JP2014147926A - Nonaqueous dispersant and nonaqueous dispersant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous dispersant capable of dispersing the dispersion of an organic powder, an inorganic powder and the like in a nonaqueous solvent in high concentration.SOLUTION: A nonaqueous dispersant is exhibited as a following formula and contains a polyether-based compound having a molecular weight of 1,000-10,000 and an HLB value obtained by a Griffin method of 1.0-5.0 (where, AO is oxyethylene; a is the average addition molar number of oxyethylene group shown as AO and is 1-10; AO is oxypropylene group; b is the average addition molar number of oxypropylene group shown as AO and is 1-30; a and b are satisfied with 0.05≤a/b≤0.75 and 5≤a+b≤30; R is a hydrogen atom or a 1-4C hydrocarbon; and n is 1-4).

Description

  The present invention relates to a non-aqueous dispersant capable of dispersing a dispersion such as an organic powder or an inorganic powder in a non-aqueous solvent, and a non-aqueous dispersion composition containing the non-aqueous dispersant. More specifically, a non-aqueous dispersant capable of dispersing the dispersion in a non-aqueous solvent at a high concentration and imparting excellent redispersibility, and a non-aqueous dispersion containing the non-aqueous dispersant The body composition.

  Non-aqueous dispersion compositions in which a dispersion such as an organic powder or an inorganic powder is dispersed in a non-aqueous solvent are used in various industrial fields. Examples of organic powders include organic pigments, and non-aqueous 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. Non-aqueous dispersion compositions containing ceramic powder include dielectric layers of multilayer ceramic capacitors, semiconductor substrates, sensors, and liquid crystal display elements. In addition to these electronic components, it is used for abrasives and refractory materials. Non-aqueous dispersion compositions containing metal powder are widely used as paints and as electronic materials for forming electrodes, for example, as conductive pastes and conductive inks.

  When preparing a non-aqueous dispersion composition, the organic powder or inorganic powder alone often has insufficient dispersibility, so the aim is to improve the fluidity and storage stability of the non-aqueous dispersion composition. Generally, a dispersant is used. Examples of the dispersant include low molecular weight dispersants such as fatty acids and aliphatic amines, and high molecular weight dispersants obtained by adding propylene oxide and ethylene oxide to amino compounds having 1 to 3 nitrogen atoms (see, for example, Patent Document 1). Proposed.

  In recent years, in electronic component applications, it has been desired to improve product characteristics such as miniaturization, low power consumption, high efficiency, and high capacity. In order to meet these requirements, ceramics and metal powder as raw materials are required. There is a demand to make the particle size of a dispersion such as a body finer, or to increase the concentration of a dispersion in a non-aqueous dispersion composition.

  However, with the demand for finer and higher concentration dispersions, conventional dispersants sometimes have insufficient dispersion, and the dispersion aggregates to increase the viscosity of the non-aqueous dispersion composition. Problems such as sedimentation of the dispersion have occurred. In the non-aqueous dispersion composition in which these problems occur, there is a problem that not only the productivity, processing characteristics, and handling properties are lowered, but also the quality of the final product is lowered. For this reason, the dispersant has a performance of being able to obtain a non-aqueous dispersion composition having a high concentration of the dispersion and having a low viscosity and to be easily redispersed even if the dispersion settles. It is requested.

  In order to solve the decrease in the initial dispersibility and redispersibility of the dispersion due to the finer dispersion, Patent Document 2 discloses a high molecular weight dispersant obtained by adding ethylene oxide and butylene oxide to a polyamine compound. Proposed. However, this dispersant was not sufficiently satisfactory for the effect on the non-aqueous dispersion composition containing the dispersion at a high concentration.

JP 55-152785 A JP-A-2-68126

  The object of the present invention is to solve the above-mentioned problem. Specifically, a dispersion such as an organic powder or an inorganic powder can be dispersed in a non-aqueous solvent at a high concentration and has excellent redispersibility. And a non-aqueous dispersion composition containing the non-aqueous dispersant.

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

  That is, the present invention relates to a polyether compound represented by the formula (1), having a molecular weight of 1,000 to 10,000, and an HLB value determined by the Griffin method of 1.0 to 5.0. And a non-aqueous dispersion composition containing the non-aqueous dispersant.

（ただしＡ^１Ｏはオキシエチレン基であり、ａはＡ^１Ｏで示されるオキシエチレン基の平均付加モル数であり、１〜１０である。Ａ^２Ｏはオキシプロピレン基であり、ｂはＡ^２Ｏで示されるオキシプロピレン基の平均付加モル数であり、１〜３０である。ａとｂは０．０５≦ａ／ｂ≦０．７５、かつ、５≦ａ＋ｂ≦３０の関係を満たす。Ｒは水素原子または炭素数１〜４の炭化水素基である。ｎは１〜４である。）

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

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

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

(Non-aqueous dispersant)
The non-aqueous dispersant of the present invention contains a polyether compound represented by the following formula (1). Hereinafter, the polyether compound represented by the formula (1) is also simply referred to as “polyether compound”.

In said Formula (1), n is 1-4.
The nitrogen atom in the polyether compound acts as an adsorption site for the dispersion. When n exceeds 4, bridging agglomeration in which the dispersant is adsorbed across the dispersions occurs, so that the agglomeration of the dispersion is promoted and the initial dispersibility and redispersibility may be lowered.

A ¹ O and A ² O are polyoxyalkylene groups, and when adsorbed on the dispersion, act as a steric repulsion site to disperse the powder well and increase the solubility in non-aqueous solvents. Can do.
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, b represents the average addition mole number of the oxypropylene group, a is 1 to 10, and b is 1 to 30. From the viewpoint of initial dispersibility and redispersibility, a and b are preferably a of 1 to 7, b of 5 to 30, and more preferably a of 1 to 5 and b of 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 are 0.05 ≦ a / b ≦ 0.75 and 5 ≦ a + b ≦ 30.

a / b means a balance between A ¹ O having a strong oleophobic property and A ² O having a strong lipophilicity in a polyether compound. If a / b is less than 0.05, the lipophilicity is too high, and thus the polyether chain expands in the non-aqueous solvent and the polyether chain tends to be entangled, whereby the initial dispersibility may be lowered. In addition, when a / b exceeds 0.75, the oleophobic property is too high, so that the solubility in a non-aqueous solvent is lowered, the polyether chain is shrunk, and the steric repulsion effect is lowered, so that the initial dispersion is reduced. May decrease. From the viewpoint of initial dispersibility, a / b is preferably 0.1 ≦ a / b ≦ 0.6, and more preferably 0.1 ≦ a / b ≦ 0.5.

  a + b means a polyether chain length per equivalent of active hydrogen bonded to a nitrogen atom, and satisfies 5 ≦ a + b ≦ 30. When a + b is less than 5, it is difficult to obtain a sufficient steric repulsion effect. When a + b is more than 30, the polyether chain tends to be entangled, so that the initial dispersibility may be lowered. From the viewpoint of initial dispersibility, a + b is preferably 5 ≦ a + b ≦ 25, and more preferably 10 ≦ a + b ≦ 25.

R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group include saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, and butyl group, and unsaturated hydrocarbon groups such as allyl group and methallyl group. Preferably they are a hydrogen atom or a C1-C4 saturated hydrocarbon group, More preferably, they are a hydrogen atom or a methyl group. If the number of carbon atoms of the hydrocarbon group represented by R exceeds 4, production may be difficult.
The plurality of R in the polyether compound may all be the same hydrocarbon group or may be two or more different hydrocarbon groups.

The molecular weight of the polyether compound is 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. On the other hand, if the molecular weight exceeds 10,000, the initial dispersibility may be lowered. The molecular weight is preferably 2,000 to 9,000, and more preferably 4,000 to 8,000, from the viewpoints of initial dispersibility and redispersibility.
In the present invention, the molecular weight is a molecular weight calculated from an amine value.

The HLB value calculated | required by the Griffin method of a polyether type compound is 1.0-5.0. When the HLB value is less than 1.0, the lipophilicity of the polyether-based compound is too high, so that the molecules are easily entangled due to the expansion of the molecules in the non-aqueous solvent, and the initial dispersibility and redispersibility may be reduced. is there. On the other hand, if the HLB value exceeds 5.0, the hydrophilicity of the polyether compound is too high, so that the solubility in a non-aqueous solvent decreases, the molecule shrinks, and the initial dispersibility and redispersibility decrease. There is a risk. The HLB value is preferably 2.0 to 5.0, more preferably 2.5 to 5.0, from the viewpoint of initial dispersibility and redispersibility.
In addition, the HLB value calculated | required by the Griffin method in this invention is described in detail in "Introduction of surfactant" (Takehiko Fujimoto, Sanyo Kasei Kogyo Co., Ltd., issued in 2007), and calculates | requires based on this description Can do.

The polyether compound in which R in formula (1) is a hydrogen atom can be produced by adding alkylene oxide to a polyethylene polyamine having 2 to 5 nitrogen atoms.
In the addition reaction of alkylene oxide, a catalyst may be used, and in some cases, the catalyst may not be used. Examples of the catalyst used for the addition reaction of alkylene oxide include alkali catalysts, such as alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydroxides, alcoholates, and alkylamines such as triethylamine. Alkanolamines such as triethanolamine can be used. In addition to the above alkali catalyst, a Lewis acid catalyst such as boron trifluoride or 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 is a catalyst as needed for the compound having a nitrogen atom as 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 gas. The alkylene oxide can be added by continuously applying pressure in the presence of.

The polyether compound in which R in the formula (1) is a hydrocarbon group having 1 to 4 carbon atoms is an alkyl halide having 1 to 4 carbon atoms in the presence of an alkali catalyst as necessary after the addition reaction of alkylene oxide. It can be produced by reacting an alkenyl halide or the like to alkyl ether or alkenyl ether.
Examples of alkyl halides include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, methyl iodide, and ethyl iodide. Examples of alkenyl halides include allyl chloride and And methallyl chloride. As the alkali catalyst at this time, an alkali metal or alkaline earth metal oxide, an alkali metal or alkaline earth metal hydroxide, an alcoholate, or the like can be used.
The amount of alkyl halide or alkenyl halide charged is 100 to 400 mol% with respect to the hydroxyl group to be reacted, and the amount of alkali catalyst is 100 to 500 mol% with respect to the hydroxyl group to be reacted. The reaction temperature is generally 60 to 180 ° C.

  The non-aqueous dispersant of the present invention containing a polyether compound may be neutralized with an organic acid or an inorganic acid. Examples of the organic acid include acetic acid, glycolic acid, oxalic acid, citric acid, lactic acid, and malic acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like. 1 type (s) or 2 or more types selected from can be used. The non-aqueous dispersant of the present invention may contain these organic acids and inorganic acids as long as the effects of the present invention are not impaired.

[Non-aqueous dispersion composition]
The non-aqueous dispersion composition of the present invention contains a non-aqueous dispersant, a dispersion, and a non-aqueous solvent.
Content of a non-aqueous dispersing agent is 0.05-20 mass% in a non-aqueous dispersion composition. If 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 commensurate with the content may not be obtained. . The content of the non-aqueous dispersant is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass from the viewpoint of initial dispersibility or redispersibility.

Examples of the dispersion contained in the non-aqueous dispersion composition of the present invention include organic powder and inorganic powder.
Organic powders include, for example, azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzimidazolone, penylene, phthalocyanine, anthrapyridine, and dioxazine. And organic pigments.
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 of metals. Or an alloy powder composed of a metal and a nonmetal, a composite powder obtained by compounding a metal powder or an alloy powder, two or more kinds of inorganic powders, or a mixed powder obtained by mixing an inorganic powder and another powder. Is mentioned.
Other inorganic powders include silicate minerals, other silicate compounds, carbonate compounds, sulfate compounds, hydroxide compounds, oxide compounds, carbonized compounds, nitride compounds, titanate compounds and the like. For example, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, silicic acid Aluminum, 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, Carbon black, graphite, rock wool, glass wool, glass fiber, carbon fiber, carbon nanofiber, carbon nanotube (single wall nanotube, double wall nanotube, multi-wall Lumpur nanotubes) each powder such as and the like.

  As the dispersion, preferably, inorganic powders such as iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, and the like, and those Alloy powders, composite powders, and mixed powders. Examples thereof include silicate minerals, other silicate compounds, carbonate compounds, sulfate compounds, hydroxide compounds, oxide compounds, carbonized compounds, nitride compounds, and titanate compounds. For example, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, silicic acid Aluminum, 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 Examples include powders. More preferably, metal powder, oxide compound powder, carbonized compound powder, nitride compound powder, titanate compound powder are used. For example, metal powder such as aluminum, nickel, cobalt, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, oxidation Powders of oxide compounds such as indium and indium tin oxide, powders of carbide compounds such as silicon carbide and tungsten carbide, powders of nitride compounds such as aluminum nitride, silicon nitride and boron nitride, titanate compounds such as barium titanate Each powder is mentioned. More preferably, metal powders such as nickel, cobalt, palladium, copper, silver, gold and platinum, powders of carbonized compounds such as silicon carbide and tungsten carbide, powders of nitride compounds such as aluminum nitride, silicon nitride and boron nitride The body is mentioned.

  The average particle size of the dispersion is preferably 0.01 to 10 μm, more preferably 0.01 to 5 μm, and still more preferably 0.01 to 1 μm, from the viewpoint of usefulness. The average particle size of the dispersion can be measured by a microtrack method.

  Content of a dispersion is 10-90 mass% normally in a non-aqueous dispersion composition, Preferably it is 30-85 mass%, More preferably, it is 55-80 mass%.

  Examples of the non-aqueous solvent (organic solvent) that serves as a dispersion medium for dispersing the dispersion in the non-aqueous dispersion composition of the present invention include aromatic hydrocarbon solvents such as toluene and xylene, and hydrocarbon 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 monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Glycols such as 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 mono n-butyl ether Ether solvent, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono n-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 monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono n-propyl ether acetate, and dipropylene glycol mono n-butyl ether Glycol ether ester solvents such as acetate, terpene solvents such as terpineol, dihydroterpineol, terpinyl acetate, and dihydroterpinyl acetate, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t -Alcohol solvents such as butanol and the like, 1 selected from these non-aqueous solvents Or it may be used two or more kinds.

The non-aqueous solvent has a solubility parameter (SP value) of 8.5 to 10.5 (cal / cm ³ ) ^1/2 from the viewpoint of improving the dispersibility of the dispersion and compatibility with the polyether compound in the present invention. Those of ² are preferred. The solubility parameter (SP value) of the non-aqueous solvent can be calculated by the Fedors method.
Specific examples of non-aqueous solvents having a solubility parameter (SP value) in the above range include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, isopropyl acetate, 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 Glycol monomethyl ether acetate, propylene glycol mono-n- butyl ether acetate, terpineol, dihydro terpineol, terpineol acetate, include dihydro terpineol acetate. One kind selected from these non-aqueous solvents may be used alone, or a mixture of two or more kinds may be used.
Moreover, even if it is a non-aqueous solvent whose solubility parameter (SP value) is outside the range of 8.5 to 10.5 (cal / cm ³ ) ^1/2 , The SP value can also be adjusted to the range.
The SP value of the mixed solvent can be obtained experimentally, and as a simple method, it can also be calculated by the sum of products 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 is adjusted by these methods can be used.

  Content of a non-aqueous solvent is 5-50 mass% normally in a non-aqueous dispersion composition, Preferably it is 10-40 mass%, More preferably, it is 15-30 mass%.

  Various additives such as other surfactants, binders, plasticizers, and antifoaming agents can be blended in the non-aqueous dispersion composition of the present invention as long as the purpose is not impaired.

The non-aqueous dispersion composition of the present invention can be produced according to a known method for producing a non-aqueous dispersion composition. For example, after adding the dispersion in a non-aqueous solvent in which the dispersant is dissolved, stirring at room temperature and mixing, after adding the non-aqueous solvent and the dispersion to the dispersion, stirring at room temperature And a method of mixing.
A known disperser can be used as a disperser for stirring, mixing, or dispersing. Examples thereof include a roll mill, a ball mill, a bead mill, a sand mill, a jet mill, a homogenizer, and a rotation / revolution mixer. Further, the dispersion treatment can be performed in an ultrasonic wave generation bath.

  Next, the present invention will be described in more detail with reference to examples and comparative examples.

Synthesis Example 1 [Synthesis of Polyether Compound 1]
In a 5 liter stainless steel pressure vessel equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blowing pipe, exhaust pipe, cooling coil, and steam jacket, diethylenetriamine (manufactured by Kanto Chemical Co., Inc., nitrogen per mole) 103 g of active hydrogen bonded to atoms: 5 equivalents) was charged, and the system was replaced with nitrogen gas. After heating up to 80 ° C. under stirring, 220 g of ethylene oxide (1 equivalent of active hydrogen bonded to nitrogen atoms) from a pressure vessel prepared separately under conditions of 80 to 100 ° C. and 0.05 to 0.5 MPa (gauge pressure) Was added while being pressurized with nitrogen gas through a gas blowing tube.
After the addition was completed, the reaction was continued 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 system was replaced with nitrogen gas. After raising the temperature to 100 ° C. with stirring, 440 g of ethylene oxide (corresponding to 2 moles per equivalent of active hydrogen bonded to a nitrogen atom) under the conditions of 100 to 120 ° C. and 0.05 to 0.5 MPa were added to a gas blowing tube. And added under pressure with nitrogen gas.
After the addition was completed, the reaction was continued under the same conditions until the internal pressure became constant. Next, 3,490 g of propylene oxide (corresponding to 12 moles per equivalent of active hydrogen bonded to a nitrogen atom) was passed through a gas blowing tube under stirring at 100 to 120 ° C. and 0.05 to 0.5 MPa. It added, pressurizing with nitrogen gas.
After the addition was completed, the reaction was continued under the same conditions until the internal pressure became constant. After cooling to 30 ° C., the reaction product was taken out from the pressure vessel into a 5-liter eggplant flask. 43 g of an adsorbent (trade name: KYOWARD 700, manufactured by Kyowa Chemical Industry Co., Ltd.) is added thereto, and the mixture is treated at 90 to 100 ° C. under 0.05 MPa in a nitrogen gas atmosphere, and the resulting salt and adsorbent are filtered off. As a result, a polyether compound 1 was obtained. The amine value of the obtained polyether compound 1 was 39.6, and the molecular weight determined from the amine value was 4,250.

In addition, the measuring method of the amine value of the polyether compound 1 is as follows.
A sample is weighed into a beaker, and neutral ethanol (ethyl alcohol (99.5 V / V%) neutralized with N / 2 hydrochloric acid standard solution using bromocresol green indicator immediately before use) is added thereto. To dissolve. Next, several drops of bromcresol green indicator were added and titrated with a N / 2 hydrochloric acid standard solution. The end point was when the green color of the solution turned yellow. The amine value was calculated from the following formula.
Amine number = (28.05 × F × A) / W
However, A: Amount of N / 2 hydrochloric acid standard solution used, F: Factor of N / 2 hydrochloric acid standard solution, W: Amount of sample collected (g)

  Further, by appropriately changing diethylenetriamine, ethylene oxide, and propylene oxide in Synthesis Example 1 to other compounds and performing operations according to Synthesis Example 1, polyether compounds 3 to 5 in Table 1 and Poly in Table 2 Ether compounds 6 to 8 were synthesized.

Synthesis Example 2 [Synthesis of Polyether Compound 2]
In an apparatus similar to that used in Synthesis Example 1, 95 g of tetraethylenepentamine (manufactured by Tosoh Corporation, active hydrogen bonded to nitrogen atom per mole: 7 equivalents) and 7.8 g of potassium hydroxide were charged. Was replaced with nitrogen gas. After the temperature was raised to 100 ° C. with stirring, 870 g of ethylene oxide (corresponding to 5 moles per equivalent of active hydrogen bonded to a nitrogen atom) under the conditions of 100 to 120 ° C. and 0.05 to 0.5 MPa was added to a gas blowing tube. And added under pressure with nitrogen gas.
After completing the addition, the reaction was continued under the same conditions until the internal pressure became constant. Next, 3,050 g of propylene oxide (corresponding to 15 mol per equivalent of active hydrogen bonded to a nitrogen atom) was passed through a gas blowing tube under stirring at 100 to 120 ° C. and 0.05 to 0.5 MPa. It added, pressurizing with nitrogen gas.
After completing the addition, the reaction was continued under the same conditions until the internal pressure became constant. After cooling to 30 ° C. or lower, 290 g of potassium hydroxide was charged, and the system was replaced with nitrogen gas. After the temperature was raised to 80 ° C., 34 g of methyl chloride was added at 80 to 100 ° C. through a gas blowing tube while being pressurized with nitrogen gas.
After the addition was completed, the reaction was continued under the same conditions until the internal pressure became constant. While blowing nitrogen gas, treatment was performed at 70 to 80 ° C. and 0.05 MPa or less for 1 hour to remove unreacted methyl chloride from the system. After cooling the internal pressure to 0.05 MPa with nitrogen gas and cooling to 60 ° C., 0.5 liter of ion-exchanged water at 60 ° C. was gradually added with stirring. After adding ion-exchange water and stirring sufficiently, it was allowed to stand in a sealed state at 60 to 70 ° C. for about 2 hours. After standing, the upper polyether layer and the aqueous layer were separated, and the polyether layer was taken in a 5-liter eggplant flask and dehydrated at 90 to 100 ° C. and 0.05 MPa or less in a nitrogen gas atmosphere. After dehydration, 40 g of an adsorbent (trade name: KYOWARD 700, manufactured by Kyowa Chemical Industry Co., Ltd.) is added, and the mixture is treated at 90 to 100 ° C. and 0.05 MPa or less in a nitrogen gas atmosphere, and the resulting salt and adsorbent are filtered. Separately, polyether compound 2 was obtained. The amine value of the obtained polyether compound 2 was 35.4, and the molecular weight determined from the amine value was 7,930. The amine value of the polyether compound 2 was measured in the same manner as in Synthesis Example 1.

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

[Examples 1-4, Comparative Examples 1-4]
Using polyether compounds 1 to 8 as a dispersant, a non-aqueous dispersion composition was prepared as follows.
In a 50 mL screw tube, weigh 2.0 g of silver powder (average particle size: 0.7 μm, measured by Microtrac method), 0.67 g of terpineol, and 0.02 g of a dispersant, and stir for 5 minutes with a rotating and rotating mixer. Thus, a slurry-like non-aqueous dispersion composition containing inorganic powder was obtained. The SP value of terpineol is 9.7 (cal / cm ³ ) ^1/2 .
The non-aqueous dispersion composition obtained using the polyether-based compounds 1 to 4 was sequentially used as Examples 1 to 4, and the non-aqueous dispersion composition obtained using the polyether-based compounds 5 to 8 was sequentially used. Comparative Examples 1 to 4 were used.

[Dispersion test]
A dispersion test was performed using the non-aqueous dispersion compositions of Examples 1 to 4 and Comparative Examples 1 to 4.
For each non-aqueous dispersion composition, using a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar), the shear viscosity for a temperature of 20 ° C. and a shear rate of 0.1 to 100 (1 / s). Was measured. Table 3 shows the shear viscosity when the shear rate is 1 (1 / s).
In addition, each non-aqueous dispersion composition that was allowed to stand at room temperature for 1 week was re-stirred for 5 minutes with a rotation and revolution type mixer, and the shear viscosity of each non-aqueous dispersion composition was measured under the same conditions. Table 3 shows the shear viscosity when the shear rate is 1 (1 / s).

The non-aqueous dispersion compositions of Examples 1 to 4 to which the polyether compounds 1 to 4 according to the present invention were added all showed good dispersibility immediately after production, and even after one week, Little change in viscosity was seen.
On the other hand, the non-aqueous dispersion composition of Comparative Example 1 to which the polyether compound 5 having an HLB value outside the specified range of the present invention was added has a small change in viscosity over time, but has a high shear viscosity immediately after production. Dispersibility was poor.
Nonaqueous dispersions of Comparative Examples 2 and 3 in which polyether compounds 6 and 7 having a structure in which the addition form of alkylene oxide in the polyether compound represented by formula (1) according to the present invention is reversed are added The body composition had a small change in viscosity over time, but the shear viscosity was extremely high immediately after production, and the dispersibility was much inferior.
In addition, the non-aqueous dispersion composition of Comparative Example 4 to which the polyether compound 8 that does not contain an ethylene oxide chain is added has not only a high shear viscosity immediately after production but also a large change in viscosity over time. From this, it can be seen that not only the dispersibility immediately after production but also the redispersibility is poor.

[Examples 5-7, Comparative Examples 5-7]
Using polyether compounds 1, 3-6, and 8 as dispersants, non-aqueous dispersion compositions were prepared as described below. In addition, the non-aqueous dispersion composition obtained using the polyether compounds 1, 3, and 4 was sequentially used as Examples 5 to 7, and obtained using the polyether compounds 5, 6, and 8. The non-aqueous dispersion composition was made into Comparative Examples 5-7 sequentially.
In a 50 mL screw tube, weigh 2.0 g of silicon nitride powder (average particle size: 1.0 μm, measured by Microtrac method), 1.08 g of ethylene glycol monobutyl ether acetate, and 0.06 g of a dispersant, and rotate and revolve. The mixture was stirred for 5 minutes with a mixer to obtain a slurry-like non-aqueous dispersion composition containing inorganic powder. The SP value of ethylene glycol monobutyl ether acetate is 8.8 (cal / cm ³ ) ^1/2 .

[Dispersion test]
A dispersion test was performed using the non-aqueous dispersion compositions of Examples 5 to 7 and Comparative Examples 5 to 7.
For each non-aqueous dispersion composition, using a dynamic viscoelastic device (Paar Physica MCR-300, manufactured by Anton Paar), the shear viscosity for a temperature of 20 ° C. and a shear rate of 0.1 to 100 (1 / s). Was measured. Table 4 shows the shear viscosity when the shear rate is 1 (1 / s).
In addition, each non-aqueous dispersion composition that was allowed to stand at room temperature for 1 week was stirred again for 5 minutes with a rotation and revolution mixer, and the shear viscosity of each non-aqueous dispersion composition was measured under the same conditions. The shear viscosity when the shear rate is 1 (1 / s) is also shown in Table 4.

The non-aqueous dispersion compositions of Examples 5 to 7 to which the polyether compound according to the present invention was added all showed good dispersibility immediately after production, and the viscosity change with time even after 1 week It was hardly seen.
On the other hand, the non-aqueous dispersion composition of Comparative Example 5 to which the polyether compound 5 having an HLB value outside the specified range of the present invention was added, and the alkylene in the polyether compound represented by the formula (1) according to the present invention The non-aqueous dispersion composition of Comparative Example 6 to which the polyether compound 6 having a structure in which the addition form of the oxide is reversed has a small change in viscosity over time, but has a very high shear viscosity immediately after production. Dispersibility was much inferior.
In addition, the non-aqueous dispersion composition of Comparative Example 7 to which the polyether compound 8 that does not contain an ethylene oxide chain in the structure is not only high in shear viscosity immediately after production, but also has a large change in viscosity over time. From this, it can be seen that not only the dispersibility immediately after production but also the redispersibility is poor.

Claims (2)

It contains a polyether compound represented by the formula (1), having a molecular weight of 1,000 to 10,000, and an HLB value determined by the Griffin method of 1.0 to 5.0. Non-aqueous dispersant.

(Wherein ^{A 1} O is an oxyethylene group, a is an average molar number of addition of oxyethylene group represented by ^{A 1} O, a 1 to 10 .A ² O is an oxypropylene group, b is A The average added mole number of the oxypropylene group represented by ² O, which is 1 to 30. a and b satisfy the relationship of 0.05 ≦ a / b ≦ 0.75 and 5 ≦ a + b ≦ 30. R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n is 1 to 4.)   A non-aqueous dispersion composition comprising the non-aqueous dispersant according to claim 1.