JPH0713214B2 - Pigment composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel pigment composition, more specifically, an ester containing a linked benzene ring, a high carbon number aromatic ring or a heterocyclic group. An object of the present invention is to provide a pigment composition which contains a compound as a dispersant or a flushing agent for pigments and is useful as a colorant for paints, printing inks, synthetic resin colorants and the like.

(Prior Art) Conventionally, a dispersant for dispersing a pigment in a paint vehicle or a printing ink varnish or flushing an aqueous filter cake into an oil vehicle or an oil varnish in the production of a paint or a printing ink, or As a flushing agent,
For example, the phospholipid lecithin has been used.

(Problems to be Solved by the Invention) However, since lecithin is a natural phospholipid, it is susceptible to oxidation and rancidity, and may be deteriorated or spoiled. Therefore, lecithin is stable and superior to these lecithins. There is a need for dispersants or flushing agents that have the same properties.

In view of the deficiencies of the above-mentioned conventional dispersants or flushing agents, the present inventors have conducted various studies to develop compounds having an affinity for various vehicles and varnishes and also an affinity for pigments. As a result, they have found that an ester compound containing a linked benzene ring, a high carbon number aromatic ring or a heterocyclic group exerts excellent properties and effects as a dispersant for pigments, and has completed the present invention. Is.

(Means for Solving Problems) That is, the present invention provides a pigment composition containing a pigment and a dispersant, wherein the dispersant is an ester compound represented by the following general formula. It is a thing.

R ₁ —O—CO—R ₂ —X or R ₁ —CO—O—R ₂ —X wherein R _{1 in} the formula is a benzene ring or an aromatic ring or heterocycle having 8 or more carbon atoms. Is a monovalent or polyvalent functional group containing a group, R ₂ is a polyvalent saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms, X is hydrogen, a hydroxyl group,
A carboxyl group or an ester residue thereof.

(Preferred Embodiment) The present invention will be described in detail with reference to the following preferred embodiments.

The dispersants used in the present invention and which are the main feature of the present invention are the specific ester compounds defined above.

In the present invention, the group of two or more linked benzene rings or the aromatic ring or the heterocyclic ring having 8 or more carbon atoms contained in the above specific ester compound includes all the conventionally known groups. A group derived from diphenylmethane, diphenylethane, diphenylpropane, diphenyl ether, diphenyl ether, diphenyl methyl ether, diphenyl sulfone, styrine benzene, biphenyl, naphthalene, fluorene, anthracene, acenaphthene, coumarin, quinoline or carbazole. .

In order to introduce the above-mentioned linked benzene ring or aromatic or heterocyclic group having 8 or more carbon atoms into an ester compound, a mono- or polyalcohol, mono- or polyphenol, mono- or polycarboxylic acid having these groups is introduced. The ester may be produced by using an acid, an acid chloride thereof, an acid anhydride or a compound having two or more kinds of groups thereof. As these high carbon number compounds, any of the conventionally known compounds belonging to the above definition can be used,
Preferred examples include the following.

Diphenylmethanecarboxylic acid, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylpropane, 4,4'-dioxydiphenylsulfone and ethylene oxide, propylene oxide, epichlorohydrin, etc. having 1 molar equivalent or more to those phenols Reaction product with an epoxy compound, diphenylcarboxylic acid, diphenyldicarboxylic acid, oxybiphenyl and a reaction product thereof with an epoxy compound such as ethylene oxide, propylene oxide, epichlorohydrin or the like in 1 molar equivalent or more, naphthol, dihydroxynaphthalene, Methyl 2-hydroxynaphthoate and a reaction product thereof with an epoxy compound such as ethylene oxide, propylene oxide, epichlorohydrin or the like in 1 molar equivalent or more. Naphthalenecarboxylic acid, naphthalenedicarboxylic acid, 3-oxy-anthracene-2-carboxylic acid, anthracenecarboxylic acid, anthraquinonecarboxylic acid, anthraquinodicarboxylic acid, fluorene alcohol, fluorenecarboxylic acid, phenanthrenecarboxylic acid, acenaphthenecarboxylic acid, Malon carboxylic acid, quinoline carboxylic acid, quinoline dicarboxylic acid, 2-oxydibenzofuran-3-carboxylic acid, 2-oxycarbazole-3-carboxylic acid and the like can be mentioned.

The ester compound used as a dispersant in the present invention is an aliphatic, alicyclic or aromatic hydroxycarboxylic acid component used to form a conventionally known ester as necessary in the above components, a carboxylic acid component, Obtained by esterification using an alcohol component.

Preferred hydroxycarboxylic acids include, for example, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, delta-hydroxyvaleric acid, ε-hydroxycaproic acid, p-hydroxyethyloxybenzoic acid and the like. .

Examples of preferred carboxylic acids include valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Behenic acid, lignoceric acid, undecylenic acid, oleic acid, lionolic acid, linoleic acid, behenic acid, dehydrated castor oil fatty acid, isostearic acid, isooctanoic acid,
Monocarboxylic acids such as abietic acid; and adipic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride,
Tetrahydrophthalic anhydride, 3,6-endo-methylene-
Tetrahydrophthalic anhydride (Nadic anhydride), Methyl-3,6-endomethylene-Tetrahydrophthalic anhydride (Methyl nadic anhydride), Hexachloroendomethylene tetrahydrophthalic anhydride (Het anhydride), Dodecenyl succinic anhydride, Polycarboxylic acids such as phthalic anhydride, tetrachlorophthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, polymerized rosin, rosin-maleic anhydride adduct, unsaturated fatty acid-maleic anhydride adduct, etc. Acid etc. are mentioned.

As the alcohol used, butyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octadecenyl alcohol. , Monoalcohols such as cyclohexyl alcohol and benzyl alcohol; 1,3-butylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, hydrogenated bisphenol A, trimethylolpropane, tris Polyhydric alcohols such as (hydroxyethyl) isocyanurate; glycols such as butyl glycol and butyl diglycol Examples thereof include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyethylene glycol fatty acid ester.

When the terminal carboxyl group or hydroxyl group of the obtained ester remains, these groups can be esterified with a monoalcohol or a monocarboxylic acid, if necessary.

For example, as monoalcohol, methyl alcohol,
Monoalcohols such as ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, dodecyl alcohol, hexadecyl alcohol, octadecyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octadecenyl alcohol, cyclohexyl alcohol, benzyl alcohol. Examples of monocarboxylic acids include acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
Examples thereof include monocarboxylic acids such as linoleic acid, behenic acid, tricyclodecanecarboxylic acid, benzoic acid, rosin and hydrogenated rosin.

The esterification reaction using these various components, the reaction of introducing an aromatic ring or heterocyclic group and the esterification reaction with the above monoalcohol or monocarboxylic acid are carried out according to conventionally known methods, for example, solvent-free. In a system or solvent solution,
A non-catalyst system or a catalyst is used in a reduced pressure system or a normal pressure system, and preferable reaction conditions are selected such as in air or under a nitrogen atmosphere.

The ester compound used in the present invention contains a benzene ring or an aromatic ring or a heterocyclic group having a high number of carbon atoms, which are linked to each other in the molecule, so that the hydrophobicity or lipophilicity is significantly increased, It is characterized in that the affinity with pigments, especially organic pigments, is remarkably improved.

Therefore, when the pigment is treated with these ester compounds, the ester compound has an affinity for the pigment and makes the surface of the pigment remarkably hydrophobic or lipophilic. However, it has a high affinity. Further, when an ester compound obtained by using a hydroxy derivative obtained by reacting a compound having a benzene ring, an aromatic ring or a heterocycle having a high carbon number as described above with an epoxy compound is used as a treating agent for a pigment, The effect was even better.

The pigment used in the present invention is a conventionally known organic pigment,
Any pigment such as an inorganic pigment and an extender pigment may be used.

For example, organic pigments include phthalocyanine-based, azo-based, condensed azo-based, anthraquinone-based, perinone-perylene-based, indigo-thioindigo-based, isoindolinone-based, azomethineazo-based, dioxazine-based, quinacridone-based, aniline black-based, tri-based Phenylmethane-based and carbon black, etc.Inorganic pigment-based, titanium oxide-based, iron oxide-based, iron hydroxide-based, chromium oxide-based, spinel-type calcined pigment, lead chromate-based, vermilion chromate-based, dark blue Examples of extender pigments such as powders, aluminum powders, bronze powders, and the like include calcium carbonate, barium sulfate, silicon oxide, and aluminum hydroxide.

In the present invention, these pigments are used not only in the form of dry fine powder, but also in the form of an aqueous filter cake or an aqueous suspension.

The pigment composition of the present invention can be obtained by blending the above ester compound in an amount of about 1 to 300 parts by weight, preferably about 3 to about 150 parts by weight, based on 100 parts by weight of the above pigment.

Of course, when mixing these two components, a conventionally known suitable organic solvent, a vehicle for an oil-based paint, a varnish for an oil-based printing ink, a binder resin for a vehicle for an oil-based coating agent, a thermoplastic resin, a thermosetting resin, etc. A resin, a plasticizer, a cross-linking agent, a catalyst and the like can be blended at the same time, and can be directly used as a paint or printing ink.

The method for obtaining the pigment composition of the present invention by mixing these essential components and optional components may be any conventionally known method, for example, ball mill, sand mill, attritor,
A typical method is mixing and kneading with a conventionally known disperser such as a horizontal continuous medium disperser, a two roll, a three roll, a pressure kneader, a Banbury mixer, and an extruder.

In particular, when using a pigment in the state of an aqueous filter cake or an aqueous suspension as the pigment, the dispersant used in the present invention alone, preferably a solution of a hydrophobic organic solvent (these organic solvents are The pigment composition of the present invention can be prepared by transferring the pigment from an aqueous phase to an organic solvent phase by a method of adding (mixing with a binder for printing ink or a coating material) to a pigment and mixing them (flushing).

The pigment composition of the present invention includes the following aspects.

(1) A composition containing a high concentration of a pigment and useful as a colorant for printing inks, paints, coating agents, synthetic resins and the like.
In this embodiment, the concentration of the pigment is 20 to 95% and the concentration of the dispersant of the present invention is 1 to 300% by weight of the pigment.

(2) A composition useful as a paint or the like, which also contains a solvent, a binder resin and the like necessary for a paint, a dispersant, a coating agent. In these compositions the pigment concentration is 0.1 to 20% by weight
And the concentration of the dispersant is 1 to 300% by weight of the pigment.

The paint includes all paints using conventionally known pigments, for example, automotive paint, architectural paint, wood paint, vehicle / equipment paint, household paint, plastic paint, precoat metal. Paint, can paint,
Marine paint, anticorrosion paint, light curing paint, electron beam curing paint,
Examples include electrostatic powder paints and vinyl sol paints.

The printing ink includes all conventionally known printing inks, and examples thereof include letterpress ink, planographic ink, intaglio gravure ink, screen ink, newspaper ink and flexo ink.

The pigment composition in the various aspects as described above may be in a solid state or in a liquid state, and water or a water-hydrophilic organic solvent mixture, an organic solvent is used as a medium in the case of a liquid state, and a fat is used as the organic solvent. Group-based, alicyclic-based, aromatic-based hydrocarbons, halogenated hydrocarbon-based, ester-based, ketone-based, glycol ether-based, alcohol-based, etc. are used, but are not particularly limited.

As the vehicle for paint, the varnish for printing ink, the vehicle for coating agent, etc., a conventionally known oily or aqueous binder material is used according to each application. For example, long oil length, medium oil length, short oil length alkyd resin, phenol modification, modified alkyd resin such as styrenated alkyd, amino alkyd resin, oil-free alkyd resin, baking acrylic resin, acrylic lacquer resin, acrylic polyol resin, Polyester resin, epoxy resin, butylated melamine resin, methylated melamine resin, urea-melamine resin, phenol resin, rosin-modified phenol resin, rosin-modified maleic acid resin, phenol-modified maleic acid resin, polyurethane resin, styrene resin, styrene acrylic resin , Styrene-diene copolymer, vinyl chloride copolymer, vinyl acetate resin, vinyl acetate copolymer, ethylene vinyl acetate resin, butyral resin, petroleum resin, modified resin such as rosin ester, maleated rosin ester, etc. , It is a boiled oil, and the like.

Examples of the thermoplastic resin include polyvinyl chloride resin, styrene resin, acrylonitrile / styrene resin, acrylic resin, methacryl-styrene resin, and ester resin.

Examples of the plasticizer include phthalic acid ester, adipic acid ester, sebacic acid ester, ester plasticizer, epoxidized soybean oil and the like.

If necessary, a conventionally known pigment dispersant or flushing agent, for example, higher aliphatic primary, secondary, or tertiary monoamine or higher aliphatic quaternary ammonium, higher aliphatic propylenediamine, or The combined use of these acetates and higher aliphatic salts does not hinder the achievement of the present invention.

(Operation / Effect) The ester compound introduced with two or more linked benzene rings or aromatic or heterocyclic groups having a high carbon number, which is used as a dispersant in the present invention, is a paint, a printing ink, a plastic colorant. In the field of colorants, such as natural pigment phospholipid, which has been used as a dispersant for pigments in the past, there is no risk of deterioration or spoilage due to oxidation or rancidity, excellent stability, and surface modification of pigments. It has an excellent effect in dispersing the pigment and the pigment in the medium.

The ester compound introduced with two or more linked benzene rings or high-carbon aromatic or heterocyclic groups used as a dispersant in the present invention is a hydrophobic compound and has an ester bond. Therefore, by the action of the charge-withdrawing property of the ester bond and the linked benzene ring, aromatic ring or heterocycle having a high carbon number, and lipophilicity of the hydrocarbon chain, the pigment is adsorbed on the surface of the pigment. To improve the dispersibility and fluidity of the pigment in the medium, and also as a flushing agent when flushing an aqueous filter cake of the pigment, etc. Since it is oily or hydrophobic, the pigment can be easily and efficiently flushed.

Next, the present invention will be described more specifically with reference to Reference Examples and Examples. In the text, parts and% are based on weight unless otherwise specified.

Reference Example 1 A four-neck glass reactor having an agitator, a thermometer, a backflow condenser with a moisture meter, and a charging port, and an oil bath were prepared. 101.1 parts (0.5 mol) of 2-naphthoxyacetic acid, 133.2 parts (0.5 mol) of oleyl alcohol and 35 parts of toluene were charged and stirred. After dissolution, the temperature was raised, and 3.5 parts of p-toluenesulfonic acid was added as a condensation catalyst.
The reaction solution was allowed to undergo an esterification reaction at 120 ° C. The progress of the reaction was examined by the amount of distilled water and the infrared absorption spectrum of the reaction product, and after 7 hours, the solvent toluene was distilled off under reduced pressure and the reaction was completed.

The obtained reaction product was a reddish brown liquid, and was confirmed to be an ester compound (dispersant 1) by the infrared absorption spectrum and the analysis chart of gel permeation chromatography.

Reaction was carried out in the same manner as in Reference Example 1 to obtain the following dispersant.

Dispersant 2; Esterification reaction product of naphthyl-1-acetic acid and tetraoxyethylene nonylphenyl ether (molar ratio 1: 1).

Dispersant 3; Esterification reaction product of tetraethylene glycol-2-naphthyl ether and oleic acid (molar ratio 1: 1).

Dispersant 4; tetraethylene glycol-2-naphthyl ether and 12
Esterification reaction product with hydroxystearic acid (molar ratio 1: 1).

Dispersant 5: Esterification reaction product of pentaethylene glycol-2-naphthyl ether and ricinoleic acid (molar ratio 1: 1).

Dispersant 6; naphthyl-1-acetic acid and 1,6-hexanediol (molar ratio
1: 1) esterification reaction product.

Dispersant 7: Esterification reaction product of pentaethylene glycol-2-naphthyl ether and castor oil fatty acid (molar ratio 1: 1).

Dispersant 8; pentaethylene glycol-2-naphthyl ether and 3,
Esterification reaction product with 6-endo-methylene-tetrahydrophthalic anhydride (molar ratio 1: 1).

Dispersant 9: Esterification reaction product of pentaethylene glycol-2-naphthyl ether and phthalic acid monooleyl ester (molar ratio 1: 1).

Dispersant 10 An esterification reaction product of 2,2-bis (hydroxypropoxyphenyl) propane and ricinoleic acid (molar ratio 1: 2).

Example 1 Copper phthalocyanine blue pigment (CI Pigment Blue 15
-4) Aqueous filter cake (pigment content 42%) 238 parts was charged into a flasher, 40 parts of Dispersant 1 was dissolved in 38.5 parts of petroleum-based ink solvent and added, and kneading was carried out according to the usual method, followed by flushing. I did. During this flushing, the water in the cake was easily liberated and the copper phthalocyanine blue pigment was transferred to the oily dispersant phase.

Further, the moisture was completely removed, and a flooded color containing a copper phthalocyanine blue pigment was obtained. An offset lithographic printing ink was prepared using the flooded color containing the copper phthalocyanine blue pigment obtained above.

Flushed de color of the copper phthalocyanine blue pigment obtained in the above (pigment content 56%) 34.8 parts offset lithographic inks formulated varnish 63.0 parts 5% cobalt drier 0.2 parts of 8% manganese drier 1.0 part isoquinolinium Solvent 1.0 parts Total 100 parts The In the above, the compounding varnish for offset lithographic ink has the following composition.

Use rosin-modified phenolic resin 35 parts dry oil 25 parts drying oil-modified isophthalic acid alkyd 10 parts isoquinolinium Solvent 29.5 parts of aluminum chelate 0.5 parts Total 100 parts ink obtained above were printed on high-quality paper with offset printing machine A clear blue print was obtained.

Further, instead of the aqueous filter cake of copper phthalocyanine blue pigment, an aqueous filter cake of disazo yellow pigment (CI Pigment Yellow 12) (pigment content 27%), Brilliant Carmine 6B pigment (CI Pigment Red 57-
Using the aqueous filter cake of 1) (pigment content 25%), the same operation as above was carried out to produce a floodside color, and then yellow and crimson offset lithographic inks were prepared.

Similarly, Lake Red C pigment (CI Pigment Red
53-1) to obtain a frassid color from the aqueous filter cake,
A gold-red ink for offset lithographic printing was obtained. In addition, a floccid color was obtained from an aqueous filter cake of copper phthalocyanine green pigment (CI Pigment Green 7) to obtain a grass ink for offset lithographic printing.

Each of them has easy water separation in the flushing, shows the transfer of the pigment to the excellent oil phase, and is easy to prepare the ink, and clear and excellent printed matter is obtained in the offset lithographic printing using these inks. Was given.

Also, instead of Dispersant 1 used in the above, Dispersants 2 to 10 were used, and the same excellent effects as above were obtained.

The carbon black pigment was kneaded and dispersed with three rolls in Example 2 Carbon black pigment 20 parts Dispersant 1 10 parts offset lithographic ink compounding formulations 65 parts Total 95 parts varnish. The carbon black pigment dispersed very well in the varnish.

Sufficiently uniformly mixed and kneaded obtained above carbon black pigment varnish dispersion 95 parts 5% cobalt drier 0.2 parts of 8% manganese drier 1.0 part isoquinolinium Solvent 3.8 parts Total 100 parts, to obtain a carbon black ink . Printing with an offset printing machine using this,
A black-colored printed matter with high blackness was obtained. Also, instead of the dispersant 1 used in the above, Dispersants 2 to 10 were used, and the same excellent effect as above was obtained.

In addition, the black ink obtained above was added to the yellow ink, the red ink, and the indigo ink obtained in the examples to obtain four colors as offset planographic process yellow ink, process red ink, process indigo ink, and process black ink. Process printing was performed, and clear and beautiful multicolor printed matter was obtained.

Example 3 Flucid color of copper phthalocyanine blue pigment obtained in Example 1 (pigment content 56%) 9.6 parts Rutile titanium white 2.0 parts Quick-drying styrenated alkyd resin 72.6 parts Xylol 6.6 parts Mineral spirits 8.8 parts 6% Naphthene sufficiently uniformly mixed and dispersed in cobalt 0.3 parts transdermal antiskinning agent 0.1 parts total 100 parts of the formulation, to obtain machine, blue quick drying enamel air drying of metallic material for vehicles or the like. When applied, a clear and beautiful paint was applied. Further, instead of the dispersant 1 used in the above, the dispersant 2 to the dispersant
10 was used, and excellent effects were obtained in the same manner as above.

Next, instead of the copper phthalocyanine blue pigment of Example 1, disazo yellow (CI Pigment Yellow 14),
Fast yellow pigment obtained by diazotizing 4-aminophthalimide and coupling with acetoacetanilide, Watching Red (CI Pigment Red 48),
Flushing was carried out in the same manner as in Example 1 using an aqueous filter cake of Carmine FB (CI Pigment Red 3) pigment to obtain a flacside color of each pigment.

These were used in place of the copper phthalocyanine pigment in the above composition of the paint, and paints of each color were obtained, and clear and beautiful coated plates were obtained.

Example 4 Copper phthalocyanine blue pigment (CI Pigment Blue 15
At dry milled pigment 10 parts Dispersant 1 5 parts of xylene 11 parts butanol 4 parts Total 30 parts -4) are dispersed in continuous horizontal medium dispersing machine, the dispersion liquid of xylene roll butanol mixed solvent of copper phthalocyanine blue pigment Was obtained.

Next, a paint was prepared with the following formulation.

Copper phthalocyanine blue and dispersant solvent dispersion 3 parts rutile titanium white, 14 parts of thermoplastic acrylic resin 70 parts of toluene 6.8 parts xylene 3.2 parts butanol 2.2 parts cellosolve 0.8 parts Total 100 parts This automobile comprising 1 obtained above Used as an acrylic lacquer enamel and applied to give a clear and beautiful coating.

Further, by using the dispersants 2 to 10 instead of the dispersant 1 used in the above, the same excellent coating as above was obtained.

Claims (3)

[Claims] 1. A pigment composition containing a pigment and a dispersant, wherein the dispersant is an ester compound represented by the following general formula. R ₁ —O—CO—R ₂ —X or R ₁ —CO—O—R ₂ —X (wherein R ₁ is a benzene ring or two or more aromatic rings or heterocycles having 8 or more carbon atoms linked together) A monovalent or polyvalent functional group containing a ring group, R ₂ is a polyvalent saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms, and X is hydrogen, a hydroxyl group, a carboxyl group or those Is the ester residue of.) 2. A diphenylmethane, diphenylethane, diphenylpropane, diphenylether, diphenylmethylether, diphenylsulfone, styrylbenzene, biphenyl, wherein two or more benzene rings or aromatic or heterocyclic groups having 8 or more carbon atoms are linked. , Naphthalene,
Fluorene, anthracene, acenaphthene, coumarin,
The pigment composition according to claim (1), which is a group derived from quinoline or carbazole. 3. A benzene ring or an aromatic ring or heterocyclic ring having 8 or more carbon atoms, which is linked by two or more, a mono- or polyalcohol, a mono- or polyphenol, a mono- or polycarboxylic acid, or two or more groups thereof. The pigment composition according to claim (1), wherein the pigment composition is introduced by a compound having the compound or a derivative thereof.