyanine sulfonic acid has a degree of substitution of 0.8 to 1.5. The composition according to claim 1 or 2, which contains, as its aluminum salt, up to 10% by weight of resin. A method for producing the composition of claim 1, comprising treating the copper phthalocyanine having a particle size in the range of 0.01 to 0.2 μm using an ion complex. The method according to claim 8, wherein the copper phthalocyanine having a particle size of 0.01 to 0.2 µm is treated with copper phthalocyanine sulfonic acid at an alkaline pH in an aqueous slurry, and then ions in the reaction system are added by adding a quaternary amine of the formula (1) as defined in claim 1. A method comprising preparing a complex. The process according to claim 8, wherein copper phthalocyanine is subjected to acid pasting or ball milling with salts and the pigment as an aqueous slurry at 70 ° C. to 90 ° C. for 1 to 20 hours with an organic solvent in which at least a part is not soluble in water. Obtained. The method of claim 10, wherein the organic solvent is a lower alkyl ester, alcohol or polyglycol of aromatic carboxylic acid. The process of claim 11 wherein the solvent is a methyl benzoate 50% emulsion in water. The method of claim 11, wherein the solvent is n-pentanol at least partially salted with a base. 14. The process according to any one of claims 8 to 13, wherein the resulting composition is treated using its resin, as its aluminum salt, with up to 10% by weight of resin. A method for producing an automotive paint system, wherein the composition according to any one of claims 1 to 4 and 5 to 7 is dispersed in water or a solvent.