JPS62161862A - Pigment composition - Google Patents

Abstract

PURPOSE:A pigment composition useful for coating compound, printing ink, etc., having improved stability free from change in quality, comprising a higher hydrocarbon group-containing phosphoric ester compound as a dispersant for pigment. CONSTITUTION:The aimed pigment composition obtained by blending (A) 100pts. wt. pigment with (B) 1-300pts.wt. phosphoric ester compound [e.g., phosphoric acid tris(n-octyl) ester, etc.,] shown by the formula (when one or more of R is 8-30C hydrocarbon and the rest R exists, R of the rest is selected from group consisting of 1-7C hydrocarbon, H, heavy metallic cation and 8-30C hydrocarbon) obtained by reacting (i) 1mol ester-forming phosphorus compound with (ii) 1-3mol higher hydrocarbon-containing hydroxy compound.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel pigment composition and a method for producing the same. agent or fuller,
The object of the present invention is to provide a pigment composition useful as a coloring agent for cold 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 to be solved by the invention) However, because 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 similar properties.

In view of the deficiencies of the above-mentioned pigment dispersants or flushing agents, the inventors conducted various research 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 phosphoric acid ester compound having a higher hydrocarbon group exhibits excellent properties and effects as a pigment dispersant.

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

R-0-P-0-R However, one or more of the three R in the formula has 8 to 3 carbon atoms.
0 hydrocarbon group, and if there is a remainder, the remaining R
a hydrocarbon group in which one or two of these have 6t to 7 carbon atoms, hydrogen,
It is selected from the group consisting of heavy metal cations and cations having a hydrocarbon group having 8 to 30 carbon atoms.

To explain the present invention in detail, the dispersant used in the present invention and which mainly characterizes the present invention is a specific phosphoric acid ester compound as defined above.

The phosphoric acid ester compound used in the present invention can be obtained by various methods, including reacting 3 mol, 2 mol, or 1 mol of a hydroxy compound having a higher hydrocarbon group with 1 mol of the ester-forming phosphorus compound. Preferably, it is obtained by

In the above, if 3 moles of the hydroxy compound are reacted with 1 mole of the ester-forming phosphorus compound, a phosphoric ester compound in which all three R's in the general formula are hydrocarbon groups can be obtained.

In addition, in the above, if 2 or 1 mole of hydroxy compound is reacted with 1 mole of the ester-forming phosphorus compound, the phosphorus compound in which one or two of the three R's are hydrocarbon groups in the above formula An acid ester compound is obtained.

As the ester-forming phosphorus compound, conventionally known phosphorus oxychloride, phosphorus pentafluoride, phosphorus trichloride, phosphoric anhydride, acetyl phosphoric acid, etc. are used. Most preferred is phosphorus oxychloride.

The reaction between the above-mentioned ester-forming phosphorus compound and hydroxy compound can be carried out using an organic solvent that is inert to these KC materials and products and that dissolves these raw materials, such as octane, petroleum ether, ligroin, Mineral spirit, aliphatic saturated hydrocarbons such as kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aliphatic hydrocarbons such as trichloroethane and tetrachloroethane, chlorine such as O-dichlorobenzene and trichlorobenzene. It is preferable to carry out the reaction in an organic solvent used in the phosphoric acid esterification reaction, such as an aromatic hydrocarbon. In addition, when using a halogenated phosphoric acid compound such as phosphorus oxychloride as the ester-forming phosphorus compound, for example, tertiary amines such as triethylamine, pyridine, 2.6
-lutidine, ■,8-diaza-bicyclo(5,4,0)
Organic bases such as undecene-7, oxides, hydroxides, carbonates, and organic acid salts of alkali metals and alkaline earth metals, actual or latent inorganic a! Preference is given to using groups such as groups as catalysts.

Furthermore, when one or two of the three R's in the above general formula are hydrogen atoms or cations as described below, the reaction between the ester-forming phosphorus compound and 1 or 2 moles of the hydroxy compound is After substantial completion, optionally after hydrolysis (if a halogenated phosphate compound is used as the ester-forming phosphorus compound), a cation source, as described below, is added to the reaction mixture to form a salt. good. Further, the addition of such a cation source can be used to prepare the pigment composition of the present invention using a phosphoric acid ester compound having one or two hydrocarbon groups and the remaining R being a hydrogen ion. It may be carried out before obtaining, during or after production.

Examples of such hydroxy compounds having 8 to 30 carbon atoms include octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and tetracosyl alcohol.

hexadecyl alcohol, octadecenyl alcohol,
These are higher hydrocarbon alcohols such as dimethylcyclohexanol, ethylcyclohexanol, and dimethylphenylmethyl alcohol, and phenols such as dimethylphenol, phenylphenol, and naphthol.

The phosphoric acid ester compound used as a dispersant in the present invention can be obtained by reacting 3 to 1 molar proportion of the above-mentioned hydroxy compound with 1 molar proportion of the above-mentioned ester-forming phosphorus compound. When reacting the above hydroxy compound at a ratio of 1 mole or 2 moles per mole of the phosphorus compound, the remaining one or two R that are not hydrocarbon groups in the general formula
can be a hydrogen atom, an inorganic heavy metal cation or an organic higher hydrocarbon cation. The inorganic cation may be a cation of a divalent or higher polyvalent metal such as magnesium, calcium, strontium, barium, manganese, iron, cobalt, nickel, zinc, aluminum, tin, and the like.

In addition, organic cations include octyl-, dodecyl-, octadecyl-, oleyl-, distearyl-, dimethyloctyl-, dimethyldecyl-, dimethyldodecyl-, dimethylhexadecyl-, dimethyloctadecyl-, dimethyloleyl-, dimethyloleyl-, Lauryl monomethyl, trioctyl amine, dimethylaniline: primary, secondary, and tertiary mono- and polyamines having 1 to 30 carbon atoms such as stearylpropylpylene diamine, octadecyltrimethylammonium, dioctadecyldimethylammonium, etc. quaternary ammonium; cations such as alkanolamines obtained by adding ethylene oxide to the above-mentioned higher aliphatic amines; These amines can be used alone or in mixtures.

Furthermore, when using higher aliphatic amines and ammoniums obtained from natural fats and oils, a mixture of amines having different carbon numbers or degrees of saturation resulting from the natural fats and oils used as raw materials may also be used as is.

The phosphoric acid ester compounds used in the present invention as described above are 3
Phosphate ester compounds in which all of the R's are hydrocarbon groups and compounds in which one or two of the three R's are higher amine cations are relatively hydrophobic dispersants,
It is suitably used as a solution in an organic solvent.

The above-mentioned phosphoric ester compounds in which all three R's are hydrocarbon groups include phosphoric ester compounds in which all three R's are higher hydrocarbon groups and two or one of the three H's. is a higher hydrocarbon group, and the remaining R is a lower hydrocarbon group.

More specific examples of the phosphoric acid ester compounds used in the present invention include the following.

Phosphoric acid tris(n-octyl) ester.

Tris(2-ethylhexyl) phosphate, tris(nonyl) phosphate, tris(decyl) phosphate, tris(dodecyl) phosphate, tris(tridecyl) phosphate.

Tris (tetradecyl) phosphate ester, tris (hentadecyl) phosphate ester, tris (hexadecyl) phosphate ester, I-lis (octadecyl) phosphate ester, tris (octadecenyl) phosphate ester, tris phosphate (mixed with lauryl) myristyl) ester, tris (tallowfurkyl) phosphate, tris (mixed tetracosyl and hexacosyl) phosphate, diisodecyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, indecyl diphenyl phosphate, etc. Phosphate triesters.

phosphoric acid di(n-octyl) ester, Phosphoric acid di(2-ethylhexyl) ester.

phosphoric acid didecyl ester, phosphoric acid ditridecyl ester, phosphoric acid ditetradecyl ester, phosphoric acid dipentadecyl ester, phosphoric acid dihexadecyl ester, phosphoric acid dioctadecyl ester, Dioctadecenyl phosphate ester.

Phosphate di(mixed lauryl and myristyl) ester, phosphate di(tallow alkyl) ester, phosphate di(mixed tetracosyl and hexacosyl) ester Phosphate diesters.

Phosphoric acid mono(n-octyl) ester, phosphoric acid mono(n-octyl) ester
-ethylhexyl) ester, phosphoric acid monodecyl ester, phosphoric acid monododecyl ester, phosphoric acid monotridecyl ester, phosphoric acid mo/tetradecyl ester, phosphoric acid monopentadecyl ester.

Phosphate monodecyl ester, Phosphate monooctadecyl ester, Phosphate monooctadecenyl ester, Phosphate mono(mixed lauryl and myristyl) ester, Phosphate mono(tallow alkyl) ester, Phosphate mono(mixed) Phosphoric acid monoesters such as tetracosyl and hexacosyl) esters.

Salts of phosphoric acid esters and heavy metals, such as zinc salt of phosphoric acid (2-ethylhexyl) ester and aluminum salt of octadecyl phosphoric acid ester.

Salts of bis(2-ethylhexyl) phosphate and 2-ethyl-1-hexanamine, salts of bis(2-ethylhexyl) phosphate and tertiary dodecaneamine, bis(2-ethylhexyl) phosphate and Salt of octadecen-1-amine, Salt of phosphoric acid dioctyl ester and N,N-dimethyl-1-octadecanamine, Salt of phosphoric acid dioctyl ester and N,N-dimethyl-1-
Salt of octadecaneamine, salt of ditridecyl phosphate and 2-ethylhexaneamine, salt of phosphorus-resistant ditetradecyl ester and 2-ethylhexaneamine, dihexadecyl phosphate and 2-ethyl ester Salts of nophosphoric acid esters and organic amines, such as salts with hexaneamine, and salts of phosphoric acid dioctadecyl ester and 2-ethylhexaneamine.

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, such as ball mill, sand mill, attritor,
A typical method is to mix and knead using a conventionally known dispersing machine such as a horizontal continuous media dispersing machine, two rolls, three rolls, pressurized Nigu, Pan Bali mixer, and 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) A composition containing a high concentration of pigment and useful as a coloring agent for printing inks, paints, coating agents, synthetic resins, etc.
In this embodiment, the concentration of the pigment is between 20 and 95% and the concentration of the dispersant of the present invention is between 1 and 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 1. These include letterpress ink, lithographic ink, gravure ink for intaglio printing, screen ink, newspaper ink, and 24-hour printing ink.

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. are used, and are not particularly limited.

In addition, as paint vehicles, printing ink varnishes, coating agent vehicles, etc., conventionally known oil-based or water-based binder materials are used depending on the application. Oil-length alkyd resin, phenol modified, modified alkyd resin such as styrenated alkyd, 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 phenolic resin, rosin-modified maleic acid resin, phenol-modified maleic acid resin, polyurethane resin, styrene resin, styrene acrylic resin, styrene-diene copolymer, vinyl chloride modified resins such as vinyl acetate resins, vinyl acetate copolymers, ethylene vinyl acetate resins, butyral resins, petroleum resins, rosin esters, maleated rosin esters, drying oils, boiling oils, and the like.

Examples of thermoplastic resins include polyvinyl chloride resin, 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 ammonium, 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.

(Function/Effect) The phosphoric acid ester compound having a higher hydrocarbon group used in the present invention has been conventionally used as a dispersant for pigments in the field of color materials such as paints, printing inks, and plasti-2 colorants. There is no risk of deterioration or putrefaction due to acetylation or rancidity as seen with lecithin, a natural phospholipid, and it has excellent stability, and has excellent effects on surface modification of pigments and dispersion of pigments into media. be.

The phosphoric acid ester compound having a higher hydrocarbon group used in the present invention is a hydrophobic compound because it does not have a woody group, and has an ester bond.
Due to the charge-absorbing property of the ester bond and the lipophilic property of the hydrocarbon chain, it adsorbs onto the surface of the pigment and improves the wettability of the pigment to the medium, improving the dispersibility and fluidity of the pigment in the medium. It is also used as a flushing agent when flushing an aqueous filter cake of pigment, etc. It makes the surface of the pigment lipophilic or hydrophobic, and it can easily and efficiently flush and shing the pigment. I can do it.

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.

Example 1 Aqueous filter cake (pigment content 42%) of copper phthalocyanine blue pigment (C,1, Pig, 'Nto Blue 15-3)
238 parts were charged into a flasher, and then the following phosphoric acid ester compound as a dispersant was dissolved in a petroleum ink solvent and added, kneaded according to a conventional method, and flushed. During this flushing, the moisture in the cake was easily converted to aS, and the copper phthalocyanine blue pigment was transferred to the oily dispersion.

Tris(tridecyl) phosphate 24.0 parts Didodecyl phosphate 6.0 parts°1 Pine xolbent 70.0°Total
100.0 parts further remove moisture completely,
A flashed color containing copper phthalocyanine blue pigment was obtained. 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 copies Rinoyu Sanri'' Kosi: Yonnyeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy 9.5 copies total: 100 copies The ink obtained above was used to print on high-quality paper using an offset printing machine to obtain a clear indigo-colored print. .

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 Carmiso 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.

Example 2 Carbon black pigment 20 parts Tris-octadecenyl phosphate 7 parts Salt of dioctyl phosphate and N,N-dimethyl-1-octadecane 3 parts Offsade 1 Ink/varnish 65 total
The carbon black pigment was kneaded and dispersed using three rolls at a blending rate of 95 parts. The Car Pump Black pigment dispersed very well 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 inkituben
3.8 total 100
The mixture was sufficiently uniformly 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 the dispersant 1 used above, dispersants 2 to 9 were used, and the same excellent effects as above were obtained 11).

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 spirits
8.8 parts 6% cobalt naphthenate 0.3
Part 1 o, t.

A total of 100 parts of the formulation was thoroughly and 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 pigment (C, I.

Pigment Blue 15-3) dry crushed pigment 10 parts tris-octadecyl phosphate 3 parts salt of bis(2-ethylhexyl) phosphate and octadecen-1-aminoester 2 parts quidyrol 11 parts bunol
41 total
A dispersion of copper phthalocyanine blue pigment in a mixed solvent of quidylol-butanol was obtained by dispersing 30 parts using a continuous horizontal media disperser.

Next, a paint was prepared using the following recipe.

Solvent dispersion containing copper phthalocyanine blue and phosphoric acid ester compound obtained above 3 parts Rutile titanium white 14 parts Thermoplastic acrylic resin
70 part dollar all 6
．． 8 parts Kijirol 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.

Claims (4)

[Claims] (1) In a pigment composition consisting of a pigment and a dispersant,
An oil-based pigment composition characterized in that the dispersant is a phosphoric acid ester compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, one or more of the three R in the formula has a carbon number of 8 to
30 hydrocarbon groups, and if there is a remainder, one or two of the remaining R's have a hydrocarbon group having 1 to 7 carbon atoms, hydrogen, a heavy metal cation, and a hydrocarbon group having 8 to 30 carbon atoms. selected from the group consisting of cations. ) (2) The pigment composition according to claim (1), wherein the dispersant is a phosphoric acid ester compound in which all three R's are hydrocarbon groups. (3) The dispersant is a phosphoric acid ester compound in which all three R's are hydrocarbon groups, and two or one R's are hydrocarbon groups and one or two of the remaining R's are hydrogen or cation. The pigment composition according to claim (1), which is a mixture with a phosphoric acid ester compound. (4) The dispersant is a phosphoric acid ester compound in which all three R's are hydrocarbon groups, and two or one R's are hydrocarbon groups and one or two of the remaining R's are hydrocarbon groups. The pigment composition according to claim 1, which is a mixture with a phosphoric acid ester compound having a cation.