JPH062222B2 - Dispersant - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a dispersant, and more particularly to a dispersant having excellent fluidity and dispersion stability in a dispersion system when a pigment, which is an insoluble fine powder, is dispersed in an organic liquid.

[Prior art]

In various coating compositions such as printing inks and paints, practically useful pigments must be composed of fine particles in order to exhibit a clear color tone and high tinting strength. Therefore, dispersion of the pigment in the non-aqueous organic liquid is one of the important steps in the production of printing inks and paints. However,
When a pigment is dispersed in a non-aqueous vehicle, it is difficult to obtain a coloring material composition having excellent fluidity and storage stability, especially at high concentrations, and various problems that affect the production process and the quality of the product It is known to cause For example, a dispersion liquid containing a pigment composed of fine particles has a high viscosity, and the viscosity is remarkably increased during dispersion, stirring, mixing, or during transportation, storage, etc., and further gelation is difficult. May be. In addition, separation of the vehicle and the pigment, sedimentation, aggregation, color separation of the mixed pigment, deterioration of coloring power, deterioration of gloss, and leveling failure may occur. In addition, coloring materials with good coating such as printing ink or paint are
It is composed of finely dispersed pigments and has a high pigment concentration. That is, in order to produce a high-concentration and finely-dispersed dispersion, a dispersant or the like is used to loosen the agglomerated particles,
In addition, maintaining stability is a requirement for obtaining a good dispersion. Various pigment dispersants have been disclosed so far. For example, coloring the pigment derivative disclosed in JP-A-59-227951 limits the pigments that can be used and is not versatile. Further, a polyester which is a dehydration condensation product of a hydroxycarboxylic acid disclosed in JP-B-54-34009 and JP-B-63-
No. 30057, the reaction product of the polyester with polyethyleneimine, JP-A No. 62-4433, the reaction product of the polyester with polyoctamethylene polyamine, JP-A No. 63-12335, the polyalkyleneimine. Dispersion of compounds obtained by further reacting the reaction product of epoxide with epoxide with polyester is effective in weakly polar organic liquids such as aliphatic petroleum fractions and aromatic hydrocarbons, but in terms of long-term storage stability. It is inferior and no dispersion effect is observed in liquids with strong polarity such as alcohols. As described above, various dispersants have been disclosed in the past, but as a pigment dispersant, a dispersant that has not yet achieved sufficient performance to solve these problems has been demanded.

[Problems to be Solved by the Invention]

INDUSTRIAL APPLICABILITY The present invention is extremely effective in preventing the aggregation of pigments in the dispersion liquid when dispersing fine powders, solids, particularly organic and inorganic pigments in various organic liquids, and forming a stable dispersion liquid. The object of the present invention is to provide a dispersant which has an extremely small odor or is substantially odorless and has no adverse effect due to coloring in practical use.

[Means and Actions for Solving the Problems]

The present invention has been made focusing on such a conventional problem. That is, the following general formulas (1) to (2) A [(CxH ₂ xO) b (CyH ₂ yO) c (CxH ₂ xO) dH] e ...
(1) A _{[(CxH 2 xO) b (CyH} 2 yO) c (B) H ] e ...
(2) (In the formula, A is a residue obtained by removing active hydrogen from a polyamine compound having e active hydrogen atoms, a polyalkyleneimine compound or a derivative thereof, x is 2 or 3, and y is 8 to 30.
, B is an integer of 0 or 1 to 50, c is an integer of 0 or 1 to 10 in part, and the average equivalent number of CyH ₂ yO per molecule is 0.6e to 10e, d is an integer of 1 to 50, e is an integer of 6 to 300, B is an oxyalkylene chain obtained by block-polymerizing or random-polymerizing ethylene oxide and / or propylene oxide), which is a dispersant. The dispersant represented by the general formulas (1) and (2) is a polyether polyol obtained by reacting a polyamine, a polyalkyleneimine or a derivative thereof as a starting material with a specific alkylene oxide in a specific order. As the starting material used in the present invention, 6 to 300 active hydrogen is contained in the molecule.
Examples of the polyamine include polyalkylenepolyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and tripropylenetetramine, polyallylamine, polyethyleneimine, polypropyleneimine, and the like.
Polyethyleneimine is not a perfect linear structure usually obtained by polymerization of ethyleneimine, but has a branched structure containing primary, secondary, and tertiary amine nitrogen, but contains 6 to 300 active hydrogens in the molecule. Any linear branched polyamine compound is effective as long as it is a heterocyclic ring partially containing nitrogen. The polyamine and polyethyleneimine have various positive chemical reactions, and if the remaining active hydrogen is in the range of 6 to 300, its derivative can be used as a starting material. Typical examples are shown below. (A) Reaction products with aldehydes and ketones (b) Reaction products with alkyl halides (c) Reaction products with isocyanates and thioisocyanates (d) Reactions with active double bonds Products (e) Reaction products with epihalohydrins (f) Reaction products with cyanamides, guanidines, urea, etc. (g) Reaction products with carboxylic acids, acid anhydrides, acyl halides, etc. One kind or two or more kinds can be used, and the alkylene oxide adduct can be easily produced by a usual method. That is, the starting polyamine compound is heated to 100 to 180 ° C. under an alkaline catalyst to
The target product is obtained by addition reaction of alkylene oxide at 10 atm. The dispersant of the present invention contains a long-chain alkylene oxide having 8 to 30 carbon atoms as an essential component as shown in the general formulas (1) and (2), and further contains ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter PO). Abbreviated) is addition-polymerized. Examples of the long-chain alkylene oxide include α-olefin oxide, and those having an alkyl group having 8 to 30 carbon atoms are effective. In this case, α-olefin oxide may be used as a mixture of two or more kinds having different carbon numbers. good. An average of 0.6 to 10 molar equivalents of α-olefin oxide needs to be added to one active hydrogen, and an excellent dispersion effect cannot be obtained outside this range. Furthermore, it is necessary to carry out addition polymerization of EO and / or PO as the alkylene oxide, and the order of the addition reaction is important for obtaining an effective dispersant. That is, when the addition order of the formula (1) is specifically described, it is starting material-α-olefin oxide-EO or PO starting material-EO or PO-α-olefin oxide-EO or PO. An average of 0.6 to 10 mole equivalents of α-olefin oxide and 1 to 50 moles of EO or PO added to 1 active hydrogen of the starting material, EO
Alternatively, after adding PO in an amount of 1 to 50 mol, α-olefin oxide is added in an average of 0.6 to 10 mol equivalent, and further, EO or PO is added in an amount of 1 to 50 mol. The compound of the formula (2) is obtained by subjecting the above-mentioned α-olefin oxide addition compound to addition polymerization of EO and / or PO in a block form or in a random form with respect to one active hydrogen in a total amount of 2 to 100 mol. Is. In this case, the block-like portion and the random-like portion may be mixed, but the addition method is preferably block-like and the degree of polymerization of one block is 5 or more, and the terminal of the compound is an oxyethylene chain. , It is effective regardless of the oxypropylene chain. Further, a derivative obtained by converting a part or all of the terminal hydroxyl groups of the above polyether polyol compound into a phosphoric acid ester and a sulfuric acid ester is also effective. The pigment dispersed in the organic liquid by the dispersant of the present invention is usually a fine powder solid having a particle size of 20 μm or less, such as titanium dioxide, red and yellow iron oxide, barium sulfate, aluminum hydroxide, Calcium carbonate, talc, clay, silica, lead uromate, zinc chromate, strontium chromate, carbon black, cadmium yellow, cadmium red, rouge, iron black, zinc white, navy blue,
Examples include inorganic pigments such as ultramarine blue, azo pigments, lakes, toners, phthalocyanine pigments, perylene, perinone pigments, isoindolinone pigments, quinacridone pigments, and organic pigments such as dioxazine pigments. As used herein, "lake" means a water-insoluble salt or complex of an organic dye precipitated on a water-insoluble inorganic carrier such as alumina, and "toner" is particularly insoluble in water of an azo dye, or Extremely poorly soluble calcium, strontium,
Also, it means a salt or a complex of barium. Examples of the organic liquid used in the dispersant according to the present invention include toluene, aromatic hydrocarbons such as xylene, mineral spirits, petroleum hydrocarbons such as mineral terpenes, chloroform, perchlorethylene, trichloroethylene, and chlorobenzene. Such as halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as isophorone, ethyl acetate, butyl acetate, amyl acetate, esters such as cellosolve acetate, alcohols such as methanol, ethanol, butanol Examples of the organic liquid include ketones, alcohols, cellosolves, and esters, and cellulosolves such as ethyl cellosolve and butyl cellosolve. Of course, two or more kinds of these may be mixed solvents, and known alkyd resins, epoxy resins, epoxy ester resins, melamine resins, acrylic resins, polyamide resins, polyurethane resins, polyester resins, vinyl chloride and vinyl chloride. A mixed system of resin, phenol resin, nitrocellulose resin, etc. may be used. Further, as an auxiliary agent for printing inks and paints, for example, a thickener, an anti-sagging agent, a color separation preventing agent, a viscoelasticity adjusting agent, a wetting agent, a defoaming agent, a rust preventive agent, a slip agent, a drier, an ultraviolet absorber. In some cases, antifouling agents, antiseptics, flame retardants, etc. may be added, but these may be included. The dispersant of the present invention is used in a proportion of 0.01 to 15% by weight, preferably 0.1 to 10% by weight, based on the whole dispersion. If the amount used is less than 0.01% by weight, the effect is small, and if it exceeds 15% by weight, the effect is not significantly improved and it is economically disadvantageous. The pigment content in the dispersion is 5 to
Although it is 80% by weight, these numerical values should be selected from various combinations according to the pigment used, the organic liquid, and the purpose of use. In using the dispersant of the present invention, any disperser may be used, and examples thereof include a ball mill, a sand mill, a visco mill, a roll mill, a kneader, an attritor, a high speed mixer and a homomixer. As the method of using the dispersant of the present invention, a method of adding it alone in an organic liquid, a method of adding a mixed composition of a pigment and a dispersant, a method of adding it to a dispersion of an organic liquid and a pigment, and any of these are intended. And the effect is obtained. The dispersant of the present invention may be used alone, and other non-aqueous dispersants such as polyoxyethylene nonylphenyl ether, sorbitan oleate, lecithin, polyoxyethylene octyl ether phosphate, calcium dodecylbenzene sulfonate. , Calcium petroleum sulfonate, fatty acid metal soap and the like may be used in combination. EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. The various dispersants used here are shown in Table 1. In addition, the part in an Example means a weight part. Example 1 Carbon black (C.I. Pigment Blac
k7) 35 parts, n-butanol 58 parts, dispersant A7 parts,
Further, 180 parts of a steel ball having a diameter of 2 mm was shaken and dispersed by a paint shaker for 2 hours. The dispersion had good deflocculation of the pigment and excellent fluidity, and was suitable for the production of gravure printing inks, and even after standing for 45 days, neither aggregation nor sedimentation was observed and good dispersion stability was exhibited. As a result of performing the same test using each of the dispersants B to Q instead of the dispersant A, the same dispersion liquid was obtained. Example 2 Carbon black (C.I. Pigment Blac
k7) 30 parts, ethanol 40 parts, toluene 20 parts, vinyl chloride-vinyl acetate copolymer resin 4 parts, dispersant D6
And 180 parts of a steel ball having a diameter of 2 mm were shaken and dispersed by a paint shaker for 3 hours. The dispersion had good deflocculation of the pigment and was suitable for the production of gravure printing inks, and even after standing for 45 days, neither aggregation nor sedimentation was observed and good dispersion stability was exhibited. As a result of performing the same test using each of the dispersants A to C and E to Q instead of the dispersant D, the same dispersion liquid was obtained. Example 3 Brilliant Carmine 6B (C.I. Pigm-ent
25 parts of Red 57), 20 parts of methyl ethyl ketone, 40 parts of ethanol, 10 parts of butyl acetate, 5 parts of dispersant A, and 200 parts of a steel ball having a diameter of 2 mm were shaken and dispersed by a paint shaker for 2 hours. The dispersion had good deflocculation of the pigment and excellent fluidity, and was suitable for the production of gravure printing inks, and even after standing for 45 days, neither aggregation nor sedimentation was observed and good dispersion stability was exhibited. As a result of performing the same test using each of the dispersants B to Q instead of the dispersant A, the same dispersion liquid was obtained. Example 4 Phthalocyanine Bull- (CI Pigme-nt B
lue15-4) 23 parts, ethanol 45 parts, methyl isobutyl ketone 22 parts, butyl acetate 5 parts, dispersant A 5 parts, and a steel ball having a diameter of 2 mm 180 parts were shaken and dispersed by a pain shaker for 3 hours. The dispersion deflocculates the pigment well and is suitable for gravure printing ink production.
No agglomeration or sedimentation was observed even after standing for a day, showing good dispersion stability. As a result of performing the same test using each of the dispersants B to Q instead of the dispersant A, the same dispersion was obtained. Example 5 Disazo Yellow AAA (CI Pigme-nt Y
Ellow 12) 23 parts, n-butanol 40 parts, methyl ethyl ketone 30 parts, dispersant J 7 parts, and a steel ball having a diameter of 2 mm 180 parts were shake-dispersed for 3 hours with a paint shaker. The dispersion had good deflocculation of the pigment and was suitable for the production of gravure printing inks, and even after standing for 45 days, neither aggregation nor sedimentation was observed and good dispersion stability was exhibited. The same dispersion was obtained using the following pigments instead of disazo yellow AAA. (1) Permanent Red 2B Barium (CI Pigmentnt Red48-1) (2) Lake Red C (〃 Red53-1) (3) Dioxazine Violet (〃 Biolet23) Example 6 Titanium oxide (CI) . Pigment Wh-ite
6) 65 parts, 20 parts of ethanol, 12 parts of butyl acetate, 3 parts of a dispersant H and 130 parts of a steel ball having a diameter of 2 mm were shaken and dispersed by a paint shaker for 2 hours. The dispersion has good deflocculation of the pigment, has excellent fluidity, and is suitable for the production of gravure printing ink, and it aggregates even after being left for 30 days.
No sedimentation was observed, indicating good dispersion stability. It showed dispersion stability instead of titanium oxide. Instead of titanium oxide, zinc white (CI Pi-gmen
t White4), barium sulfate (CI Pigm)
ent White21), or dark blue (CI Pig)
The same dispersion was obtained using ment Ble 27). Comparative Example 1 Carbon black (CI Pigment Blac
The same test as in Example 1 was carried out using 25 parts of k7), 65 parts of n-butanol, and 10 parts of dispersant R, and as a result, a gelled mixture was obtained immediately after shaking and a dispersion could not be obtained. The same test was performed using each of the dispersants S to U instead of the dispersant R, and as a result, a gel mixture was similarly obtained, and no dispersion was obtained.

【The invention's effect】

The pigment dispersant according to the present invention shows particularly excellent coloring properties, coating gloss and fluidity, and storage stability when applied to a surface coating material, for example, when used in the production of non-aqueous paints and printing inks. It can be improved. That is, it is possible to mention flocculation, flooding, floating prevention, and leveling improvement by stabilizing the pigment dispersion state. In particular, it is useful when preparing a pigment dispersion for producing a gravure printing ink. The pigment dispersion referred to here is a system consisting of pigment-organic solvent-dispersant, and since a printing ink can be easily prepared by blending with a desired vehicle according to the purpose of use, the number of Ikibees is large. It is possible to reduce the width. Furthermore, compared with ordinary printing inks, since it is possible to knead meat at a much higher pigment concentration in a short time compared to ordinary printing inks, it is possible to reduce the labor cost, electric power, and running cost required for milling, and to disperse. Since good fluidity can be maintained even if the pigment concentration in the liquid is increased, storage and transportation costs can be reduced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09D 11/02 PTG 7415-4J

Claims (2)

[Claims] 1. The following general formulas (1) to (2) A [(CxH ₂ xO) b (CyH ₂ yO) c (CxH ₂ xO) dH] e ...
(1) A _{[(CxH 2 xO) b (CyH} 2 yO) c (B) H ] e ...
(2) (In the formula, A is a residue obtained by removing active hydrogen from a polyamine compound having e active hydrogen atoms, a polyalkyleneimine compound or a derivative thereof, x is 2 or 3, and y is 8 to 30.
, B is an integer of 0 or 1 to 50, c is an integer of 0 or 1 to 10 in part, and the average equivalent number of CyH ₂ yO per molecule is 0.6e to 10e, d is an integer of 1 to 50, e is an integer of 6 to 300, B is an oxyalkylene chain obtained by block-polymerizing or randomly polymerizing ethylene oxide and / or propylene oxide). 2. The dispersant according to claim 1, wherein the dispersion medium is one or more organic liquids selected from alcohols, ketones, cellosolves, and esters.