JPS62161863A - Pigment composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel pigment composition, and more specifically, the present invention relates to a novel pigment composition. The purpose of the present invention is to provide a pigment composition useful as a coloring material for painted paints, printing inks, synthetic resin colorants, etc.

(Prior Art) Conventionally, in the production of paints and printing inks, dispersants or For example, the phospholipid lecithin has been used as a flushing agent.

(Problem to be solved by the invention) However, since lecithin is a natural phospholipid, it is easily susceptible to oxidation and deterioration, and there is a risk of deterioration and putrefaction. What is needed is a dispersant or flushing agent with similar properties.

In view of the deficiencies of the above-mentioned pigment dispersants or flushing agents, the present inventors have conducted various studies on compounds that have an affinity for various vehicles and varnishes, and also have an affinity for pigments. The present invention was completed based on the discovery that a polyester compound substantially free of carboxyl groups exhibits excellent properties and effects as a pigment dispersant.

(Means for Solving the Problems) That is, 5 the present invention provides a pigment composition containing a pigment and a dispersant, in which the dispersant is a polyester compound represented by the following general formula that does not substantially contain carboxyl groups. A pigment composition characterized by the following.

R10+COR20+i-X However, R1 in the formula is a hydrocarbon group having 1 to 30 carbon atoms, R2 is a divalent hydrocarbon group having 4 to 30 carbon atoms,
statement is a positive integer greater than or equal to 2, and X is hydrogen or -COR
3 (wherein R3 is a hydrocarbon group of 1 to 30).

To explain the invention in detail, the dispersant used in the invention and which primarily characterizes the invention is a particular polyester compound as defined above.

The molecular weight of the polyester compound used in the present invention is not particularly limited, but it ranges from monomer dimer to average molecular weight of 10. OOO or less, preferably 500 to 5,00
It is 0th place.

Such a polyester compound is obtained by esterifying the terminal carboxyl group of a self-condensate of hydroxycarboxylic acid having both a hydroxyl group and a carboxyl group in the molecule. Preferred hydroxycarboxylic acids are
A hydroxycarboxylic acid containing a hydrocarbon chain having 4 to 3 carbon atoms, such as lysyllic acid, 12-hydroxystearin, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid,
Hydroxycarboxylic acids such as p-hydroxyethyloxybenzoic acid, 2-hydroxynaphthalene-3-carboxylic acid, and 2-hydroxynaphthalene-6-carboxylic acid are included. These hydroxycarboxylic acids can be used alone or as a mixture.

Furthermore, the alcohol used to esterify the terminal carboxyl group of the polyester compound obtained from the above-mentioned hydroxycarboxylic acid is as follows.

An alcohol having 1 to 30 carbon atoms, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, These include hexadecyl alcohol, octadecyl alcohol, tetracosyl alcohol, hexadecyl alcohol, octadecenyl alcohol, cyclohexyl alcohol, benzyl alcohol, and the like.

These polyesterification reactions and esterification reactions with alcohol are carried out according to conventionally known methods, for example, in a solvent-free system, in a solvent solution, in a non-catalytic system, or in a reduced pressure system using a catalyst. Alternatively, the reaction may be carried out by selecting preferable reaction conditions such as in a normal pressure system, in air, or under a nitrogen atmosphere.

The above polyester compound is characterized in that the terminal carboxyl group, which is a hydrophilic group, is esterified with alcohol to make the entire compound hydrophobic or lipophilic. Therefore, when processed into a pigment, the surface of the pigment is made hydrophobic or lipophilic, and it also has an affinity for oily media.

The pigments used in the present invention are conventionally known organic pigments,
Any pigment such as an inorganic pigment or an extender pigment may be used.

For example, organic pigments include phthalocyanine, azo, condensed azo, anthraquinone, perinone/perylene, indigo/thioindigo, isoindolinone,
Azomethine azo series, dioxazine series, quinacridone series,
These include aniline black, triphenylmethane, and carbon black, and inorganic pigments include titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel fired pigments, lead chromate, and chromium. Extender pigments include acid vermilion pigments, navy blue pigments, aluminum powder, bronze powder, etc., and extender pigments include calcium carbonate pigments, barium sulfate pigments, silicon oxide pigments, aluminum hydroxide pigments, and the like.

In the present invention, these pigments are used not only in the form of a 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 polyester compound in an amount of about 1 to 300 parts by weight, preferably about 3 to about 150 parts by weight, per 100 parts by weight of the above pigment.

Of course, when mixing these two components, conventionally known suitable organic solvents, binder resins such as oil-based paint vehicles, oil-based printing ink varnishes, oil-based coding agent vehicles, thermoplastic resins, thermosetting resins, etc. A resin, a plasticizer, a crosslinking agent, a catalyst, etc. can be added at the same time, and the composition can be used directly as a paint, printing ink, etc.

The method of mixing these essential components and optional components to obtain the pigment composition of the present invention may be any conventionally known method. For example, a ball mill, a sand mill, an attritor,
A typical method is mixing, kneading, and grinding using a conventionally known dispersing machine such as a horizontal continuous media dispersing machine, two rolls, Miki roll, pressurized Nigu, Pan Bali mixer, or extruder.

In particular, when using a pigment in the form of an aqueous filter cake or an aqueous suspension, the dispersant used in the present invention may be used alone, preferably in a solution of a hydrophobic organic solvent (these organic solvents are The pigment composition of the present invention can be obtained by adding the pigment to the pigment (which may contain a binder for printing ink or paint) and mixing it (flushing) to transfer the pigment from the aqueous phase to the organic solvent phase.

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

(1) Compositions containing pigments at high concentrations and suitable for printing inks and coatings. In this embodiment, the concentration of the pigment is 20-95% and the concentration of the dispersant of the invention is 1-300% by weight of the pigment.

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

Paints include all conventionally known paints that use pigments, such as automotive paints, architectural paints, wood paints, vehicle and equipment paints, household paints, plastic paints, and pre-coated metal paints. paint, can paint,
Marine paint, anti-corrosion paint, light curing paint, electron beam curing paint,
These include electrostatic powder paints and vinyl sol paints.

The printing ink includes all conventionally known printing inks, such as letterpress ink, lithographic ink, intaglio gravure ink, screen ink, newspaper ink, flexographic ink, and the like.

The pigment compositions in the various embodiments described above may be either solid or liquid. In the case of liquid, the medium used is water, a water-hydrophilic organic solvent mixture, or an organic solvent. Hydrocarbons, alicyclics, aromatic hydrocarbons, halogenated hydrocarbons, esters, ketones, glycol ethers, alcohols, etc. can be used, and are not particularly limited.

Furthermore, as paint vehicles, printing ink varnishes, coating agent vehicles, etc., conventionally known oil-based or water-based paint materials are used depending on the purpose. For example, Nagaura long, medium length, and short length alkyd resins, modified alkyd resins such as phenol-modified and styrenated alkyds, amino alkyd resins, oil-free alkyd resins, acrylic resins for baking, acrylic lunker resins, acrylic polyol resins, and polyesters. 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, Modified resins such as styrene-diene copolymers, vinyl chloride copolymers, vinyl acetate resins, vinyl acetate copolymers, ethylene vinyl acetate resins, butyral resins, petroleum resins, rosin esters, maleated rosin esters, drying oils , boiled oil, etc.

The thermoplastic resin is polyvinyl chloride resin.

These are styrene resin, acrylonitrile-styrene resin, acrylic resin, methacryl-styrene resin, and polyester resin.

Examples of the plasticizer include phthalate ester, adipate ester, sebacate ester, polyester plasticizer, and epoxidized soybean oil.

In addition, if necessary, conventionally known pigment dispersants or flushing agents, such as higher aliphatic primary, secondary, and tertiary monoamines, higher aliphatic quaternary heptammonium, and higher aliphatic propylene diamine. or their acetates,
The combined use of higher aliphatic salts and the like does not hinder the achievement of the present invention.

(Effects and Effects) The polyester compound that is substantially free of carboxyl groups used in the present invention is a natural phosphor compound that has been used as a dispersant for pigments in the field of color materials such as paints, printing inks, and plastic colorants. It has no fear of deterioration or putrefaction due to oxidation or rancidity as seen with the lipid lecithin, has excellent stability, and has excellent effects on surface absorption of pigments and dispersion of pigments into media.

The polyester compound used in the present invention that does not substantially contain carboxyl groups is a hydrophobic compound because it does not have a hydrophilic group, and since it has an ester bond, the charge of the ester bond is It adsorbs to the surface of the pigment due to its absorption properties and lipophilic properties of hydrocarbon chains, improves the wettability of the pigment to the medium, and improves the dispersibility and fluidity of the pigment in the medium. It can also be used as a flushing agent when flushing an aqueous filter cake of pigment, etc., to make the surface of the pigment lipophilic or hydrophobic, making it possible to flush the pigment easily and efficiently.

Next, the present invention will be specifically explained with reference to Examples. In addition,
In the text, parts or percentages are by weight unless otherwise specified.

In the present invention, the following dispersant was used.

Dispersant 1: Methyl ester of poly-12-hydroxystearic acid (average molecular weight t, ooo to 1.200) Dispersant 2: Benzyl ester of poly-12-hydroxystearic acid (average molecular weight 800 to 1.000 > minutes! & agent 3; Methyl ester of polyricinoleic acid (average molecular weight 1,300 to 1,500) M agent 4; Poly 12
-butyl ester of hydroxystearic acid (average molecular weight 800-1°) Dispersant 5; butyl ester of polyricinoleic acid (average molecular weight 1,200-1,500) dispersant 6; dodecyl ester of poly-12-hydroxystearic acid (average Molecular weight 1,100-1,300) Molecule [FI7; Oleyl ester of polyricinoleic acid (
(average molecular weight: 900-1,100) Dispersant 8: tridecyl ester of poly-12-hydroxystearic acid (average molecular weight: 900-1,100) Dispersant 9: oleyl ester of poly-ε-hydroxycaproic acid (average molecular weight: 800-1,100) 1.100) Example 1 Aqueous filter cake of copper phthalocyanine blue pigment (C,1, Pigment Blue 15-3) (pigment content 42%) 2
38 parts were placed in a flasher, 40 parts of dispersant 1 was dissolved in 38.5 parts of petroleum-based inquinlebento, and the mixture was kneaded and flashed according to a conventional method. During this flushing, water in the cake was easily liberated, and the copper phthalocyanine blue pigment was transferred to the oily dispersion.

Furthermore, water was completely removed to obtain a flashed color containing a copper phthalocyanate blue pigment. An offset lithographic printing ink was prepared using the flashed color containing the copper phthalocyanine blue pigment obtained above.

Flashed color of the copper phthalocyanine blue pigment obtained above (pigment content 56%) 34.8 parts Mixed varnish for offset lithographic ink 63.0 parts 5% Cobalt dryer 0° 2 parts 8% Manganese dryer 1.0 parts In the above, The blended varnish for offset lithographic ink has the following composition.

Rosin modified phenolic resin 35 parts drying oil
25 parts dry oil-modified isophthalic acid alkyd 10 parts ink solvent 2
9.5 parts aluminum chelate 0.5 go
A total of 100 copies were printed on high-quality paper using an offset printing machine using the ink obtained above to obtain a clear indigo-colored printed matter.

In addition, instead of the aqueous filter cake of copper phthalocyanine blue pigment described above, an aqueous filter cake of disazo yellow pigment (C, 1, pigment yellow 12) (pigment content 27
%), aqueous filter cake of Brilliant Carmino 6B pigment (C,1, Pigment Red 57-1) (pigment content 2
5%) to prepare flashed colors in the same manner as above, and then yellow and red offset lithographic inks were prepared respectively.

In the same manner, a flashed color was obtained from an aqueous filter cake of Lake Red C pigment (C, 1, Pigment Red 53-1), and a full red ink for offset lithography was obtained. Further, a flashed color was obtained from an aqueous filter cake of copper phthalocyanine green pigment (C, 1, Pigment Green 7), and a grass ink for offset lithography was obtained.

In each case, water is easily separated during flushing, the pigment shows excellent transfer to the oil phase, the ink is easy to prepare, and offset lithographic printing using these inks produces clear and excellent prints. It was done.

Also, instead of dispersant 1 used above, dispersant 2
~Dispersant 9 was used, and excellent effects similar to those described above were obtained.

Example 2 Carbon black pigment 20 parts dispersant 1
10 parts offsade 1 ink
・Varnish 651 total
Carbon black pigment was kneaded and dispersed using a Miki roll in a blend of 95 parts. The Car Pump Black pigment dispersed very well in the varnish.

Varnish dispersion of carbon black pigment obtained above 95 parts 596 Cobalt dryer 0.2 parts 8% Manganese dryer I, o parts Ink solvent
3.8゜Total 1
00 parts were sufficiently uniformly mixed and kneaded to obtain carbon black ink. This was used to print with an offset printing machine to obtain a black printed matter with a high degree of blackness. In addition, dispersant 2 to dispersant 9 were used in place of dispersant 1 used above, and the same excellent effects as above were obtained.

In addition, the black ink obtained above was added to the yellow ink, red ink, and blue ink obtained in the example to produce four colors of process yellow ink, process red ink, process blue ink, and process black ink for offset lithography. Process printing was performed and clear and beautiful multicolor printed matter was obtained.

Example 3 Flashed color of the 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 Kijirol
6.6 parts mineral spirit,)
8.8 parts 6% cobal naphthenate)
0.3 parts 7, + (direction - 0,1 total 100 parts) was sufficiently uniformly mixed and dispersed to obtain a blue quick-drying enamel that dries at room temperature for metal materials such as machines and vehicles. When applied, the paint was clear and beautiful.

Next, in place of the copper phthalocyanine blue pigment of Example 1, disazo yellow (C,1, Pigment Yellow 14
), fast yellow pigment made by diazotizing 4-aminophthalimide and coupling with acetoacedoanilide, Watching Red (C,1, Pigment Red 48), Chikaramin FB (C,1, Pigment Red 3)
Flushing was carried out in the same manner as in Example 1 using the aqueous filter cake of each pigment to obtain flushed colors of each pigment.

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

Example 4 Copper phthalocyanine blue 114 (C, I.

Pigment Blue 15-3) dry crushed pigment 10 parts dispersion 1
5th part pheasant roll
11 parts bunol
A total of 30 parts of 4 were dispersed using a continuous horizontal media disperser to obtain a dispersion of copper phthalocyanine blue pigment in a mixed solvent of quizyrol-butanol.

Next, a paint was prepared using the following recipe.

Solvent dispersion containing copper phthalocyanine blue obtained above and salt of dispersant l 3 parts Rutile titanium white 14 parts Thermoplastic acrylic resin 70 parts Doluol
6.8 parts Kijirole 3.2 parts Butanol 2.2 parts Cellosolve
0.8□Total
100 parts of this was applied as an acrylic lacquer enamel for automobiles, and a clear and beautiful coating was obtained.

Also, in place of dispersant 1 used above, dispersant 2
- 9 was used, and excellent coatings were obtained in the same manner as above.

Claims (1)

[Claims] (1) A pigment composition containing a pigment and a dispersant, wherein the dispersant is a polyester compound represented by the following general formula and substantially free of carboxyl groups. R1O-[COR2O]-l-X [However, R1 in the formula is a hydrocarbon group having 1 to 30 carbon atoms, R2 is a divalent hydrocarbon group having 4 to 30 carbon atoms, and 1 is 2 is a positive integer greater than or equal to X, and X is hydrogen or -CO
R3 (wherein R3 is a hydrocarbon group of 1 to 30)]