TW201428027A - Non-aqueous dispersant and non-aqueous dispersion composition - Google Patents

Abstract

This invention provides a non-aqueous dispersant which can disperse dispersions such as the organic powder or inorganic powder at a high concentration in a non-aqueous solvent and at the same time provide excellent re-dispersivity. The non-aqueous dispersant of this invention is characterized by containing a polyether compound represented by formula (1), having a molecular weight of 1,000 to 10,000 and an HLB value of 1.0 to 5.0 obtained by the Griffin method, wherein A1O is an oxyethylene group, and a is the average addition molar number of the oxyethylene group represented by A1O and is 1 to 10; A2O is an oxypropylene group, and b is the average addition molar number of the oxypropylene group represented by A2O and is 1 to 30; a and b both satisfy 0.05≤a/b≤0.75 and 5≤a+b≤30. R is hydrogen or C1-4 hydrocarbyl. n is 1 to 4.

Description

Non-aqueous dispersant and non-aqueous dispersion composition

The present invention belongs to a non-aqueous dispersant and a non-aqueous dispersion composition containing the non-aqueous dispersant, and the non-aqueous dispersant can disperse a dispersion such as an organic powder or an inorganic powder in a non-aqueous solvent. More specifically, the present invention relates to a non-aqueous dispersant and a non-aqueous dispersion composition containing the non-aqueous dispersant, which can disperse the dispersion in a non-aqueous solvent at a high concentration and impart excellent properties thereto. Redistribution.

A nonaqueous dispersion composition in which a dispersion such as an organic powder or an inorganic powder is dispersed in a nonaqueous solvent is used in various industrial fields. Examples of the organic powder include an organic pigment, and a non-aqueous dispersion composition containing an organic pigment is used in a coating material, a printing ink, an ink for inkjet, a resist for a color filter, a writing instrument ink, and the like. Further, examples of the inorganic powder include a ceramic powder and a metal powder, and a non-aqueous dispersion composition containing a ceramic powder is used for a dielectric layer, a semiconductor substrate, a sensor, and a liquid crystal display element in which a ceramic capacitor is laminated. In addition to the electronic components, it is also used for abrasive materials, refractory materials, and the like. Further, a nonaqueous dispersion composition containing a metal powder is widely used as a coating material, and is also widely used as an electronic material for forming an electrode, for example, as a conductive paste or a conductive ink.

When preparing a non-aqueous dispersion composition, when it is an organic powder or an inorganic powder alone Since there are many cases where the dispersibility is insufficient, a dispersing agent is usually used for the purpose of improving the fluidity and storage stability of the non-aqueous dispersion composition. As a dispersing agent, a low molecular weight dispersing agent such as a fatty acid or an aliphatic amine is proposed, and a high molecular weight dispersing agent obtained by adding propylene oxide and ethylene oxide to an amine compound having 1 to 3 nitrogen atoms is proposed (for example, a reference patent) Literature 1) and so on.

In recent years, in the use of electronic components, it is desired to improve product characteristics such as miniaturization, low power consumption, high efficiency, and high capacity. In order to meet these requirements, it is desired to use a dispersion of a ceramic or a metal powder as a raw material. The diameter is made fine or the dispersion in the non-aqueous dispersion composition is increased in concentration.

However, as the dispersion of the dispersion is required to be finer and higher, dispersion in the conventional dispersant may be insufficient, and the dispersion of the dispersion may cause problems such as thickening of the non-aqueous dispersion composition and sedimentation of the dispersion. . In the non-aqueous dispersion composition which causes these problems, not only the productivity, the processing property and the handleability are lowered, but also the quality of the final product is lowered. Therefore, the dispersant is required to have a non-aqueous dispersion composition capable of obtaining a high-concentration dispersion and having a low viscosity, and can be easily redispersed even if the dispersion settles.

In order to solve the problem of the initial dispersibility and the redispersibility of the dispersion by refining the dispersion, Patent Document 2 proposes a high molecular weight obtained by adding ethylene oxide and butylene oxide to a polyamine compound. Dispersant. However, the dispersant does not sufficiently satisfy the effect of the nonaqueous dispersion composition containing a high concentration dispersion.

Prior art literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 55-152785

Patent Document 2: Japanese Patent Laid-Open No. 2-68126

An object of the present invention is to provide a non-aqueous dispersant and a non-aqueous dispersion composition containing the non-aqueous dispersant, which can be used as a dispersion of an organic powder or an inorganic powder. The high concentration is dispersed in the non-aqueous solvent while imparting excellent redispersibility.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a polyether compound having a specific structure having a predetermined molecular weight and an HLB value can solve the above problems.

In other words, the present invention is a non-aqueous dispersant and a non-aqueous dispersion composition containing the non-aqueous dispersant, and the non-aqueous dispersant is obtained by the Griffin method having a molecular weight of 1,000 to 10,000 as shown in the formula (1). The composition of the polyether compound having an HLB value of 1.0 to 5.0.

Wherein A ¹ O is oxyethylene and a is an oxyethylene group represented by A ¹ O ( The average addition mole number of the base) is 1 to 10. A ² O is oxypropylene ( Base), b is the average addition mole number of the oxypropylene group represented by A ² O, which is 1 to 30. a and b meet 0.05 a/b 0.75 and 5 a+b 30 relationship. R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n is 1~4.

According to the present invention, a dispersion such as an organic powder or an inorganic powder can be dispersed in a nonaqueous solvent at a high concentration, and excellent redispersibility can be imparted thereto.

Hereinafter, embodiments of the nonaqueous dispersing agent and the nonaqueous dispersion composition of the present invention will be sequentially described.

[Non-aqueous dispersant]

The nonaqueous dispersing agent of the present invention contains a polyether compound represented by the following formula (1). In addition, the polyether compound represented by the formula (1) is also simply referred to as "polyether compound" hereinafter.

In the above formula (1), n is 1 to 4.

The nitrogen atom in the polyether compound acts as an adsorption site relative to the dispersion use. When n exceeds 4, the flocculation of the dispersion is promoted by the generation of a flocculating agent which is dispersed and adsorbed between the dispersions, and the initial dispersibility and redispersibility may be lowered.

A ¹ O and A ² O are polyoxyalkylene groups, and when adsorbed onto the dispersion, they act as steric repulsion sites, so that the powders are well dispersed and the solubility in a non-aqueous solvent can be improved.

A ¹ O is an oxyethylene group having ² carbon atoms, and A ² O is an oxypropylene group having 3 carbon atoms. a represents the average addition mole number of the oxyethylene group, and b represents the average addition mole number of the oxypropylene group, a is 1 to 10, and b is 1 to 30. From the viewpoints of initial dispersibility and redispersibility, a and b are preferably a from 1 to 7, and b is from 5 to 30; further preferably, a is from 1 to 5 and b is from 5 to 25.

The average addition mole number a of the oxyethylene group represented by A ¹ O and the average addition mole number b of the oxypropylene group represented by A ² O have 0.05 a/b 0.75 and 5 a+b 30 relationship.

a/b represents the balance between the oleophobic A ¹ O of the polyether chain and the lipophilic A ² O in the polyether compound. When a/b is less than 0.05, the lipophilicity is too high, so that the polyether chain expands in the nonaqueous solvent, and the polyether chain becomes entangled, so that the initial dispersibility may be lowered. Further, when a/b exceeds 0.75, the oleophobicity is too high, so the solubility in the nonaqueous solvent is lowered, the polyether chain is shrunk, the steric repellency is lowered, and the initial dispersibility may be lowered. From the standpoint of initial dispersibility, a/b is preferably 0.1 a/b 0.6, further preferably 0.1 a/b 0.5.

a+b represents a polyether chain length per 1 equivalent of active hydrogen bonded to a nitrogen atom, satisfying 5 a+b 30. When a+b is less than 5, it is difficult to obtain a sufficient steric repellency effect, and when it exceeds 30, the polyether chain becomes entangled, and thus the initial dispersibility may be lowered. From the standpoint of initial dispersibility, a+b is preferably 5 a+b 25, further preferably 10 a+b 25.

R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. As a hydrocarbon group, a A saturated hydrocarbon group such as a group, an ethyl group, a propyl group or a butyl group, or an unsaturated hydrocarbon group such as an allyl group or a methallyl group. Preferred is a hydrogen atom or a saturated hydrocarbon group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group. When the number of carbon atoms of the hydrocarbon group represented by R exceeds 4, preparation may become difficult.

A plurality of R in the polyether compound may be all the same hydrocarbon group, or may be two or more different hydrocarbon groups.

The polyether compound has a molecular weight of 1,000 to 10,000. When the molecular weight is less than 1,000, not only the initial dispersibility may be lowered, but also sufficient redispersibility may not be obtained. Further, when the molecular weight exceeds 10,000, the initial dispersibility may be lowered. The molecular weight is preferably from 2,000 to 9,000, and more preferably from 4,000 to 8,000, from the viewpoint of initial dispersibility and redispersibility.

Further, in the present invention, the molecular weight is a molecular weight calculated from an amine value.

The HLB value of the polyether compound obtained by the Griffin method is 1.0 to 5.0. When the HLB value is less than 1.0, the lipophilicity of the polyether compound is too high, so that the molecules become easily entangled with each other by the expansion of molecules in the nonaqueous solvent, and the initial dispersibility and redispersibility may be lowered. Further, when the HLB value exceeds 5.0, the hydrophilicity of the polyether compound is too high, so that the solubility in the nonaqueous solvent is lowered, so that the molecular shrinkage, the initial dispersibility and the redispersibility may be lowered. The HLB value is preferably from 2.0 to 5.0, and more preferably from 2.5 to 5.0, from the viewpoints of initial dispersibility and redispersibility.

In addition, the HLB value obtained by the Griffin method in the present invention is described in detail in "Introduction to Surfactants" (Sanyo Kasei Industrial Co., Ltd., issued in 2007), and can be obtained based on the description.

The polyether compound in which R in the formula (1) is a hydrogen atom can be obtained by adding an alkylene oxide to a polyethene polyamine having 2 to 5 nitrogen atoms.

A catalyst may be used for the addition reaction of the alkylene oxide, and a catalyst may not be used depending on the case. Examples of the catalyst used in the addition reaction of the alkylene oxide include a basic catalyst. For example, an alkali metal or an alkaline earth metal oxide, an alkali metal or an alkaline earth metal hydroxide, an alcoholate or a triethylamine can be used. And other alkylamines; alkanolamines such as triethanolamine. Further, in addition to the above basic catalyst, a Lewis acid catalyst such as boron trifluoride or tin tetrachloride may be used. The amount of the catalyst used is generally 0.01 to 5.0% by mass based on the mass after completion of the addition reaction.

The addition reaction of an alkylene oxide can be carried out, for example, by a method of reacting a compound having a nitrogen atom with respect to a raw material at 50 to 200 ° C and 0.02 to 1.0 MPa in an inert gas atmosphere such as argon or nitrogen. The alkylene oxide is added while continuously pressurizing in the presence of a catalyst.

The polyether compound in which R in the formula (1) is a hydrocarbon group having 1 to 4 carbon atoms can be used in an amount of 1 to 4 carbon atoms in the presence of a basic catalyst after the addition reaction of alkylene oxide. The alkyl halide or the halogenated alkene is reacted to obtain an alkyl etherification or an alkenyl etherification.

Examples of the halogenated alkane include methyl chloride, ethyl chloride, chloropropane, chlorobutane, methyl bromide, ethyl bromide, methyl iodide, and ethyl iodide; and examples of the halogenated alkene include allyl chloride. , methyl allyl chloride, and the like. As the basic catalyst at this time, an alkali metal, an alkaline earth metal oxide, an alkali metal or an alkaline earth metal hydroxide, an alcoholate or the like can be used.

The amount of the halogenated alkane or halogenated alkene added is 100 to 400 mol% with respect to the hydroxyl group of the reaction; and the amount of the basic catalyst is 100 to 500 mol% with respect to the hydroxyl group of the reaction. Further, the reaction temperature is usually carried out at 60 to 180 °C.

The nonaqueous dispersing agent of the present invention containing a polyether compound can be neutralized with an organic acid or a mineral acid. Examples of the organic acid include acetic acid, glycolic acid, oxalic acid, citric acid, lactic acid, and malic acid; and examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. One or two or more selected from the group consisting of these organic acids and inorganic acids are used. The nonaqueous dispersing agent of the present invention may contain these organic acids and inorganic acids within the range not impairing the effects of the present invention.

[Non-aqueous dispersion composition]

The nonaqueous dispersion composition of the present invention contains a nonaqueous dispersant, a dispersion, and a nonaqueous solvent.

The content of the non-aqueous dispersion agent is 0.05 to 20% by mass in the non-aqueous dispersion composition. When the content is less than 0.05% by mass, sufficient initial dispersibility and redispersibility may not be obtained, and even if the content exceeds 20% by weight, an effect corresponding to the content may not be obtained. The content of the non-aqueous dispersant is preferably from 0.1 to 15% by mass, and more preferably from 0.5 to 10% by mass, from the viewpoint of initial dispersibility or redispersibility.

The dispersion contained in the non-aqueous dispersion composition of the present invention may, for example, be an organic powder or an inorganic powder.

Examples of the organic powder include azos, diazos, condensed azos, thioindigos, indanthrones, quinacridones, anthraquinones, benzimidazolones, anthracenes, and the like. Phthalocyanines, purines and pyrimidines ) and organic pigments such as dioxazines.

Examples of the inorganic powder include metal powders such as iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, and platinum, and two or more kinds thereof. An alloy powder composed of a metal or a metal and a non-metal, a composite powder obtained by combining a metal powder or an alloy powder, and a mixed powder obtained by mixing two or more inorganic powders or inorganic powders with other powders.

Other examples of the inorganic powder include various powders such as a niobate mineral, another antimony compound, a carbon oxide compound, a sulfur oxide compound, a hydroxide, an oxide, a carbide, a nitride, and a titanium oxide compound. For example, kaolin, clay, talc, mica, bentonite, dolomite, Calcium citrate, magnesium citrate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum citrate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, Iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, tantalum carbide, tungsten carbide, aluminum nitride, tantalum nitride, boron nitride, barium titanate, carbon black, graphite, rock wool, glass wool, Various powders such as glass fiber, carbon fiber, carbon nanofiber, carbon nanotube (single-walled nanotube, double-walled nanotube, multi-walled nanotube).

As the dispersion, preferred examples of the inorganic powder include metal powders of iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, and the like. And their alloy powders, composite powders, mixed powders. Further, each of the powders of a citrate mineral, another oxime compound, a carbon oxide compound, a oxysulfide compound, a hydroxide, an oxide, a carbide, a nitride, and a titanium oxide compound may be mentioned. For example, kaolin, clay, talc, mica, bentonite, dolomite, calcium citrate, magnesium citrate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, and hydroxide can be cited. Iron, aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, antimony carbide, tungsten carbide, aluminum nitride, tantalum nitride, nitrogen Powder of boron and barium titanate. More preferably, it is a metal powder, a powder of an oxide, a powder of a carbide, a powder of a nitride, or a powder of a titanium oxide compound. For example, metal powders of aluminum, nickel, cobalt, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, etc., zirconia, magnesia, alumina, titania, iron oxide, oxidation a powder of an oxide such as zinc, indium oxide or indium tin oxide; a powder of a carbide such as tantalum carbide or tungsten carbide; a powder of a nitride such as aluminum nitride, tantalum nitride or boron nitride; or titanium such as barium titanate Each powder of an oxygen compound. Further, examples thereof include metal powders such as nickel, cobalt, palladium, copper, silver, gold, and platinum, and powders of carbides such as tantalum carbide and tungsten carbide, and aluminum nitride, tantalum nitride, boron nitride, and the like. Nitride powder.

The average particle diameter of the dispersion is preferably 0.01 to 10 μm, more preferably 0.01 to 5 μm, still more preferably 0.01 to 1 μm from the viewpoint of usefulness. In addition, the average particle size of the dispersion can be microtracked ( The method is measured.

The content of the dispersion is usually 10 to 90% by mass, preferably 30 to 85% by mass, and more preferably 55 to 80% by mass in the nonaqueous dispersion composition.

In the non-aqueous solvent composition of the present invention, the non-aqueous solvent (organic solvent) which is a dispersing agent for dispersing the dispersion may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene or a hydrocarbon such as cyclohexane. Solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and γ-butyrolactone Ester solvent, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol single Methyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether and dipropylene glycol single positive Glycol ether solvent such as butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ethyl acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, C Alcohol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate And glycol ether ester solvents such as dipropylene glycol mono-n-butyl ether acetate, terpene solvents such as terpineol, dihydroterpineol, terpene acetate and dihydrofurfuryl acetate, methanol, ethanol, An alcohol solvent such as n-propanol, isopropanol, n-butanol, isobutanol or t-butanol may be used alone or in combination of two or more kinds selected from these nonaqueous solvents.

The solubility parameter (SP value) of the nonaqueous solvent is preferably 8.5 to 10.5 (cal/cm ³ ) ^1/2 from the viewpoint of improving the dispersibility of the dispersion and the compatibility with the polyether compound in the present invention. In addition, the solubility parameter (SP value) of the nonaqueous solvent can be calculated by the Fedors method.

Specific examples of the nonaqueous solvent having a solubility parameter (SP value) in the above range include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, and acetic acid. Propyl ester, n-butyl acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, Propylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono-n-butyl ether acetate, terpineol, dihydroterpineol, terpene acetate, dihydrofurfuryl acetate. One or a mixture of two or more selected from these nonaqueous solvents may be used alone.

In addition, even if the solubility parameter (SP value) is a nonaqueous solvent outside the range of 8.5 to 10.5 (cal/cm ³ ) ^1/2 , the SP value can be adjusted to the above range by combining two or more kinds of nonaqueous solvents. .

The SP value of the mixed solvent can be experimentally determined, and can be calculated as a simple method by the sum of the products of the molar fraction and the SP value of each nonaqueous solvent. In the nonaqueous dispersion composition of the present invention, a mixed solvent in which the SP value is adjusted by these methods can be used.

The content of the nonaqueous solvent in the nonaqueous dispersion composition is usually 5 to 50% by mass, preferably 10 to 40% by mass, and more preferably 15 to 30% by mass.

In the non-aqueous dispersion composition of the present invention, various additives such as other surfactants, binders, plasticizers, and antifoaming agents may be mixed within a range not impairing the object.

The nonaqueous dispersion composition of the present invention can be dispersed according to a known nonaqueous system. The preparation method of the body composition is carried out. For example, a method in which a dispersion is added to a nonaqueous solvent in which a dispersant is dissolved, and then stirred and mixed at room temperature; a nonaqueous solvent and a dispersant are added to the dispersion, and then stirred and mixed at room temperature. Method etc.

As the dispersing machine for stirring, mixing or dispersing, a known dispersing machine can be used. For example, a roll mill, a ball mill, a bead mill, a sand mill, a jet mill, a homogenizer, a self-rotating public-transition mixer, etc. are mentioned. Further, the dispersion treatment may be carried out in an ultrasonic generation bath.

[Examples]

Next, the present invention will be further described in detail by way of examples and comparative examples.

Synthesis Example 1 [Synthesis of Polyether Compound 1]

In a stainless steel 5-liter capacity pressure vessel equipped with a mixer, a pressure gauge, a thermometer, a safety valve, a blowpipe, an exhaust pipe, a cooling coil and a steam hood, 103 g of diethylenetriamine (Kantong Chemical) was added. The system was replaced with an active hydrogen bonded to a nitrogen atom per 1 mol of nitrogen gas: 5 equivalents. After stirring, the temperature was raised to 80 ° C, and then 220 g of ethylene oxide was added from a separately prepared pressure-resistant container by a nitrogen gas under pressure of 80 to 100 ° C and 0.05 to 0.5 MPa (gauge pressure). (The active hydrogen bonded to the nitrogen atom is equivalent to 1 mole per 1 equivalent).

After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. After cooling to 40 ° C, 3.9 g of potassium hydroxide was added, and the inside of the system was replaced with nitrogen. After heating to 100 ° C under stirring, 440 g of ethylene oxide (per 1 equivalent of nitrogen atom-bonding activity) was added through a gas blowing tube while being pressurized by nitrogen at 100 to 120 ° C and 0.05 to 0.5 MPa. Hydrogen is equivalent to 2 moles).

After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. Connect Under stirring, 3,490 g of propylene oxide was added through a blowing pipe under the conditions of 100 to 120 ° C and 0.05 to 0.5 MPa by nitrogen gas pressure (the active hydrogen bonded to the nitrogen atom per equivalent of 12 is equivalent to 12). Moore).

After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. After cooling to 30 ° C, the reactants were taken out from the pressure vessel and placed in a 5 liter capacity eggplant bottle.

To which 43 g of adsorbent was added (trade name: 700, manufactured by Kyowa Chemical Industry Co., Ltd., under a nitrogen atmosphere at 90 to 100 ° C and 0.05 MPa or less, and the resulting salt is separated from the adsorbent by filtration to obtain a polyether compound 1. The obtained polyether compound 1 had an amine value of 39.6, and the molecular weight determined from the amine value was 4,250.

Further, the method for measuring the amine value of the polyether compound 1 is as follows.

Weigh the sample in a beaker, add neutral ethanol to it (use bromocresol green indicator before use, neutralize ethanol (99.5V/V%) with N/2 hydrochloric acid standard solution) and dissolve it. . Next, a few drops of bromocresol green indicator were added and titrated with N/2 hydrochloric acid standard solution to determine the end point when the liquid changed from green to yellow. The amine value was calculated by the following formula.

Amine value = (28.05 × F × A) / W

Wherein, the amount of A:N/2 hydrochloric acid standard solution; the coefficient of F:N/2 hydrochloric acid standard solution; W: the amount of sample taken (g).

Further, by changing the diethylenetriamine, ethylene oxide, and propylene oxide in Synthesis Example 1 into other compounds as appropriate, and operating in Synthesis Example 1, the polyether compounds 3 to 5 of Table 1 were synthesized. The polyether compounds 6 to 8 of Table 2.

Synthesis Example 2 [Synthesis of Polyether Compound 2]

In the same apparatus as that used in Synthesis Example 1, 95 g of tetraethylene was added. Pentaamine (manufactured by Tosoh Corporation, active hydrogen bonded to one mole of nitrogen atom: 7 equivalents) and 7.8 g of potassium hydroxide were replaced with nitrogen gas. After heating to 100 ° C under stirring, 870 g of ethylene oxide (per 1 equivalent of nitrogen atom-bonding activity) was added through a gas blowing tube while being pressurized with nitrogen at 100 to 120 ° C and 0.05 to 0.5 MPa. Hydrogen is equivalent to 5 moles).

After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. Then, under stirring, 3,050 g of propylene oxide was added by a nitrogen gas under a condition of 100 to 120 ° C and 0.05 to 0.5 MPa (the active hydrogen bonded to the nitrogen atom per equivalent is equivalent to 15). Moore).

After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. After cooling to 30 ° C or lower, 290 g of potassium hydroxide was added, and the inside of the system was replaced with nitrogen. After the temperature was raised to 80 ° C, 34 g of methyl chloride was added through a gas blowing tube while being pressurized by nitrogen gas at 80 to 100 ° C.

After the addition was completed, the reaction was carried out under the same conditions until the internal pressure became constant. The treatment was carried out for 1 hour at 70 to 80 ° C and 0.05 MPa or less while blowing nitrogen gas, and unreacted methyl chloride was removed from the system. The internal pressure was 0.05 MPa with nitrogen, and after cooling to 60 ° C, 0.5 liter of deionized water of 60 ° C was gradually added under stirring. After adding deionized water and stirring well, it was allowed to stand at 60 to 70 ° C for about 2 hours in a sealed state. After standing, the upper polyether layer was separated from the aqueous layer, and the polyether layer was taken out and placed in a 5-liter capacity eggplant-shaped flask, and dehydrated at 90 to 100 ° C and 0.05 MPa or less under a nitrogen atmosphere. After dehydration, add 40g of adsorbent (trade name: 700, manufactured by Kyowa Chemical Industry Co., Ltd., under a nitrogen atmosphere at 90 to 100 ° C and 0.05 MPa or less, and the resulting salt is separated from the adsorbent by filtration to obtain a polyether compound 2. The obtained polyether compound 2 had an amine value of 35.4, and the molecular weight determined from the amine value was 7,930. Further, the amine value of the polyether compound 2 was measured in the same manner as in Synthesis Example 1.

The molecular weights and HLB values of the synthesized polyether compounds 1 to 8 can be shown in Tables 1 and 2. Further, the molecular weight was calculated from the measured amine value, and the HLB value was determined by the Griffin method.

Formula (4)

[Examples 1 to 4, Comparative Examples 1 to 4]

Using the polyether compounds 1 to 8 as a dispersing agent, a nonaqueous dispersion composition was prepared as described below.

Weigh 2.0 g of silver powder (average particle diameter: 0.7 μm, measured by micro-tracking method), 0.67 g of terpineol and 0.02 g of dispersant in a 50 mL spiral tube, and stir for 5 minutes with a self-rotating public mixer. A slurry-like non-aqueous dispersion composition containing an inorganic powder. Further, the SP value of terpineol was 9.7 (cal/cm ³ ) ^1/2 .

The nonaqueous dispersion compositions obtained by using the polyether compounds 1 to 4 were used as the examples 1 to 4 in this order, and the nonaqueous dispersion compositions obtained by using the polyether compounds 5 to 8 were sequentially used as Comparative Examples 1 to 4.

[Dispersion test]

The dispersion test was carried out using the nonaqueous dispersion compositions of Examples 1 to 4 and Comparative Examples 1 to 4.

For each non-aqueous dispersion composition, a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar Co., Ltd.) was used, and the shear viscosity with respect to a temperature of 20 ° C and a shear rate of 0.1 to 100 (1/s) was performed. Determination. The shear viscosity at a shear rate of 1 (1/s) is shown in Table 3.

Further, each nonaqueous dispersion composition which was allowed to stand at room temperature for one week was rotated. The male transition mixer was further stirred for 5 minutes, and the shear viscosity of each of the nonaqueous dispersion compositions was measured under the same conditions. The shear viscosity at a shear rate of 1 (1/s) is shown together in Table 3.

The non-aqueous dispersion compositions of Examples 1 to 4 to which the polyether compounds 1 to 4 of the present invention were added exhibited good dispersibility immediately after preparation, and even after one week, substantially no viscosity was observed. Variety.

On the other hand, the non-aqueous dispersion composition of Comparative Example 1 in which the polyether compound 5 having the HLB value outside the range specified in the present invention was added, although the change in viscosity with time was small, the shear viscosity was high immediately after the preparation. Poor dispersion.

a non-aqueous dispersion composition of Comparative Examples 2 and 3 having a polyether compound 6 and 7 having a structure opposite to the addition form of alkylene oxide in the polyether compound represented by the formula (1) of the present invention, Although the change in viscosity over time is small, the shear viscosity is extremely high and the dispersibility is very poor immediately after preparation.

Further, the non-aqueous dispersion composition of Comparative Example 4 to which the polyether compound 8 having no ethylene oxide chain in its structure was added was not only high in shear viscosity immediately after preparation, but also elapsed time. Since the viscosity change is also large, it is understood that not only the dispersibility immediately after the preparation is poor, but also the redispersibility is poor.

[Examples 5 to 7, Comparative Examples 5 to 7]

Using the polyether compounds 1, 3 to 6, and 8 as a dispersing agent, a nonaqueous dispersion composition was prepared as described below. Further, the nonaqueous dispersion compositions obtained by using the polyether compounds 1, 3 and 4 were sequentially used as Examples 5 to 7, and the nonaqueous dispersion compositions obtained by using the polyether compounds 5, 6 and 8 were sequentially used. Comparative Examples 5 to 7.

Weigh 2.0 g of tantalum nitride powder (average particle size: 1.0 μm, determined by micro-tracking method), 1.08 g of ethylene glycol monobutyl ether acetate, and 0.06 g of dispersant in a 50 mL spiral tube. The conversion mixer was stirred for 5 minutes to obtain a slurry-form non-aqueous dispersion composition containing an inorganic powder. Further, the SP value of ethylene glycol monobutyl ether acetate was 8.8 (cal/cm ³ ) ^1/2 .

[Dispersion test]

The dispersion test was carried out using the nonaqueous dispersion compositions of Examples 5 to 7 and Comparative Examples 5 to 7.

For each non-aqueous dispersion composition, a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar Co., Ltd.) was used, and the shear viscosity with respect to a temperature of 20 ° C and a shear rate of 0.1 to 100 (1/s) was performed. Determination. The shear viscosity at a shear rate of 1 (1/s) is shown in Table 4.

Further, each of the non-aqueous dispersion compositions which were allowed to stand at room temperature for one week was further stirred for 5 minutes in a self-rotating conversion mixer, and the shear viscosity of each of the non-aqueous dispersion compositions was measured under the same conditions. The shear viscosity at a shear rate of 1 (1/s) is shown together in Table 4.

The non-aqueous dispersion compositions of Examples 5 to 7 to which the polyether compound of the present invention was added exhibited good dispersibility immediately after preparation, and the change in viscosity with time was not substantially observed even after one week.

On the other hand, the non-aqueous dispersion composition of Comparative Example 5 in which the polyether compound 5 having the HLB value outside the range specified in the present invention is added, and the polyether having the formula (1) and the present invention are added. In the non-aqueous dispersion composition of Comparative Example 6 in which the polyether compound 6 having a structure in which the alkylene oxide has an opposite addition structure to the compound, although the change in viscosity with time is small, the shear viscosity is extremely high and dispersed immediately after the preparation. Very poor sex.

Further, the non-aqueous dispersion composition of Comparative Example 7 to which the polyether compound 8 having no ethylene oxide chain in its structure was added was not only high in shear viscosity immediately after preparation, but also had a large change in viscosity over time. It was found that not only the dispersibility immediately after the preparation was poor, but also the redispersibility was poor.

Claims (2)

A non-aqueous dispersant comprising a polyether compound having a molecular weight of 1,000 to 10,000 and a HLB value of 1.0 to 5.0 as determined by the Griffin method as shown in the formula (1). Wherein, A ¹ O is oxyethylene, a is an average addition mole number of oxyethylene groups represented by A ¹ O, which is 1 to 10; A ² O is oxypropylene, and b is A ² The average addition molar number of oxypropylene groups represented by O, which is 1 to 30; a and b satisfy 0.05 a/b 0.75 and 5 a+b a relationship of 30; R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and n is 1 to 4. A nonaqueous dispersion composition comprising the nonaqueous dispersant according to claim 1.