JPH0568514B2 - - Google Patents

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel pigment composition, and more specifically to a paint using a polyester compound substantially free of carboxyl groups as a pigment dispersant or flushing agent. The purpose of the present invention is to provide a pigment composition useful as a coloring material for printing inks, synthetic resin colorants, and the like.

(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 that the invention is trying to solve) However, since lecithin is a natural phospholipid, it is susceptible to oxidation and rancidity, and there is a risk of deterioration and spoilage. What is needed is a dispersant or flushing agent with 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, the present invention provides a pigment composition containing a pigment and a dispersant, in which the dispersant self-condenses a hydroxycarboxylic acid having a hydrocarbon group having 4 to 30 carbon atoms. This pigment composition is obtained by polymerization, is a polyester represented by the following general formula, and is substantially free of carboxyl groups.

R ₁ O-[COR ₂ O]n-X [However, R ₁ in the formula is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R ₂ is a divalent hydrocarbon group having 4 to 30 carbon atoms. is a group, n is a positive integer of 2 or more,
X is a hydrogen atom or -COR ₃ (However, R ₃ has 1 to 1 carbon atoms
30 hydrocarbon groups). (Preferred Embodiment) To explain the present invention in detail, the dispersant used in the present invention and which mainly characterizes the present invention is a specific polyester compound as defined above.

The polyester compound used in the present invention is a self-condensation product of hydroxycarboxylic acid containing a hydrocarbon chain having 4 to 30 carbon atoms, and the molecular weight of the polyester compound is not particularly limited. Heavy to average molecular weight of 10,000 or less, preferably 500 to 5,000.

Such a polyester compound can be obtained by esterifying the terminal carboxyl group of a self-condensation polymer of hydroxycarboxylic acid having both a hydroxyl group and a carboxyl group in the molecule.

Preferred hydroxycarboxylic acids have 4 to 4 carbon atoms.
Hydroxycarboxylic acids containing 30 hydrocarbon chains, such as ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acids, hydrogenated castor oil fatty acids, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, p-hydroxyethyl oxybenzoic acid,
2-hydroxynaphthalene-3-carboxylic acid, 2
-Hydroxycarboxylic acids such as -hydroxynaphthalene-6-carboxylic acid. 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 hydroxycarboxylic acid is as follows:
Alcohols having 1 to 30 carbon atoms, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, hexadecyl alcohol, octadecyl alcohol, tetracosyl alcohol, Examples include hexacosyl 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 using a catalyst, in a reduced pressure system, or in a normal pressure system, in air, or under a nitrogen atmosphere. The reaction is carried out by selecting preferable reaction conditions, such as, for example.

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 rendered hydrophobic or lipophilic, and it also has an affinity for oily media.

As the pigment used in the present invention, all conventionally known organic pigments, inorganic pigments, extender pigments, etc. can be used.

For example, organic pigments include phthalocyanine, azo, condensed azo, anthraquinone, penolin/perylene, indigo/thioindigo, isoindolinone, azomethine azo, dioxazine, quinacridone, aniline black, and trifluorocarbon pigments. Inorganic pigments include titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel fired pigments, lead chromate, vermilion chromate, and navy blue. Examples of extender pigments include calcium carbonate, barium sulfate, silicon oxide, and aluminum hydroxide.

In the present invention, these pigments can be 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 contains about 1 to 300 parts by weight of the polyester compound and 100 parts by weight of the pigment as described above.
It can be obtained by blending in an amount of about 3 to about 150 parts by weight, preferably about 3 to about 150 parts by weight.

Of course, when blending 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 plasticizer, a crosslinking agent, a catalyst, etc. can be added at the same time, and the composition can be used as it is in paints, printing inks, etc.

The method of mixing these essential components and optional components to obtain the pigment composition of the present invention may be a conventionally known method, such as a ball mill, a sand mill, an attritor, a horizontal continuous media disperser, a two-roll mill, a three-roll mill, etc. A typical method is to mix, knead, and grind using a conventionally known dispersing machine such as a pressure kneader, Banbury mixer, or extruder.

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

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

(1) Contains pigments in high concentration and is used in printing inks, paints,
A composition useful as a coating agent, a coloring agent for synthetic resins, etc. In this embodiment the pigment concentration is between 20 and 95
% by weight, and the concentration of the dispersant of the present invention is from 1 to 300% by weight of the pigment.

(2) A composition useful as a paint, etc., containing a solvent, a binder resin, etc. necessary as a paint, a dispersant, and 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.

Paints include all paints that use conventionally known pigments, such as automotive paints, architectural paints, wood paints, vehicle and equipment paints, household paints, plastic paints, pre-coated metal paints, Examples include can paints, marine paints, anti-corrosion paints, photo-curable paints, electron beam-curable paints, electrostatic powder paints, vinyl sol paints, and the like.

The printing ink includes all conventionally known printing inks, such as letterpress ink, lithographic ink, intaglio gravure ink, stencil screen ink, newspaper ink, and flexo ink.

The pigment compositions in various embodiments as described above are
It may be solid or liquid; in the case of liquid, water, a water-hydrophilic organic solvent mixture, or an organic solvent is used as the medium, and the organic solvent may be aliphatic, alicyclic, or aromatic. Hydrocarbons, halogenated hydrocarbons, esters, ketones, glycol ethers, alcohols, etc. are used, and there are no particular limitations.

Furthermore, as the paint vehicle, printing ink varnish, coating agent vehicle, etc., conventionally known oil-based or water-based vehicle materials can be used depending on the purpose. For example, alkyd resins with long oil length, medium oil length, and short oil length, phenol modified resins,
Modified alkyd resins such as styrenated alkyds,
Amino alkyd resin, oil-free alkyd resin, acrylic resin for baking, acrylic lacquer resin, acrylic polyol resin, polyester resin, epoxy resin, butylated melamine resin, methylated melamine resin, urea-melamine resin, phenolic 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 - Modified resins such as vinyl acetate resin, butyral resin, petroleum resin, rosin ester, maleated rosin ester, drying oil, boiling oil and the like.

Thermoplastic resins include polyvinyl chloride resin,
Styrene resin, acrylonitrile-styrene resin, acrylic resin, methacryl-styrene resin,
Examples include polyester resins.

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 ammonium, and higher aliphatic propylenic acid, may be used. The combined use of amines or their acetates, higher aliphatic salts, etc. does not hinder the achievement of the objects of the present invention.

(Action/Effect) The polyester compound substantially free of carboxyl groups used in the present invention is used in the field of coloring materials such as paints, printing inks, and plastic colorants.
It has excellent stability without the risk of deterioration or putrefaction due to oxidation or rancidity as seen in the natural phospholipid lecithin, and has excellent effects on surface modification of pigments and redispersion into media.

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

(Example) Next, the present invention will be described in more detail with reference to Examples. In the text, parts or percentages are based on 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 1000-1200) Dispersant 2: Benzyl ester of poly-12-hydroxystearic acid (average molecular weight 800-1000) Dispersant 3: Methyl ester of polyricinoleic acid (Average molecular weight 1300-1500) Dispersant 4: Butyl ester of poly 12-hydroxystearic acid (Average molecular weight 800-1000) Dispersant 5: Butyl ester of polyricinoleic acid (Average molecular weight 1200-1500) Dispersant 6: Poly 12 - Dodecyl ester of hydroxystearic acid (average molecular weight 1100-1300) Dispersant 7; Oleyl ester of polyricinoleic acid (average molecular weight 900-1100) Dispersant 8; Dodecyl ester of poly-12-hydroxystearic acid (average molecular weight 900-1100) ) Dispersant 9; oleyl ester of poly-ε-hydroxycaproic acid (average molecular weight 900-1100) Example 1 Copper phthalocyanine blue pigment (CI Pigment Blue 15-3) aqueous filter cake (pigment content 42
%) was placed in a flasher, 40 parts of Dispersant 1 dissolved in 38.5 parts of petroleum-based ink solvent was added, kneaded and flushed according to a conventional method.

During this flushing, the water content of the cake was easily liberated, and the copper phthalocyanine blue pigment was transferred to the oily dispersant phase.

Furthermore, water was completely removed to obtain a flushed color containing copper phthalocyanine blue pigment.
An offset lithography ink was prepared using the flat color containing the copper phthalocyanine blue pigment obtained above.

Copper phthalocyanine blue pigment flatusid color obtained above (purity 56%) 34.8 parts Mixed varnish for offset plate ink 63.0 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts Ink Solberlo 1.0 parts Total 100 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 Drying oil modified isophthalic acid alkyd 10 parts Ink solvent 29.5 parts Aluminum chelate 0.5 parts Total 100 parts Using the ink obtained above, print on high quality paper with an offset printing machine. A clear blue print was obtained.

Also, instead of the aqueous filter cake of copper phthalocyanine blue pigment, disazo yellow pigment (C.
Proceed as above using an aqueous filter cake of Pigment Yellow 12) (pigment content 27%) and an aqueous filter cake of brilliant carmine 6B pigment (CI Pigment Red 57-1) (pigment content 25%). A flush color was prepared by using the inks, and then yellow and red offset lithographic inks were prepared respectively.

Similarly, a flush color was obtained from an aqueous filter cake of Laked C pigment (CI Pigment Red 53-1), and a gold red ink for offset lithography was obtained. Also, a flush color was obtained from an aqueous filter cake of copper phthalocyanine green pigment (CI Pigment Green 7), and a grass ink for offset lithography was obtained.

In each case, water was easily separated during flushing, showed excellent transition to an oil phase, and the inks were easy to prepare, and using these inks, clear and excellent prints were obtained in offset lithography.

Furthermore, Dispersant 2 to Dispersant 9 were used in place of Dispersant 1 used above, and the same excellent effects as above were obtained.

Example 2 Carbon black pigment 20 parts Dispersant 1 10 parts Mixed varnish for offset lithographic ink 65 parts A total of 95 parts of carbon black pigment was kneaded and dispersed using three rolls. The carbon black pigment was very well dispersed in the varnish.

Varnish dispersion of carbon black pigment obtained above 95 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts Isoxol vent 3.8 parts A total of 100 parts were thoroughly mixed and kneaded to obtain a 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.

Further, in place of Dispersant 1 used above, Dispersants 2 to 9 were used, and excellent effects similar to those described above were obtained.

In addition, the black ink obtained above was added to the yellow ink, red ink, and blue ink obtained in the examples to obtain 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 Flush color of copper phthalocyanine blue pigment obtained in Example 1 (purity 56%) 9.6 parts Rutile titanium white 2.0 parts Quick-drying styrenated alkyd resin 72.6 parts Xylol 6.6 parts Mineral spirits 7.6 parts 6 % cobalt naphthenate 0.3 parts anti-skinning agent 0.1 part A total of 100 parts was thoroughly mixed and dispersed to obtain a blue quick-drying enamel that dries at room temperature for metal materials such as machinery and vehicles. When applied, the paint was clear and beautiful.

Next, in place of the copper phthalocyanine blue pigment of Example 1, disazo yellow (CI pigment yellow 14), a fast yellow pigment prepared by diazotizing 4-aminophthalimide and coupling it with acetoacetanilide, and a watching red pigment were used. (CI Pigment Red 48) and Carmine FB (CI Pigment Red 3) were used for flushing in the same manner as in Example 1 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 Dry and crushed pigment of copper phthalocyanine blue pigment (CI Pigment Blue 15-3) 10 parts Dispersant 1 2 parts Xylol 13 parts Butanol 5 parts Total 30 parts were dispersed in a continuous horizontal media disperser, and copper A dispersion of phthalocyanine blue pigment in a xylene/butanol mixed solvent was obtained.

Next, a paint was prepared using the following recipe.

Solvent dispersion containing copper phthalocyanine blue obtained above and dispersant 1 3 parts Rutile titanium white 14 parts Thermoplastic acrylic resin 70 parts Toluene 6.8 parts Xylol 3.2 parts Butanol 2.2 parts Cellosolve 0.8 parts Total 100 parts It was applied as an acrylic lacquer enamel and a clear and beautiful painting was obtained.

Further, by using Dispersant 2 to Dispersant 9 in place of Dispersant 1 used above, excellent coating materials were obtained in the same manner as above.

Claims (1)

[Scope of Claims] 1. A pigment composition containing a pigment and a dispersant, wherein the dispersant is obtained by self-condensation polymerization of a hydroxycarboxylic acid having a hydrocarbon group having 4 to 30 carbon atoms, and has the following general formula: A pigment composition characterized by being a polyester represented by the formula and substantially free of carboxyl groups. R ₁ O-[COR ₂ O] _o -X [However, R ₁ in the formula is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R ₂ is a divalent hydrocarbon group having 4 to 30 carbon atoms. is a group, n is a positive integer of 2 or more,
X is a hydrogen atom or -COR ₃ (However, R ₃ has 1 to 1 carbon atoms
30 hydrocarbon groups). ]