KR102535901B1 - Nonaqueous dispersant and nonaqueous dispersion composition - Google Patents

Abstract

(R 은 탄소수 1 ∼ 22 의 직사슬 혹은 분기사슬형의 탄화수소기이다. A¹O 는 옥시에틸렌기이며, m 은 1 ∼ 30 이다. A²O 는 탄소수 3 ∼ 4 의 옥시알킬렌기이며, n 은 1 ∼ 30 이다. 0.1 ≤ m/n ≤ 10, 또한 5 ≤ m ＋ n ≤ 40 의 관계를 만족한다. a 는 방향 고리의 수이며, 1 ∼ 2 이다. M 은 수소 원자, 암모늄 또는 알칸올암모늄을 나타낸다.)(Project) To provide a non-aqueous dispersant capable of dispersing a fine particle dispersion in a non-aqueous solvent at a high concentration and imparting excellent dispersion stability.
(Means for solution) The non-aqueous dispersing agent represented by Formula (1) is provided.
[Formula 1]

(R is a linear or branched hydrocarbon group having 1 to 22 carbon atoms. A ¹ O is an oxyethylene group, m is 1 to 30. A ² O is an oxyalkylene group having 3 to 4 carbon atoms, and n is 1 to 30. 0.1 ≤ m/n ≤ 10, and satisfies the relationship 5 ≤ m + n ≤ 40. a is the number of aromatic rings and is 1 to 2. M is a hydrogen atom, ammonium or alkanol represents ammonium.)

Description

Non-aqueous dispersant and non-aqueous dispersion composition {NONAQUEOUS DISPERSANT AND NONAQUEOUS DISPERSION COMPOSITION}

The present invention relates to a non-aqueous dispersant used for dispersing a dispersion such as organic or inorganic powder into a non-aqueous solvent, and a non-aqueous dispersion composition containing the non-aqueous dispersant. More specifically, a non-aqueous dispersant capable of dispersing a dispersion in a high concentration in a non-aqueous solvent with a small amount of addition and imparting excellent dispersion stability, and a non-aqueous dispersion composition containing the non-aqueous dispersant It is about.

BACKGROUND OF THE INVENTION Non-aqueous dispersion compositions in which dispersions such as organic powders or inorganic powders are dispersed in non-aqueous solvents are used in various industrial fields. Organic powders include, for example, organic pigments, and nonaqueous dispersion compositions containing organic pigments are used in paints, printing inks, inkjet inks, color filter resists, writing instrument inks, and the like. Examples of the inorganic powder include ceramic powder and metal powder, and the non-aqueous dispersion composition containing the ceramic powder is a dielectric layer of a multilayer ceramic capacitor, a semiconductor substrate, various sensors, and electronic components such as liquid crystal display elements. In addition, it is used for abrasive materials and fireproof materials. In addition, a non-aqueous dispersion composition containing metal powder is widely used as an electronic material for forming electrodes, for example, as a conductive paste or conductive ink.

In recent years, in electronic parts applications, improvement in product characteristics such as miniaturization, high capacity, and high efficiency of parts has been demanded. In order to satisfy these demands, micronization of dispersions such as ceramic powder and metal powder as raw materials, High concentration of the dispersion in the dispersion composition is required. When preparing a non-aqueous dispersion composition, organic powder or inorganic powder alone is often insufficient in dispersibility, so for the purpose of improving the fluidity and storage stability of the non-aqueous dispersion composition, a dispersant is generally used is being used As this dispersant, many polymeric dispersants such as polyacrylic acid and copolymers thereof, copolymers of polyoxyalkylene derivatives and maleic anhydride, etc. have been proposed so far.

However, in the case of a conventional polymeric dispersant, along with micronization, cross-linking aggregation in which the dispersant adsorbs between particles easily occurs, resulting in a problem of deterioration in initial dispersibility. In addition, since the surface area of the dispersion increases, the surface free energy of the dispersion increases, and the dispersion system tends to become unstable. For this reason, even once dispersed, the dispersion agglomerated again in order to reduce the apparent surface area of the dispersion, making it difficult to stably maintain the dispersion state. Problems such as thickening of the non-aqueous dispersion composition and sedimentation of the dispersion occur due to the decrease in initial dispersibility and dispersion stability accompanying the micronization of the dispersion. In the non-aqueous dispersion composition in which these problems occur, not only productivity, processing properties, and handling properties are reduced, but also lead to deterioration in the quality of the final product.

Therefore, the dispersing agent is required to have the ability to stably disperse the dispersion without settling over a long period of time while being able to obtain a low-viscosity non-aqueous dispersion composition containing the dispersion at a high concentration.

In order to solve these problems, Patent Document 1 proposes an esterified product of polyoxyethylene monophenyl ether and a cyclic carboxylic acid, but the effect on a non-aqueous dispersion composition containing a fine particle dispersion can be sufficiently satisfied. it wasn't Further, in Patent Literature 2, esterified products of polyoxypropylene monomethacryl ether and trimellitic anhydride each having improved lipophilicity are proposed, but the effects of the composition are not sufficiently satisfactory.

Japanese Unexamined Patent Publication No. 62-106838 Japanese Unexamined Patent Publication No. 2007-144402

As described above, an object of the present invention is to solve the above problems, and in detail, a fine particle dispersion having a particle size of 1 μm or less can be dispersed in a non-aqueous solvent at a high concentration, and excellent dispersion stability can be imparted. It is to provide a non-aqueous dispersing agent.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyether ester compound comprising a polyether having a specific structure and a tricarboxylic acid anhydride can solve the above problems.

That is, the present invention is the following [1] to [3].

[1] A non-aqueous dispersing agent represented by the following formula (1).

[Formula 1]

(In formula (1),

R is a linear or branched hydrocarbon group having 1 to 22 carbon atoms.

A ¹ O is an oxyethylene group, m is an average number of added moles of an oxyethylene group represented by A ¹ O, and is 1 to 30.

A ² O is an oxyalkylene group having 3 to 4 carbon atoms, and n is the average added mole number of the oxyalkylene group represented by A ² O, and is 1 to 30.

m and n satisfy the relationship of 0.1 ≤ m/n ≤ 10 and 5 ≤ m + n ≤ 40.

a is the number of aromatic rings and is 1-2.

M represents a hydrogen atom, ammonium or alkanolammonium.)

[2] The non-aqueous dispersant according to [1], wherein A ² O is an oxypropylene group having 3 carbon atoms.

[3] A non-aqueous dispersion composition containing the non-aqueous dispersant of [1] or [2], the non-aqueous solvent, and a dispersion dispersed by the non-aqueous dispersant.

According to the present invention, a fine particle dispersion such as organic powder or inorganic powder having a particle size of 1 μm or less can be dispersed in a non-aqueous solvent at a high concentration, and excellent dispersion stability can be imparted.

Hereinafter, embodiments of the non-aqueous dispersant and the non-aqueous dispersion composition of the present invention are sequentially described.

(non-aqueous dispersant)

The non-aqueous dispersant of the present invention contains a polyether ester compound composed of a polyether represented by the following formula (1) and a tricarboxylic acid anhydride. In addition, the ester compound which consists of the polyether represented by Formula (1) and tricarboxylic acid anhydride is also simply called a "polyether ester type compound" below.

[Formula 2]

R is a linear or branched hydrocarbon group having 1 to 22 carbon atoms. As R, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, a linear saturated hydrocarbon group such as a behenyl group, isopropyl group, isobutyl group, t-butyl group, isopentyl group, isooctyl group, 2-ethylhexyl group, isononyl group, 3,5,5-trimethylhexyl group, isodecyl group, isostearyl group, 2-oxygen branched saturated hydrocarbon groups such as tildecyl group, 2-octyldodecyl group, and 2-hexyldecyl group; unsaturated hydrocarbon groups such as allyl group, (meth)acrylic group, palmitoyl group, oleyl group, and linoleyl group; can You may use these 1 type or in mixture of 2 or more types. From the viewpoint of solubility in non-aqueous solvents and initial dispersibility, it is preferably a linear or branched saturated hydrocarbon group or unsaturated hydrocarbon group having 4 to 18 carbon atoms, more preferably a branched saturated hydrocarbon group having 4 to 18 carbon atoms. It is Ki.

A ¹ O and A ² O are polyoxyalkylene groups, and when adsorbed to a dispersion, they act as a steric repulsion site, thereby favorably dispersing the dispersion and improving solubility in non-aqueous solvents.

A ¹ O is a C 2 oxyethylene group, A ² O is a C 3-4 oxyalkylene group, preferably a C 3 oxypropylene group. m represents the average number of added moles of an oxyethylene group, n represents the average number of added moles of an oxyalkylene group having 3 to 4 carbon atoms, m is 1 to 30, and n is 1 to 30.

From the viewpoints of initial dispersibility and dispersion stability, m is more preferably 3 or more, and particularly preferably 4 or more. Moreover, as for m, it is more preferable that it is 25 or less, and it is especially preferable that it is 20 or less.

Moreover, it is especially preferable that n is 3 or more from a viewpoint of initial dispersibility and dispersion stability. Moreover, n is more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less.

The average added mole number m of oxyethylene groups represented by A ¹ O and the average added mole n number of oxyalkylene groups represented by A ² O have a relationship of 0.1 ≤ m/n ≤ 10 and 5 ≤ m + n ≤ 40. .

m/n means the balance between the highly hydrophilic A ¹ O and the highly lipophilic A ² O of the polyether chain in the polyether ester compound. If m/n is less than 0.1, since the lipophilicity is too high, the initial dispersibility and dispersion stability may decrease because the polyether chain expands in a non-aqueous solvent and the polyether chain becomes easily entangled. Also, when m/n exceeds 10, the hydrophilicity is too high, so that the solubility in non-aqueous solvents is reduced, and the polyether chain is contracted to reduce the steric repulsive effect, so the initial dispersibility may be reduced.

From such a viewpoint, m/n is more preferably 0.2 or more, still more preferably 0.5 or more, and particularly preferably 0.7 or more. Moreover, as for m/n, 8 or less are more preferable, and 7 or less are especially preferable.

m + n means the polyether chain length, and satisfies 5 ≤ m + n ≤ 40. If m + n is less than 5, it becomes difficult to obtain a sufficient steric repulsion effect, and if it exceeds 40, the polyether chains become easily entangled and the initial dispersibility may decrease. As for m+n, it is especially preferable that it is 6 or more from a viewpoint of initial dispersibility and dispersion stability. Moreover, as for m+n, it is more preferable that it is 35 or less, it is still more preferable that it is 30 or less, and it is especially preferable that it is 25 or less.

a represents the number of aromatic rings and is 1-2. The aromatic ring in the polyether ester compound is derived from tricarboxylic acid anhydride, and the carboxyl group bonded to the aromatic ring functions as an adsorption site for the dispersion. By having the carboxyl group on the same aromatic ring, it becomes more easily adsorbed to the dispersion, so from the viewpoint of initial dispersibility, a = 1 is preferable.

The chemical formula in the case of a = 1 is shown in formula (1A), and the chemical formula in the case of a = 2 is shown in formula (1B).

[Formula 3]

[Formula 4]

M is a hydrogen atom or ammonium or alkanolammonium, preferably a hydrogen atom or alkanolammonium, more preferably a hydrogen atom.

Next, the manufacturing method of the polyether ester type compound represented by Formula (1) is demonstrated.

The polyether ester type compound represented by Formula (1) can be manufactured by the 1st process of manufacturing polyether, and the 2nd process of making the polyether obtained at the 1st process and tricarboxylic acid anhydride react.

A 1st process is demonstrated.

Polyether can be produced by adding an alkylene oxide to an alcohol having a linear or branched hydrocarbon group having 1 to 22 carbon atoms.

Examples of the catalyst used for the addition reaction of alkylene oxide include alkali catalysts, examples of which include oxides and hydroxides of alkali metals and alkaline earth metals, alcoholates, alkylamines such as triethylamine, and alkanes such as triethanolamine. Olamines can be used. In addition to the above alkali catalysts, Lewis acid catalysts such as boron trifluoride and tin tetrachloride can be used. As for the usage-amount of a catalyst, 0.01-5.0 mass % is common with respect to the mass after completion|finish of addition reaction.

The addition reaction of the alkylene oxide can be carried out, for example, by adding the alkylene oxide continuously under pressure at 50 to 200°C and 0.02 to 1.0 MPa under an inert gas atmosphere such as argon or nitrogen gas.

Next, the 2nd process is demonstrated.

Tricarboxylic acid anhydrides used in the second step include trimellitic acid anhydride, 1,2,3-benzene tricarboxylic acid anhydride, 1,2,5-naphthalene tricarboxylic acid anhydride, 1,4,5- and aromatic tricarboxylic acid anhydrides of naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride and 1,2,8-naphthalene tricarboxylic acid anhydride.

The reaction ratio in the second step is preferably 0.7 < (H) / (T) < 1.2, when the number of moles of the hydroxyl group of the monoalkyl polyether is (H) and the number of moles of the tricarboxylic acid anhydride is (T). and more preferably (H)/(T) = 1.

You may use a catalyst in a 2nd process. Examples of the catalyst include tertiary amine compounds, such as triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0] -7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. are mentioned.

Both the first step and the second step may be performed without a solvent, or a suitable dehydration organic solvent may be used. The solvent used in the reaction may be removed by an operation such as distillation after completion of the reaction, or may be used as a part of the product as it is. The reaction temperature is 80 to 180°C, preferably 90 to 160°C, more preferably 100 to 140°C.

The polyether ester compound of the present invention may be neutralized with an amine. Examples of the amine include alkylamines such as ammonia, methylamine, dimethylamine, and ethylamine, and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and one or two or more selected from these can be used.

(Non-aqueous dispersion composition)

The non-aqueous dispersion composition of the present invention contains a non-aqueous dispersing agent, a dispersion, and a non-aqueous solvent.

Here, the total mass of the non-aqueous dispersant, the dispersion and the non-aqueous solvent is 100% by mass.

In this case, the content of the non-aqueous dispersant is preferably from 0.05 to 20% by mass. If the content of the non-aqueous dispersant is less than 0.05% by mass, sufficient initial dispersibility and dispersion stability may not be obtained, and even if the content exceeds 20% by mass, there is a possibility that an effect commensurate with the content may not be obtained. The content of the non-aqueous dispersant is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass from the viewpoints of initial dispersibility and dispersion stability.

Examples of the dispersion contained in the non-aqueous dispersion composition of the present invention include organic powder and inorganic powder.

Examples of the organic powder include azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzoimidazolone, phenylene, phthalocyanine, and anthrapyridine. , and organic pigments such as dioxazine systems.

As the inorganic powder, for example, metal powder such as iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, two or more types of metals or Alloy powder composed of metal and nonmetal, composite powder obtained by combining metal powder or alloy powder, and mixed powder obtained by mixing two or more types of inorganic powder or inorganic powder with other powder are exemplified.

In addition, inorganic powders include powders such as silicate minerals, other silicic acid compounds, carbonate compounds, sulfuric acid compounds, hydroxide compounds, oxidized compounds, nitrated compounds, carbonized compounds, and titanic acid compounds. For example, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, aluminum silicate, magnesium silicate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, zirconium oxide , magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, tungsten carbide, aluminum nitride, silicon nitride, boron nitride, barium titanate, calcium titanate, strontium titanate, carbon black , glass fibers, carbon fibers, carbon nanofibers, and carbon nanotubes (single-wall nanotubes, double-wall nanotubes, multi-wall nanotubes) and the like.

As the dispersion, preferably, metal powders such as nickel, cobalt, palladium, copper, silver, gold, and platinum, powders of oxide compounds such as zirconium oxide, magnesium oxide, aluminum oxide, iron oxide, zinc oxide, indium tin oxide, and titanic acid It is a powder of titanic acid compounds, such as barium, calcium titanate, and strontium titanate.

The average particle diameter of the dispersion is preferably 0.01 to 1 µm, more preferably 0.01 to 0.7 µm, and particularly preferably 0.01 to 0.5 µm from the viewpoint of usefulness. The average particle size of the dispersion can be measured by an electron microscopy method using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) or a microtrack method (laser diffraction/scattering method).

When the total amount of the non-aqueous dispersant, the dispersion and the non-aqueous solvent is 100% by mass, the content of the dispersion is usually 10 to 90% by mass, preferably 30 to 85% by mass, in the non-aqueous dispersion composition. , More preferably, it is 55-80 mass %.

Examples of the non-aqueous solvent (organic solvent) serving as a dispersion medium for dispersing the dispersion in the non-aqueous dispersion composition of the present invention include aromatic hydrocarbon-based solvents such as toluene and xylene, hydrocarbon-based solvents such as cyclohexane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and γ-butyrolactone; Ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monon-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol ethers such as glycol monon-propyl ether, propylene glycol monon-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monon-propyl ether, and dipropylene glycol monon-butyl ether Solvent, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl acetate, ethylene glycol monon-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monon-butyl ether acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, dipropylene glycol mono-ethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, and dipropylene glycol mono-n -Glycol ether ester solvents such as butyl ether acetate, terpene solvents such as terpineol, dihydroterpineol, terpineol acetate and dihydroterpinylacetate, methanol, ethanol, n-propanol, isopropanol, n-butanol and alcohol solvents such as isobutanol and t-butanol, and one or two or more selected from these non-aqueous solvents can be used.

The non-aqueous solvent has a solubility parameter (SP value) of 8.5 to 12.5 ⁽ cal/cm 3 ) ^1/2 from the viewpoint of improving the dispersibility of the dispersion and compatibility with the polyether ester compound in the present invention. desirable. In addition, the solubility parameter (SP value) of non-aqueous solvents can be calculated by Hansen's formula, and details thereof are in “SP value basics, application and calculation method” (written by Hideki Yamamoto, published by Information Agency, published in 2006). It is described, and it is obtained based on this description.

Specific examples of non-aqueous solvents having a solubility parameter (SP value) within the above range include toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. , ethylene glycol monoethyl ether, ethylene glycol monon-butyl ether, diethylene glycol monoethyl ether, diethylene glycol monon-butyl ether, propylene glycol monomethyl ether, propylene glycol monon-butyl ether, ethylene glycol monoethyl ether Acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-n-butyl ether acetate, terpineol, di and hydroterpineol, terpinyl acetate, dihydroterpinyl acetate, isopropanol and n-butanol. One type selected from these non-aqueous solvents may be used alone, or two or more types may be used as a mixture.

In addition, even if the solubility parameter (SP value) is ^a non-aqueous solvent outside the range of 8.5 to 12.5 (cal/cm 3 ) ^1/2 , the SP value can be adjusted within the above range by combining two or more types of non-aqueous solvents.

The SP value of the mixed solvent can be obtained experimentally, or, as a simple method, it can also be calculated by summing the product of the mole fraction of each non-aqueous solvent and the SP value. In the non-aqueous dispersion composition of the present invention, a mixed solvent whose SP value has been adjusted by these methods can be used.

The content of the non-aqueous solvent is usually 5 to 50% by mass, preferably 10 to 40% by mass, and more preferably 10 to 30% by mass in the non-aqueous dispersion composition.

In the non-aqueous dispersion composition of the present invention, various additives such as other surfactants, binders, plasticizers, and antifoaming agents can be blended within a range that does not impair the purpose.

The non-aqueous dispersion composition of the present invention can be prepared according to a known method for producing a non-aqueous dispersion composition. For example, a method of adding a dispersion to a non-aqueous solvent in which the dispersion is dissolved and then stirring and mixing at room temperature, a method of adding a non-aqueous solvent and a dispersant to the dispersion and then stirring and mixing at room temperature, and the like. can be heard

As a dispersing device for stirring, mixing or dispersing, a known dispersing device can be used. For example, a roll mill, a ball mill, a bead mill, a sand mill, a homogenizer, a disper, an autorotation/revolution type mixer, and the like. Dispersion treatment can also be performed in an ultrasonic generating bath.

Example

Next, the present invention will be described in more detail by examples and comparative examples.

(Synthesis Example 1: Synthesis of polyether ester compound 1)

3,5,5-trimethyl-1-hexanol (trade name: 288 g (2 mol) of Nonanol, manufactured by KH Neochem Co., Ltd. and 2 g of potassium hydroxide were charged, and the temperature was raised to 120°C while stirring after nitrogen substitution. While stirring, 705 g (16 mol) of ethylene oxide was added from a separately prepared pressure-resistant container under conditions of 120°C and 0.05 to 0.50 MPa (gauge pressure) through a gas blow-in tube while pressurizing with nitrogen gas. After completion of the addition, the reaction was continued under the same conditions until the internal pressure became constant. Subsequently, in the same manner as above, 349 g (6 mol) of propylene oxide was added, and after the completion of the addition, the mixture was reacted under the same conditions until the internal pressure became constant. Thereafter, the reactant was taken out of the pressure vessel, neutralized with hydrochloric acid to a pH of 6 to 7, treated at 100 ° C. for 1 hour under reduced pressure to remove the contained moisture, and finally filtered to remove the salt, and g of polyether was obtained. The hydroxyl value of the obtained polyether was 84, and the molecular weight determined from the hydroxyl value was 668.

Next, 267 g (0.4 mol) of the polyether obtained above and 77 g of trimellitic anhydride (manufactured by Kanto Chemical Co., Ltd.) 0.4 mol) was injected and it was made to react at 120 degreeC for 4 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydrides were half-esterified, and the reaction was terminated. Thus, polyether ester compound 1 was obtained.

Further, 3,5,5-trimethyl-1-hexanol, ethylene oxide and propylene oxide in Synthesis Example 1 were appropriately changed to other compounds, and operations were carried out in accordance with Synthesis Example 1 to obtain polyether esters in Table 1. Compounds 2 to 7 and polyether ester compound 8 of Formula (2) were synthesized.

The synthesized polyether ester compounds 1 to 7 are shown in Table 1, and the compound 8 is shown in formula (2).

[Formula 5]

R is a mixture of linear/branched hydrocarbon groups having 10 to 16 carbon atoms.

(Examples 1 to 5, Comparative Examples 1 to 3)

A non-aqueous dispersion composition was prepared as follows using the polyether ester compounds 1 to 8 as a dispersant.

In a 50 ml screw tube, 20.0 g of barium titanate powder (average particle size: 0.05 μm, measured by electron microscopy using SEM), 5.0 g of propylene glycol monomethyl ether acetate, and 1.4 g of a dispersing agent were weighed, and a rotating and rotating mixer was stirred for 5 minutes to carry out preliminary dispersion. Then, a slurry-like non-aqueous dispersion composition was obtained by dispersing in a bead mill for 4 hours using 0.5 mm zirconia beads. In addition, ^the SP value of propylene glycol monomethyl ether acetate is 8.7 (cal/cm 3 ) ^1/2 .

The non-aqueous dispersion compositions obtained using the polyether ester compounds 1 to 5 were referred to as Examples 1 to 5, and the non-aqueous dispersion compositions obtained using the polyether ester compounds 6 to 8 were referred to as Comparative Examples 1 to 3. did

(variance test)

A dispersion test was conducted using the non-aqueous dispersion compositions of Examples 1 to 5 and Comparative Examples 1 to 3.

For each non-aqueous dispersion composition, the shear viscosity was measured at a temperature of 20°C and a shear rate of 0.1 to 100 (1/s) using a dynamic viscoelastic apparatus (Paar Physica MCR-300, manufactured by Anton Paar). Table 2 shows the shear viscosity when the shear rate is 1 (1/s).

In addition, the shear viscosity of each non-aqueous dispersion composition left undisturbed at room temperature for 1 week was measured under the same conditions. Table 2 also shows the shear viscosity when the shear rate is 1 (1/s).

All of the non-aqueous dispersion compositions of Examples 1 to 5 in which the polyetherester compounds 1 to 5 according to the present invention were added showed good dispersibility immediately after production, and no change in viscosity over time even after one week. could hardly be seen.

On the other hand, polyether ester compounds 6 and 7 in which m/n is outside the range, and polyether having a structure in which the addition form of the alkylene oxide in the polyether ester compound represented by formula (1) related to the present invention is reversed Since the non-aqueous dispersion compositions of Comparative Examples 1 to 3 to which the ester compound 8 was added not only had a high shear viscosity immediately after preparation but also a large change in viscosity over time, not only dispersibility immediately after preparation but also dispersion stability. It can also be seen that it is inferior.

(Examples 6 to 9, Comparative Examples 4 to 6)

Using the polyether ester compounds 1 to 4, 6, 7 and 8 as dispersants, non-aqueous dispersion compositions were prepared as follows. Further, the nonaqueous dispersion compositions obtained using the polyetherester compounds 1 to 4 were referred to as Examples 6 to 9, and the nonaqueous dispersion compositions obtained using the polyetherester compounds 6 to 8 were used as Comparative Examples 4 to 9. 6.

In a 50 ml screw tube, 20.0 g of barium titanate powder (average particle diameter: 0.05 μm, measured by electron microscopy using SEM), 5.0 g of toluene/ethanol mixed solvent (1/1, mass ratio), and 1.4 g of dispersant were weighed and agitated for 5 minutes with a rotating and revolving mixer to perform preliminary dispersion. Then, a slurry-like non-aqueous dispersion composition was obtained by using 0.5 mm zirconia beads and dispersing in a bead mill for 4 hours. In addition, the SP value of the toluene/ ^{ethanol mixed solvent (1/1, mass ratio) is 11.4 (cal/cm 3 ) 1/2 .}

(variance test)

A dispersion test was conducted using the non-aqueous dispersion compositions of Examples 6 to 9 and Comparative Examples 4 to 6.

For each non-aqueous dispersion composition, the shear viscosity was measured at a temperature of 20°C and a shear rate of 0.1 to 100 (1/s) using a dynamic viscoelastic apparatus (Paar Physica MCR-300, manufactured by Anton Paar). Table 3 shows the shear viscosity when the shear rate is 1 (1/s).

In addition, the shear viscosity of each non-aqueous dispersion composition left undisturbed at room temperature for 1 week was measured under the same conditions. Table 3 also shows the shear viscosity when the shear rate is 1 (1/s).

All of the non-aqueous dispersion compositions of Examples 6 to 9 to which the polyetherester compounds 1 to 4 according to the present invention were added showed good dispersibility immediately after production, and no change in viscosity over time even after one week. could hardly be seen.

On the other hand, polyether ester compounds 6 and 7 in which m/n is outside the range, and polyether having a structure in which the addition form of the alkylene oxide in the polyether ester compound represented by formula (1) related to the present invention is reversed Since the non-aqueous dispersion compositions of Comparative Examples 4 to 6 to which the ester compound 8 was added not only had a high shear viscosity immediately after preparation but also a large change in viscosity over time, not only the dispersibility immediately after preparation but also the dispersion stability. It can also be seen that it is inferior.

(Examples 10 to 12, Comparative Examples 7 to 9)

Using the polyether ester compounds 1, 3, 4, 6, 7 and 8 as dispersants, non-aqueous dispersion compositions were prepared as follows. In addition, the non-aqueous dispersion compositions obtained using the polyether ester compounds 1, 3 and 4 were referred to as Examples 10 to 12, and the non-aqueous dispersion compositions obtained using the polyether ester compounds 6 to 8 were used as comparative examples. It was set as 7-9.

In a 50 ml screw tube, 20.0 g of barium titanate powder (average particle size: 0.1 μm, measured by electron microscopy using SEM), 5.0 g of toluene/ethanol mixed solvent (3/7, mass ratio), and 0.4 g of dispersant were weighed and agitated for 5 minutes with a rotating and revolving mixer to perform preliminary dispersion. Then, a slurry-like nonaqueous dispersion composition was obtained by dispersing for 3 hours in a bead mill using 1.0 mm zirconia beads. In addition, the SP value of the toluene/ ^{ethanol mixed solvent (3/7, mass ratio) is 12.0 (cal/cm 3 ) 1/2 .}

(variance test)

A dispersion test was conducted using the non-aqueous dispersion compositions of Examples 10 to 12 and Comparative Examples 7 to 9.

For each non-aqueous dispersion composition, the shear viscosity was measured at a temperature of 20°C and a shear rate of 0.1 to 100 (1/s) using a dynamic viscoelastic apparatus (Paar Physica MCR-300, manufactured by Anton Paar). Table 4 shows the shear viscosity when the shear rate is 1 (1/s).

In addition, the shear viscosity of each non-aqueous dispersion composition left undisturbed at room temperature for 1 week was measured under the same conditions. Table 4 also shows the shear viscosity when the shear rate is 1 (1/s).

The non-aqueous dispersion compositions of Examples 10 to 12 to which the polyetherester compounds 1, 3 and 4 were added according to the present invention all exhibited good dispersibility immediately after production, and their viscosity over time even after 1 week The change was barely visible.

On the other hand, polyether ester compounds 6 and 7 in which m/n is outside the range, and polyether having a structure in which the addition form of the alkylene oxide in the polyether ester compound represented by formula (1) related to the present invention is reversed Since the non-aqueous dispersion compositions of Comparative Examples 7 to 9 to which the ester compound 8 was added not only had a high shear viscosity immediately after preparation but also a large change in viscosity over time, not only the dispersibility immediately after preparation but also the dispersion stability. It can also be seen that it is inferior.

[Examples 13 to 15, Comparative Examples 10 to 12]

Using the polyether ester compounds 1, 3, 4, 6, 7 and 8 as dispersants, non-aqueous dispersion compositions were prepared as follows. In addition, the non-aqueous dispersion compositions obtained using the polyether ester compounds 1, 3 and 4 were referred to as Examples 13 to 15, and the non-aqueous dispersion compositions obtained using the polyether ester compounds 6 to 8 were used as comparative examples. It was set as 10-12.

In a 50 ml screw tube, 20.0 g of aluminum oxide powder (average particle size: 0.4 μm, measured by laser diffraction), 5.0 g of toluene/ethanol mixed solvent (1/1, mass ratio), and 0.2 g of dispersant were weighed and rotated Pre-dispersion was performed by stirring for 5 minutes with an orbital mixer. Then, a slurry-like nonaqueous dispersion composition was obtained by dispersing in a bead mill for 3 hours using 1.0 mm zirconia beads.

[Distributed test]

A dispersion test was conducted using the non-aqueous dispersion compositions of Examples 13 to 15 and Comparative Examples 10 to 12.

For each non-aqueous dispersion composition, the shear viscosity was measured at a temperature of 20°C and a shear rate of 0.1 to 100 (1/s) using a dynamic viscoelastic apparatus (Paar Physica MCR-300, manufactured by Anton Paar). Table 5 shows the shear viscosity when the shear rate is 1 (1/s).

In addition, the shear viscosity of each non-aqueous dispersion composition left undisturbed at room temperature for 1 week was measured under the same conditions. Table 5 also shows the shear viscosity when the shear rate is 1 (1/s).

All of the non-aqueous dispersion compositions of Examples 13 to 15 to which the polyetherester compounds 1, 3 and 4 according to the present invention were added showed good dispersibility immediately after preparation and good dispersion stability even after one week. showed up

On the other hand, polyether ester compounds 6 and 7 in which m/n is outside the range, and polyether having a structure in which the addition form of the alkylene oxide in the polyether ester compound represented by formula (1) related to the present invention is reversed Since the non-aqueous dispersion compositions of Comparative Examples 10 to 12 to which the ester compound 8 was added not only had a high shear viscosity immediately after preparation but also a large change in viscosity over time, not only the dispersibility immediately after preparation but also the dispersion stability. It can also be seen that it is inferior.

Claims (3)

A non-aqueous dispersing agent represented by the following formula (1).
[Formula 1]

(In formula (1),
R is a linear or branched hydrocarbon group having 1 to 22 carbon atoms.
A ¹ O is an oxyethylene group, m is an average number of added moles of an oxyethylene group represented by A ¹ O, and is 1 to 25.
A ² O is an oxypropylene group having 3 carbon atoms, n is the average added mole number of the oxypropylene group represented by A ² O, and is 1 to 20.
m and n satisfy the relationship of 0.1 ≤ m/n ≤ 8 and 5 ≤ m + n ≤ 30.
a is the number of aromatic rings and is 1-2.
M represents a hydrogen atom, ammonium or alkanolammonium.) A non-aqueous dispersion composition comprising the non-aqueous dispersant according to claim 1, a non-aqueous solvent, and a dispersion dispersed by the non-aqueous dispersant. delete