JPS6164323A - Pigment dispersant - Google Patents

Abstract

PURPOSE:To improve the dispersing stability of pigment, by preparing a dispersant from a reaction product of acid anhydride represented by a specific general formula and polyoxyethylene glycol monoether represented by a specific general formula. CONSTITUTION:A pigment dispersant is prepared from a carboxyl group- containing polyether ester compound being a reaction product of 5-(2,5- dioxotetrahydro-3-franyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride represented by formula I and polyoxyethylene glycol monoether represented by formula II (wherein R is a 6-20C alkyl group, an alkenyl group or an aralkyl group and n is 2 or more). It is pref. to react 2-3mol of polyoxyethylene glycol monoether represented by the formula II with 1mol of acid anhydride represented by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides particularly improved fluidity and dispersion stability for the dispersion of inorganic or organic pigments in organic liquids. It relates to compounds that have properties that impart properties, and its scope of application extends to the general field of various printing inks and paints, such as lithographic inks, gravure inks, and metal inks.

In general, practically useful pigments that exhibit high tinting power, excellent gloss, and clear color tones are composed of fine particles in compositions for various light coatings such as printing inks and paints.

However, when fine particles such as various known pigments are dispersed in non-aqueous vehicles such as offset inks, gravure inks, and paints, it is difficult to obtain dispersions with excellent fluidity and storage stability. This often causes various problems that significantly affect the manufacturing process and the quality of the resulting product.

That is, dispersions containing pigments consisting of fine particles often exhibit high viscosity, which makes handling difficult when forcing the product out of the dispersion machine or during transportation, and in some cases, significantly increases the viscosity during storage. It may thicken and become unusable.

A non-aqueous printing ink or coating is a pigment dispersion in which the pigment is added to an organic liquid containing a vehicle polymer and other auxiliaries; the rheological properties of the dispersion are essentially depends on the nature of the pigment, which consists of fine particles.

In other words, it may be extremely viscous and show almost no fluidity, or it may have poor wettability with organic liquids and not disperse at all.
In systems where the viscosity of the dispersion increases significantly over time, the pigment is present in substantially complete K or extremely aggregated state, and this type of colorant only has poor fluidity. Suddenly,
The coloring power is inferior compared to coloring materials with good dispersibility], and the coated surface lacks smoothness, so the gloss tends to be significantly lower.

Many attempts have been made to prevent the above-mentioned agglomeration of pigments, and these attempts have been recognized to be effective to some extent.

For example, in British Patent No. 949,739, R
represents an aliphatic group, or R1 and R2 together with the nitrogen atom to which they are bonded represent a heterocyclic group, and m is 1 to 4.
shows. ) The use of aggregation-inhibiting 7 talocyanine derivatives represented by 1. +41
．． No. 4o7 describes a dispersant for cyanine pigments obtained by reacting copper 7-merocyanine sulfochloride with p-dodecylaniline. Needless to say, however, pigments treated with these phthalocyanine derivatives can only be used in limited applications where the color tone is similar.

Furthermore, JP-A-55-112273 discloses that certain polyurea derivatives are effective for pigment dispersion, and British Patent No. 1,473,380 states that 12 It has been reported that an acid amide obtained by dehydrating hydroxystearic acid and 3-nomethylaminopropylamine is effective as a dispersant.
No. 34009, UK Patent No. 1.342,746 and US Patent No. 3.778,287 F! In the AIIE book, 1
Dispersants related to I-reesters obtained by dehydrating 2- and hydroxycardoic acids such as droxystearic acid or salts thereof have been reported, and furthermore, dispersants related to terminal alkylamino groups derived from the polyesters or 4- British Patent No. 1,373,66 describes that esters or amides having an ammonium base are effective as pigment dispersants.
No. 0 and Japanese Patent Publication No. 57-25251.

However, although all of these dispersants have been shown to have a certain degree of performance, they are still not sufficient, and for example, in baking-type metallic inks and metallic paints, there is a phenomenon in which the adhesion of the paint film to the metal decreases. Is recognized.

[Problems to be solved by the present invention]

The purpose of the present invention is to improve the adhesion between pigment dispersions and metals when dispersing various pigments in various organic liquids depending on the purpose, since conventional dispersants cannot be used for all types of dispersion. In view of the problems with power, dispersibility of metal powder pigments, etc.,
A dispersion that allows pigments to be easily and finely dispersed in any case, maintains the dispersion stability of the pigment in the dispersed organic liquid, and improves the adhesive strength between the organic liquid and metal. The aim is to provide agents for

[Means for Solving the Problems] As a result of extensive research, the present inventors have discovered that when dispersing fine powdery solids, especially organic and inorganic pigments, in a non-polar organic liquid, We have discovered a new group of compounds that are extremely effective in preventing the aggregation of pigments and forming stable dispersions.

The pigment dispersant of the present invention has 5-(2,
5-Dioxotetrahydro-3-furanyl)-3-methyl-3-7chlorohexene-1,2-dicalde7 acid anhydride (hereinafter referred to as py(rylene maleic anhydride adduct)), and the general formula (IDRO+CH2cH2o+-Ha[ ) (In the formula, R means an alkyl, alknyl, or aralkyl group having 6 to 20 carbon atoms, and n is 2 or more.) It consists of a group-containing polyetherester compound.

Piperylene maleic anhydride adduct is
1955, 3-methyl-4-cyclohexene-1,2- obtained by the reaction of trans- or cis-1,3-pentadiene with maleic anhydride.
It is obtained by reacting dicargenic acid anhydride with maleic anhydride, and is not only useful as a raw material for heat-resistant/IJ amide resin, but also
As described in the specification of No. 14, it is a compound useful as a curing agent for epoxy resins, but it has a power/L/de obtained by reacting with polyoxyethylene glycol monoether represented by the general formula Ql). It has not been previously known that a xyl group-containing I group-containing terether ester compound powder is useful as a powder.

Examples of the compound represented by formula 01) used in the present invention include ? Lyoxyethylene lauryl ether, phoroxyethylene cetyl ether, polyoxyethylene stearyl ether, ? Lyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether,
Examples include polyoxyethylene nonylphenyl ether. Oxyethylene a and n in this compound are 2 or more. Of course, this compound may be a single compound, but it may also be a mixture of the exemplified compounds in any molar ratio. It goes without saying that it may be a mixture of compounds with different n's in the oxyethylene chain, or it may be an oxypropylene chain added to the oxyethylene chain as long as it does not cause any hindrance. In particular, this polyoxyethylene glycol monoether is a mixture in which n has an average value of 2 to 40 and is commercially available as a nonionic surfactant, and is suitable from that point of view. .

When such birylene maleic anhydride adduct and I-lyoxyethylene glycol monoester are called an acid component and an alcohol component, respectively, the reaction ratio of these acid components and alcohol components is preferably 1 mole of the acid component and the dialcohol component. 2 to 3 equivalents of each alone or as a mixture. In short, it is sufficient that the caroxyl group is contained in a sufficient proportion to exhibit the dispersion effect aimed at by the present invention. If the alcohol component is less than 2 equivalents relative to the acid component,
Cal? The acid anhydride group remains, and if more than 3 equivalents are reacted, esterification will proceed excessively and the content of carboxyl group will decrease, and in either case, the desired performance will decrease, so this is not suitable. .

The esterification reaction of the same components can be carried out using known catalysts such as valine a.
12 in the presence of ', p-toluenesulfonic acid, methanesulfonic acid, tetra-n-butyl titanate, etc.
It is carried out by removing the produced water from the system while heating to 0 to 200°C, preferably 140 to 185°C, preferably by passing nitrogen gas over the reaction mixture, or by azeotroping the reaction with water. It is advantageous to carry out the reaction in the presence of an aromatic hydrocarbon that forms a mixture, such as toluene or xylene, and to remove the produced water azeotropically from the system (of course, the piperylene maleic anhydride adduct is Because it is a thing,
It goes without saying that if 2 equivalents or less of the alcohol component is added stoichiometrically, only esterification by addition reaction will occur and no water will be distilled out). The degree of progress of the esterification reaction can be determined by measuring the acid value or measuring the residual degree of the raw alcohol component by high performance liquid chromatography.

Examples of the organic liquid used in the dispersant of the present invention include aromatic hydrocarbons such as toluene and xylene, petroleum hydrocarbons such as mineral spirits and mineral turpentine, monorhodanide hydrocarbons such as chloroform and chlorobenzene, Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexene, and isophorone, and esters such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate, but of course mixed solvents of two or more of these It may also be a mixed system with known alkyd resins, epoxy ester resins, melamine resins, acrylic resins, polyamide resins, -urethane resins, vinyl resins, nitrocellulose resins, etc.

Fine powdery solids, usually having a diameter of 20 microns or less, which are dispersed in organic liquids by the dispersants of the present invention include titanium dioxide, red and yellow iron oxides, barium sulfate, aluminum hydroxide, calcium carbonate, Merck Various inorganic pigments, azo pigments, azo lakes, including colorants, fillers, conductive materials, magnetic materials, etc., clay, lead chromate, strontium chromate, carden black, metal powders such as aluminum, brass, iron, etc. Examples include organic pigments such as pigments, phthalocyanine pigments, isoindolinone pigments, and quinacridone pigments.

The relative proportion of the dispersant according to the invention in the dispersion liquid is 0.1 to 100%, preferably 0.1% to the pigment content.
The pigment content in the dispersion is preferably 5 to 80%, preferably 10 to 7%.
It is 0%.

〔Effect of the invention〕

The pigment dispersants according to the invention, when used in surface coating applications, for example in the production of non-aqueous ink, lacquers and printing inks, exhibit particularly good color strength, film gloss and fluidity;
It exhibits storage stability and improves fluidity, especially for burn-out metal inks with epoxy ester/melamine resin vehicles, as well as improves the metallurgy of the paint film, as is often the case with conventional dispersant formulations. It has the advantage that no decrease in adhesive strength is observed.

Further application advantages include that compared to ordinary printing inks, it can be milled in a much shorter time with a much higher pigment concentration, which reduces labor, electricity, and milling consumable costs. Since good fluidity is maintained even if the pigment concentration in the liquid is increased, storage and transportation costs can be reduced.

The advantages of the pigment dispersant according to the present invention are (a) improved efficiency of pigment dispersion time; , prevention of floating, improvement of leveling, prevention of color separation, etc.

〔Example〕

The present invention will be described in more detail below with reference to Examples, but of course the gist and scope of the present invention are not limited by these Examples.

In addition, parts in the examples mean parts by weight.

Example 1 Preester A Epicron ■B-4400 (Dainippon Ink Chemical Co., Ltd.:
5-(2,5-dioquinetetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarzenic anhydride) 66.1.9. Emuldan ■ 105 (Kao Seki #, manufactured by Co., Ltd.: polyoxyethylene lauryl ether, HLB = 9.7) 181.0 #, a mixture of toluene 20jI and tetra-n-butyl titanate sail 1
1! was added and stirred at 120° C. for 5 hours in a nitrogen stream. Next, volatile matter was removed by keeping at 120° C. for 3 hours under a reduced pressure of 30 mHg, and 247. O, F pale reddish brown, transparent;
A viscous oil was obtained. The acid value of this thing is 112 m9K
OH/F Teah7'c.

Example 2-Reester B Epic c+ 7■B -440066,11,x-=r
903 (, ff IJ oxyethylene 7 nonylphenyl ether, HLB = 7.8) 279
．． 0, F, tetra-n- in a mixture of xylene 40.9
0.2.9 of butyl titanate was added, and the mixture was heated to reflux at 180° C. for 7 hours in a nitrogen stream, and water of 4.4.9 was separated using a Dean-Stark trap. 30% of the reaction product
The volatiles were removed by keeping at 160° C. for 4 hours under the reduced pressure of wIHH to obtain a light reddish brown, transparent, viscous oil. The acid value of this product was 41 moKoH/I.

Example 3 Polyester C Epipo 7 ■ B -440066, IJi', Nirkl'n ■ 905 (d? IJ Oxyethylene 7 Nonylphenyl Ether, T (LB = 9.2) 2
04.0 g, tetra-n- in a mixture of 309 toluene
Butyl titanate sail II was added, and the mixture was stirred at 120° C. for 5 hours in a nitrogen stream. 150 under a vacuum of 30 tmHg at
The volatiles were removed by keeping at 0.degree. C. for 3 hours to give a light reddish brown, clear, viscous oil 270,O,F. The acid value of this thing is 1
It was 11.6m9KOH/y.

Example 471? Lyester D Epicron ■B -440066,1,F,:x -t
k) f:y■404 (<lioxyethylene oleyl ether, HLB = 8.8) 240.2,
P, ) Ruen 30. F was mixed, 0.1 g of tetra-n-butyl titanate) was added, and the mixture was stirred at 120° C. for 5 hours in a nitrogen stream. The reaction product was heated under a reduced pressure of 30 mHg.
The volatiles were removed by holding at 50° C. for 3 hours, yielding a pale tan, clear, viscous oil 306.0.9. The acid value of this product was 88.1m9KOH/, F. Example 5f! Lyester E Epicron ■B -440026,4! ! , Emalden ■810 (yl"lioxyethylene octylphenyl ether, HLB = 13.1) 119.7.9
, ) 0.19% of tetra-n-butyl titanate was added to the mixture of 20I of toluene, and the mixture was stirred at 150°C for 3 hours.

The mixture was then kept at the same temperature for 30 m) under reduced pressure (H) for 3 hours to remove low boilers, yielding a pale yellow-brown, viscous oil of 146.ON.

The acid value of this product was 76.8 m9KOH/7.

Example 6 1-(2'-sulfo-4'-methylphenylaso)-
2-naphthol-3-cal? calcium acid v-13
Department, $! J ester AL5 m and 'cF) Luene 5.
5 parts of the mixture was combined with 10 parts of rasp beads having a particle size of 4 mm and shaken for 3 hours in a Dobeville paint shaker to peptize and disperse the mixture. The dispersion was suitable for use in gravure printing inks and showed no tendency to agglomerate or settle for at least one week - Example 6 parts of Furchill type titanium white 5R-IA (manufactured by Sakai Chemical Co., Ltd.), I-Reester B A mixture of 5 parts of O2 and 3.5 parts of xylene was shaken for 3 hours in a Red Devil paint shaker with 10 parts of ceramic galls having a particle size of 4 to cause peptization and dispersion. The dispersion exhibited good fluidity and was suitable for use in gravure printing inks, and did not aggregate or settle for at least one week.

Example 8 Thioxide R-CR (rutile titanium white coated type manufactured by BTP) 6 parts, ? A mixture of 0,006 parts of diester and 3.4 parts of isophorone was poured into a ceramic mold with a particle size of 4 m.
The mixture was shaken for 3 hours using a Dovpil paint shaker to sufficiently deflocculate and disperse the mixture. The dispersion was suitable for the production of gravure printing inks and showed no tendency to flocculate or settle for at least one week.

Example 9 15 parts of calcium lake of 1-(2'-sulfo-47-methyl-5'-chlorophenyl 7zo)-2-naphthol-3-cargenic acid, 2.4 parts of polyester D, and 25 parts of toluene were mixed, The mixture was peptized and dispersed by shaking for 1 hour in a paint shaker manufactured by Red Devil Co., Ltd. together with steel peel having a particle size of 3 m. The dispersion exhibited good fluidity and was suitable for producing gravure printing inks, and no agglomeration or sedimentation was observed for at least one week.

Example 10 Rutile type titanium white SR-IA (manufactured by Sakai Chemical Co., Ltd.) 6.5 parts polyester KO, 5 parts, xylene 3 parts, 10 parts of ceramic tea with a particle size of 3 was added and mixed in a paint shaker. The mixture was shaken for 4 hours to fully deflocculate and disperse.

The dispersion exhibited good fluidity and showed no tendency to flocculate for at least one week, making it suitable for the production of gravure printing inks.

Claims (1)

[Scope of Claims] 1. 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride represented by formula (I), and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) General formula (II) RO-(CH_2CH_2O)-_nH(
II) (In the formula, R means an alkyl, alkenyl or aralkyl group having 6 to 20 carbon atoms, and n is 2 or more.) A carboxyl group obtained by reacting with polyoxyethylene glycol monoether represented by A pigment dispersant comprising a polyether ester compound. 2. Claim 1, wherein the carboxyl group-containing polyether ester compound is obtained by reacting 2 to 3 moles of polyoxyethylene glycol monoether with 1 mole of acid anhydride (I). Pigment dispersant as described. 3. Polyoxyethylene glycol monoether is n
Pigment dispersant according to claim 1, which is a mixture known as nonionic surfactants, having an average value of 2 to 40.