JP2014040573A - Ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition with low dynamic surface tension comprising an alkylene oxide adduct and a colorant.SOLUTION: The ink composition comprises as essential components: an alkylene oxide adduct (A) represented by the general formula (1) with alkyleneoxy groups having a distribution of added moles, in which a distribution constant c obtained from the equation (1) derived from the Weibull distribution law is 1.0 or less; and a colorant (B).

Description

  The present invention relates to an ink composition having a low dynamic surface tension over a wide surface life.

  In the printing industry, the paper industry, and the paint industry, water-based technology is being promoted from the viewpoint of environmental problems in recent years. However, in the case of water-based systems, the drying speed is slower and the production speed is slower than that of solvent-based systems.Therefore, there is no choice but to cope with higher speeds associated with improved productivity, and inks suitable for high-speed printing and high-speed coating. There is a demand for improved performance of paper coating agents. From such a background, in the water-based ink and water-based paint industry, an ink composition having a low surface tension is required for wetting, penetrating and dispersibility imparting to a substrate, and an alkylene oxide is added to a specific alcohol. Ink compositions using added nonionic surfactants have been proposed (Patent Documents 1 and 2).

JP 2007-91624 A JP 2011-509334 A

However, in the compositions of Patent Documents 1 and 2, the static surface tension is low, but the dynamic surface tension is not low, and improvements are demanded in applications such as printing and coating.
An object of the present invention is to provide an ink composition having a low dynamic surface tension over a wide surface life.

［式中、Ｌｎ(ｎ₀₀／ｎ₀)は(ｎ₀₀／ｎ₀)の自然対数を意味し、ｖは脂肪族アルコール１モル当たりに付加したアルキレンオキサイドの平均付加モル数を表し、ｎ₀₀は反応に用いた脂肪族アルコールのモル数、ｎ₀は未反応の脂肪族アルコールのモル数を表す。］ That is, the present invention is an alkylene oxide adduct represented by the following general formula (1), wherein the alkyleneoxy group has an addition molar distribution, and is derived from the following mathematical formula (1) derived from Weibull's distribution rule. It is an ink composition containing as essential components an alkylene oxide adduct (A) and a colorant (B) whose required distribution constant c is 1.0 or less.
R ¹ O (AO) mH (1)
[Wherein, R ¹ is an aliphatic hydrocarbon group having 6 to 10 carbon atoms; AO is an alkyleneoxy group having 2 to 4 carbon atoms; m is a number of 3 to 14 representing the average number of added moles of alkylene oxide. ]

[Wherein Ln (n ₀₀ / n ₀ ) means the natural logarithm of (n ₀₀ / n ₀ ), v represents the average number of moles of alkylene oxide added per mole of aliphatic alcohol, and n ₀₀ Represents the number of moles of aliphatic alcohol used in the reaction, and n ₀ represents the number of moles of unreacted aliphatic alcohol. ]

  Since the ink composition of the present invention has a low dynamic surface tension over a wide surface life, the ink droplet spreads when the ink lands on the recording medium, and the image density can be improved.

  The ink composition of the present invention is an ink composition containing the alkylene oxide adduct (A) and the colorant (B) represented by the general formula (1) as essential components, and the alkylene oxide adduct (A) is The alkyleneoxy group has an addition molar distribution, and the distribution constant c obtained from the following formula (1) derived from the Weibull distribution rule is 1.0 or less.

R ¹ in the general formula (1) is an aliphatic hydrocarbon group having 6 to 10 carbon atoms, and may be a linear or branched aliphatic hydrocarbon group or a saturated or unsaturated aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group having 6 to 10 carbon atoms include hexyl group, heptyl group, octyl group, nonyl group, decyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, hexenyl group, heptenyl group, An octenyl group, a nonenyl group, a decenyl group, etc. are mentioned.
Among these, from the viewpoint of dynamic surface tension lowering ability, a branched aliphatic hydrocarbon group having 6 to 10 carbon atoms is preferable, and more preferably, 7 carbon atoms having 1 to 6 branched chains having 1 to 3 carbon atoms. 10 to 10 branched aliphatic hydrocarbon groups, particularly preferably 4,6-dimethyl-1-octyl group and 3,5,5-trimethyl-1-hexyl group.
If the number of carbon atoms is less than 6, it is not preferable because the surface activity decreases. On the other hand, if the number of carbon atoms exceeds 10, the static surface tension decreases, but the dynamic surface tension with a short surface life is high, which is not preferable.

  AO in the general formula (1) is an alkyleneoxy group having 2 to 4 carbon atoms, and specific examples include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group.

  M in the general formula (1) is a number of 3 to 14 representing the average number of added moles of alkylene oxide. The number is preferably 4 to 10, more preferably 4 to 7. If m is less than 3, the solubility in water is insufficient, and if m exceeds 14, the dynamic surface tension increases, which is not preferable. Since the alkylene oxide adduct (A) in the present invention has a distribution in the number of added moles, it has high solubility in water and can exhibit dynamic surface tension lowering ability.

In the present invention, the alkylene oxide adduct (A) is an aliphatic oxide ethylene oxide (hereinafter abbreviated as EO) adduct, 1,2-propylene oxide (hereinafter abbreviated as PO). ) Adduct, 1,2-, 1,3-, 2,3- or 1,4-butylene oxide (hereinafter abbreviated as BO), EO and PO random adduct, EO / PO block addition , PO / EO block adduct, EO and BO random adduct, EO / BO block adduct and BO / EO block adduct.
Among these, a PO / EO block adduct represented by the following general formula (2) is preferable from the viewpoint of dynamic surface tension lowering ability.

［式中、Ｒ^２は炭素数６〜１０の脂肪族炭化水素基；ｎはプロピレンオキサイドの平均付加モル数を表す３〜１０の数、ｋはエチレンオキサイドの平均付加モル数を表す０〜４の数であり、かつ、３≦ｎ＋ｋ≦１４を満たす数である。］

[Wherein R ² is an aliphatic hydrocarbon group having 6 to 10 carbon atoms; n is a number of 3 to 10 representing the average number of added moles of propylene oxide, k is 0 to 4 representing the average number of added moles of ethylene oxide. And a number satisfying 3 ≦ n + k ≦ 14. ]

R ² in the general formula (2) is the same as R ¹ in the general formula (1), and the preferred range is also the same. In general formula (2), n is a number of 3 to 10 representing the average number of added moles of propylene oxide, k is a number of 0 to 4 representing the average number of added moles of ethylene oxide, and satisfies 3 ≦ n + k ≦ 14. Is a number. n is preferably a number from 3 to 8, and k is preferably a number from 0 to 2.

  Weibull's distribution constant c represents the ratio of the reaction rate constant when 1 mole of alkylene oxide reacts with 1 mole of an aliphatic alcohol alkylene oxide adduct and the reaction rate when 1 mole of alkylene oxide reacts with an aliphatic alcohol. Specifically, it is calculated from Equation (1). ["Nonionic surfactants", pages 28-34, Martin J. et al. Sick, Dekker (1967)]. The smaller the value of c, that is, the smaller the unreacted alcohol content, the narrower the molecular weight distribution.

この式で、Ｌｎ(ｎ₀₀／ｎ₀)は(ｎ₀₀／ｎ₀)の自然対数を意味し、ｖは脂肪族アルコール１モル当たりに付加したアルキレンオキサイドの平均付加モル数を表し、ｎ₀₀は反応に用いた脂肪族アルコールのモル数、ｎ₀は未反応の脂肪族アルコールのモル数を表す。

In this formula, Ln (n ₀₀ / n ₀ ) means the natural logarithm of (n ₀₀ / n ₀ ), v represents the average number of moles of alkylene oxide added per mole of aliphatic alcohol, and n ₀₀ Represents the number of moles of the aliphatic alcohol used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol.

C of the alkylene oxide adduct (A) is 1.0 or less, preferably 0.8 or less.
When c exceeds 1.0, it is not preferable from the viewpoint of odor derived from unreacted alcohol and ability to reduce dynamic surface tension.

The alkylene oxide adduct (A) in the present invention can be obtained by adding an alkylene oxide (C) having 2 to 4 carbon atoms to an aliphatic alcohol (a) having 6 to 10 carbon atoms.
Examples of the aliphatic alcohol (a) having 6 to 10 carbon atoms include alcohols having a linear or branched chain aliphatic hydrocarbon group.
Specifically, hexyl alcohol, isohexyl alcohol, heptyl alcohol, isoheptyl alcohol, octyl alcohol, isooctyl alcohol, nonyl alcohol, isononyl alcohol, decyl alcohol, isodecyl alcohol, hexenyl alcohol, heptenyl alcohol, octenyl alcohol , Nonenyl alcohol, decenyl alcohol and the like.
Among these, from the viewpoint of dynamic surface tension lowering ability, a branched aliphatic alcohol having 7 to 10 carbon atoms is preferable, and more preferably, 7 to 10 carbon atoms having 1 to 6 branched chains having 1 to 3 carbon atoms. Is a branched aliphatic alcohol. An aliphatic alcohol having less than 6 carbon atoms is not preferable because the surface activity is reduced. In addition, although the static surface tension is lowered with an aliphatic alcohol having more than 10 carbon atoms, it is not preferable because the ability to reduce the dynamic surface tension with a short surface life is low.

  Specific examples of the alkylene oxide (C) having 2 to 4 carbon atoms include EO, PO, and BO.

Although there is no restriction | limiting in particular as a manufacturing method of an alkylene oxide adduct (A), For example, the following method is mentioned.
An aliphatic alcohol (a) having 6 to 10 carbon atoms is charged into a pressurized reaction vessel, and an alkylene oxide (C) having 2 to 4 carbon atoms is blown in the presence of an acidic catalyst (D) [aliphatic alcohol (a) 1 The reaction is carried out at normal pressure or under pressure. The reaction temperature is usually 50 to 200 ° C., and the reaction time is usually 2 to 20 hours. After completion of the addition reaction of the alkylene oxide (C), the catalyst is neutralized and treated with an adsorbent to remove and purify the catalyst to obtain the alkylene oxide adduct (A1).
By adding an alkali catalyst (F) to the alkylene oxide adduct (A1) thus obtained and reacting the same or different alkylene oxide (C) with the same method as above, the desired alkylene An oxide adduct (A) is obtained.

Examples of the acidic catalyst (D) include perhalogenic acid (salt), sulfuric acid (salt), phosphoric acid (salt), nitric acid (salt), and perfluoroalkylsulfonic acid metal salt. The metal for forming the salt is not particularly limited, but a divalent or trivalent metal is preferable from the viewpoint of the Weibull distribution constant described later. These metals include Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al, Cd, Ti, Hf, Cr, Mo, Mn, Fe, Pd, and rare earth atoms, and more preferably Mg, Zn, Ca, Sr, Ba, Al, Cu, Cd, Ti, Cr, Fe, and rare earth atoms, particularly preferably Mg, Zn, Al, Ti, Fe, and Sc.
Examples of the halogen of the perhalogen acid (salt) include chlorine, bromine and iodine, and chlorine is preferred from the viewpoint of the Weibull distribution constant.
As the perfluoroalkylsulfonic acid metal salt, trifluoromethanesulfonate and pentafluoroethanesulfonate are preferable. More preferred is scandium triflate.
The acidic catalyst (D) is preferably a divalent or trivalent metal perchlorate and a perfluoroalkylsulfonic acid metal salt, more preferably a metal perchlorate selected from Mg, Zn and Al. , Trifluoromethanesulfonate and pentafluoroethanesulfonate, particularly preferably magnesium perchlorate, zinc perchlorate, aluminum perchlorate and scandium triflate.
The amount of the acidic catalyst (D) used is preferably 0.001 to 1% by weight based on the weight of the alkylene oxide adduct (A1) from the viewpoint of reaction rate and economy. More preferably, it is 0.003-0.8 weight%, Most preferably, it is 0.005-0.5 weight%.

Alkali catalysts (F) include alkali metal or alkaline earth metal (lithium, sodium, potassium, cesium, magnesium, calcium, barium, etc.) hydroxides and alkoxides (methoxide, ethoxide, propoxide, butoxide, etc.), tertiary Examples include amines (such as triethylamine and trimethylamine) and quaternary ammonium salts (such as tetramethylammonium hydroxide), and potassium hydroxide, sodium hydroxide, and cesium hydroxide are preferable.
The amount of the alkali catalyst (F) used is preferably 0.0001 to 1% by weight based on the weight of the alkylene oxide adduct (A) from the viewpoints of reaction rate and economy. More preferably, it is 0.001 to 0.5 weight%.

  In the ink composition of the present invention, the dynamic surface tension at a surface lifetime at 25 ° C. of 100 ms is preferably 35 mN / m or less. As a result, the spread of the ink droplets when the ink lands on the recording medium is increased, and the image density can be improved.

It is known that the dynamic surface tension of a liquid such as ink is generally measured by a vibration jet method, a meniscus method, a maximum bubble pressure method or the like. It is based on a pressure method (bubble pressure method), and can be measured using, for example, a bubble pressure type dynamic surface tension meter BP-2 manufactured by KRUSS.
In dynamic surface tension measurement by the maximum bubble pressure method, gas is sent from a gas supply source to the probe, and bubbles are generated from the tip of the probe immersed in ink. By changing the gas flow rate at this time, the gas generation speed is changed, and the surface tension is measured by the pressure applied to the bubbles from the ink that changes accordingly. When the bubble radius becomes equal to the radius of the probe tip, the maximum pressure (maximum bubble pressure) is indicated.
The surface life in the present invention refers to the time from when a bubble leaves a probe after a maximum bubble pressure and a new surface is formed until the next maximum bubble pressure is reached.

  The content of (A) in the ink composition of the present invention is 0.2 to 20% by weight, preferably 0.5 to 10% by weight.

  As the colorant (B), pigments and dyes such as inorganic pigments and organic pigments conventionally used in paints and inks can be used.

  Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

  Organic pigments include β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone and other soluble azo pigments, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetanilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as sindrinone, quinacridone, dioxazine, perinone, and perylene.

  Specific examples of dyes include yellow dyes, as coupling components, phenols, naphthols, anilines, pyrazolones, pyridones, or aryl or heteryl azo dyes having open-chain active methylene compounds, coupling components as open-chains Examples include azomethine dyes having an active methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes It is done.

  For magenta dyes, as coupling components, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) Aryl or heteryl azo dyes having, as coupling components, azomethine dyes having a pyrazolone or pyrazolotriazoles, arylidene dyes, styryl dyes, merocyanines such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes And quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of the coupling component include phenols, naphthols, anilines, aryl or heteryl azo dyes having pyrrolopyrimidinone or pyrrolotriazinone derivatives, and indigo / thioindigo dyes.

  The particle diameter of the colorant (B) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm, as an average particle diameter.

  The content of the colorant (B) in the ink composition of the present invention is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight, based on the weight of the ink composition. It is.

  The ink composition of the present invention can contain a pigment dispersant, a water-soluble organic solvent, a pH adjuster, an antioxidant and the like as necessary.

  By using the pigment dispersant, the dispersibility of the pigment is improved, and the storage stability of the ink composition of the present invention can be improved. As a pigment dispersant, a pigment dispersant (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184, manufactured by Big Chemie Japan Co., Ltd. Or 2020), pigment dispersants manufactured by Ajinomoto Fine Techno Co., Ltd. (Ajisper PB711, PB821, PB814, PN411, PA111, etc.) and pigment dispersants manufactured by Nihon Lubrizol Corp. (Solspers 5000, 12000, 32000, 33000, 39000, etc.). It is done. These pigment dispersants may be used alone or in combination of two or more. The addition amount of the pigment dispersant is not particularly limited, but it is preferably used in the ink composition in the range of 0 to 10% by weight, more preferably 0.2 to 8% by weight.

  Examples of water-soluble organic solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethylene glycol alkyl ether acetate, propylene glycol alkyl ether acetate, etc.) ), Alcohol (methanol, ethanol, normal propanol, isopropanol, glycerin, butanol, etc.) and the like. These may be used alone or in combination of two or more. The content of the water-soluble organic solvent in the ink composition is preferably 1 to 60% by weight.

The ink composition of the present invention has a low dynamic surface tension over a wide surface life and can be used in fields such as printing and coating. In particular, it can be suitably used as an inkjet ink in the printing field, and can be particularly suitably used as an aqueous ink. When used in the above applications, the ink composition containing the alkylene oxide adduct (A) and the colorant (B) of the present invention as essential components is an anionic surfactant (fatty oil) within the range not impairing the effects of the present invention. Group salts, alkyl sulfates, alkyl sulfate esters, alkyl sulfosuccinates, etc.), cationic surfactants (alkyl ammonium salts, etc.), amphoteric surfactants (alkyl amide betaines, alkylamide sulfobetaines, etc.), alkylenes of the present invention Other surfactants such as nonionic surfactants (such as polyoxyethylene acetylene glycol ether) other than the oxide adduct (A) may be blended.
The content of the surfactant other than (A) is preferably 0.2 to 5% by weight based on the weight of the ink composition, and one or more of these may be used in combination.

The ink composition of the present invention disperses an alkylene oxide adduct (A), a colorant (B) and, if necessary, a pigment dispersant, a surfactant other than (A), a water-soluble organic solvent, and other components. Or it melt | dissolves and also manufactures by stirring and mixing as needed. This stirring and mixing can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like, and can also be performed by a stirrer using a stirring blade, a magnetic stirrer, a high-speed disperser, or the like.
The colorant (B) is preferably contained as a pigment dispersion produced by dispersing a pigment and a pigment dispersant in water and further stirring and mixing as necessary. Stirring and mixing can be performed by the same method as in the production of the ink composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1> [Synthesis of 2-ethyl-1-hexanol EO4 mol adduct (A-1)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 130 parts of 2-ethyl-1-hexanol (1 mol part) and 1 part of aluminum perchlorate nonahydrate (0.002 mol part) The mixture was purged with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 80 ° C., 88 parts (2 mol parts) of EO were added dropwise over 10 hours while adjusting the pressure to be 0.2 MPaG or less, and then aged at 95 ° C. for 5 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent (KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.) is added and the mixture is stirred for 1 hour at 70 ° C. An EO2 molar adduct (a-1) of ethyl-1-hexanol was obtained. After adding 0.1 part of potassium hydroxide to the obtained (a-1), the temperature was raised to 70 ° C. and dehydration was performed under reduced pressure for 1 hour. The temperature was raised to 140 ° C., 88 parts (2 mol parts) of EO were added dropwise over 3 hours while adjusting the pressure to be 0.5 MPaG or less, and then aged at 140 ° C. for 2 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent (KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.) is added and the mixture is stirred for 1 hour at 70 ° C. An EO4 molar adduct (A-1) of ethyl-1-hexanol was obtained. {(A-1) is a compound in which R ¹ in the general formula (1) is a 2-ethyl-1-hexyl group, AO is an ethyleneoxy group, m is 4, and c is 0.50}.
The method of calculating the Weibull distribution constant c is as follows.
The distribution constant c was obtained from the above formula (1) derived from the Weibull distribution law. The amount of unreacted alcohol was measured using gas chromatography under the following conditions.
Model: Gas chromatograph GC-14B (manufactured by Shimadzu Corporation)
Detector: FID column: Glass column (inner diameter = about 3 mm, length = about 2 m)
Column filler: Silicon GE SE-30 5%
Column temperature: 90 ° C. to 280 ° C. Temperature increase rate = 4 ° C./min Carrier gas: Nitrogen sample: 50% acetone solution injection amount: 1 μl
Quantification: Quantification was performed using an alcohol having 2 or 3 carbon atoms less than the alcohol used as an internal standard substance.

<Production Example 2> [Synthesis of EO6 mol adduct (A-2) of 2-ethyl-1-hexanol]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 130 parts of 2-ethyl-1-hexanol (1 mol part) and 1 part of aluminum perchlorate nonahydrate (0.002 mol part) Was added, the temperature was raised to 70 ° C., and dehydration was performed under reduced pressure for 1 hour. The temperature was raised to 80 ° C., 88 parts (2 mol parts) of EO were added dropwise over 10 hours while adjusting the pressure to be 0.2 MPaG or less, and then aged at 95 ° C. for 5 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent (KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.) is added and the mixture is stirred for 1 hour at 70 ° C. An EO2 molar adduct (a-2) of ethyl-1-hexanol was obtained. After adding 0.2 parts of potassium hydroxide to the obtained (a-2), the mixture was purged with nitrogen and sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 140 ° C., 176 parts (4 mol parts) of EO was added dropwise over 5 hours while adjusting the pressure to be 0.5 MPaG or less, and then aged at 140 ° C. for 2 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent (KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.) is added and the mixture is stirred for 1 hour at 70 ° C. An EO6 molar adduct (A-2) of ethyl-1-hexanol was obtained. {(A-2) is a compound in which R ¹ in the general formula (1) is a 2-ethyl-1-hexyl group, AO is an ethyleneoxy group, m is 6, and c is 0.60}.

<Production Example 3> [Synthesis of EO4 molar adduct (A-3) of 3,5,5-trimethyl-1-hexanol]
In the same manner as in Production Example 1, except that 130 parts (1 mole part) of 2-ethyl-1-hexanol was changed to 144 parts (1 mole part) of 3,5,5-trimethyl-1-hexanol, 3, 5, An EO4 molar adduct (A-3) of 5-trimethyl-1-hexanol was obtained {(A-3) represents R ¹ in the general formula (1) is a 3,5,5-trimethyl-1-hexyl group, AO is an ethyleneoxy group, m is 4, and c is 0.52.}

<Production Example 4> [Synthesis of EO6 molar adduct (A-4) of 3,5,5-trimethyl-1-hexanol]
In the same manner as in Production Example 2, except that 130 parts (1 mole part) of 2-ethyl-1-hexanol was changed to 144 parts (1 mole part) of 3,5,5-trimethyl-1-hexanol, 3, 5, An EO4 molar adduct (A-4) of 5-trimethyl-1-hexanol was obtained {(A-4) represents R ¹ in the general formula (1) is a 3,5,5-trimethyl-1-hexyl group, AO is an ethyleneoxy group, m is 6, and c is 0.58}.

<Production Example 5> [Synthesis of decanol EO5 molar adduct (A-5)]
Manufactured except that 130 parts (1 mole part) of 2-ethyl-1-hexanol was changed to 158 parts (1 mole part) from decanol [manufactured by KH Neochem Co., Ltd.] and 176 parts of EO were changed to 132 parts (3 mole parts). in the same manner as in example 2, EO 5 mole adduct of decanol (a-5) was obtained {(a-5) may, ^{R 1} in the general formula (1) is a decyl group, AO is an ethyleneoxy group, m is 5 , C is 0.57}.

<Production Example 6> [Synthesis of decanol EO2 mol (EO5 mol / PO1 mol) random adduct (A-6)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping cylinder, 158 parts (1 mole part) of decanol [manufactured by KH Neochem Co., Ltd.] and 1 part of magnesium perchlorate hexahydrate (0.004 mole) Part) was added, the temperature was raised to 80 ° C., and dehydration was performed under reduced pressure for 1 hour. The temperature was raised to 95 ° C., 88 parts (2 mol parts) of EO were added dropwise over 10 hours while adjusting the pressure to be 0.2 MPaG or less, and then aged at 95 ° C. for 5 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and the mixture is stirred for 1 hour at 70 ° C., and then the adsorption treatment agent is filtered to remove decanol. EO2 molar adduct (a-6) was obtained. After adding 0.5 part of potassium hydroxide to the obtained (a-6), the temperature was raised to 95 ° C. and dehydration was performed under reduced pressure for 1 hour. The temperature was raised to 140 ° C., and a mixture of EO 220 parts (5 mol parts) and PO 58 parts (1 mol parts) was added dropwise over 5 hours while adjusting the pressure to be 0.5 MPaG or less. Aged for 2 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and the mixture is stirred for 1 hour at 70 ° C., and then the adsorption treatment agent is filtered to remove decanol. EO2 mol (EO5 mol / PO1 mol) random adduct (A-6) was obtained. {(A-6) is a compound in which R ¹ in the general formula (1) is a decyl group, AO is an ethyleneoxy group and a propyleneoxy group, m is 8, and c is 0.82.}

<Production Example 7> [Synthesis of 1-nonanol EO6 mol adduct (A-7)]
In the same manner as in Production Example 2, except that 130 parts (1 mole part) of 2-ethyl-1-hexanol was changed to 144 parts (1 mole part) of 1-nonanol, an EO6 mole adduct (A-7) of decanol was obtained. The obtained {(A-7) is a compound in which R ¹ in the general formula (1) is an n-nonyl group, AO is an ethyleneoxy group, m is 6, and c is 0.60}.

<Production Example 8> [Synthesis of PO4 mol adduct (A-8) of 3,5,5-trimethyl-1-hexanol]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 144 parts of 3,5,5-trimethyl-1-hexanol (1 mol part) and 0.5 parts of potassium hydroxide (0.009 mol part) ), Purged with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 130 ° C., and PO 232 parts (4 mol parts) was added dropwise over 10 hours while adjusting the pressure to be 0.2 MPaG or less, followed by aging at 140 ° C. for 5 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and the mixture is stirred for 1 hour at 70 ° C., and then the adsorption treatment agent is filtered. A PO4 molar adduct (A-8) of 5,5-trimethyl-1-hexanol was obtained. {(A-8) is a compound in which R ¹ in the general formula (1) is a 3,5,5-trimethyl-1-hexyl group, AO is a propyleneoxy group, m is 6, and c is 0.55}.

<Production Example 9> [Synthesis of PO3 mol EO2 mol adduct (A-9) of 3,5,5-trimethyl-1-hexanol]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 144 parts of 3,5,5-trimethyl-1-hexanol (1 mol part) and 0.5 parts of potassium hydroxide (0.009 mol part) ), Purged with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 130 ° C., and 174 parts (3 mole parts) of PO was added dropwise over 9 hours while adjusting the pressure to 0.2 MPaG or less, and then aged at 140 ° C. for 5 hours. Next, 88 parts (2 mole parts) of EO was added dropwise over 5 hours while adjusting the pressure to be 0.5 MPaG or less, and then aged at 140 ° C. for 2 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and the mixture is stirred for 1 hour at 70 ° C., and then the adsorption treatment agent is filtered. A PO3 mol EO2 mol adduct (A-8) of 5,5-trimethyl-1-hexanol was obtained. {(A-9) is a compound in which R ¹ in the general formula (2) is a 3,5,5-trimethyl-1-hexyl group, n is 3, k is 2, and c is 0.84}.

<Comparative Production Example 1> [Synthesis of EO15 molar adduct (A′-1) of 3,5,5-trimethyl-1-hexanol]
EO15 mol adduct (A′-1) of 3,5,5-trimethyl-1-hexanol was the same as Production Example 2 except that EO 176 parts (4 mol parts) was changed to EO572 parts (13 mol parts). {(A′-1) is a compound in which R ¹ in the general formula (1) is a 3,5,5-trimethyl-1-hexyl group, AO is an ethyleneoxy group, and m is 15}.

<Comparative Production Example 2> [Synthesis of EO2 molar adduct (A′-2) of 3,5,5-trimethyl-1-hexanol]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 144 parts (1, mol part) of 3,5,5-trimethyl-1-hexanol and 1 part of aluminum perchlorate nonahydrate (0. 002 mol part) was added, sealed with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 80 ° C., 88 parts (2 mol parts) of EO were added dropwise over 10 hours while adjusting the pressure to be 0.2 MPaG or less, and then aged at 95 ° C. for 5 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and the mixture is stirred for 1 hour at 70 ° C., and then the adsorption treatment agent is filtered. An EO2 molar adduct (A′-2) of 5,5-trimethyl-1-hexanol was obtained {(A′-2) represents R ¹ in the general formula (1) is 3,5,5-trimethyl-1 -A hexyl group, AO is an ethyleneoxy group, m is 2, and c is 0.38}.

<Comparative Production Example 3> [Synthesis of 2-ethyl-1-hexanol EO6 mol adduct (A'-3)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 144 parts (5 mole parts) of 3,5,5-trimethyl-1-hexanol, 0.5 parts (0.009 mole parts) of potassium hydroxide The mixture was purged with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 140 ° C., 264 parts (6 mol parts) of EO was added dropwise over 5 hours while adjusting the pressure to be 0.2 MPaG or less, and then aged at 160 ° C. for 2 hours. Next, after cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and the mixture is stirred for 1 hour at 70 ° C. An EO6 molar adduct (A′-3) of ethyl-1-hexanol was obtained {(A′-3) is R ¹ in the general formula (1) is a 2-ethyl-1-hexyl group, and AO is ethyleneoxy A compound wherein m is 6 and c is 3.54; }

<Comparative Production Example 4> [Synthesis of n-dodecyl alcohol EO 6 mol adduct (A'-4)]
Except for changing 130 parts (1 mole part) of 2-ethyl-1-hexanol to 186 parts (1 mole part) of n-dodecyl alcohol, in the same manner as in Production Example 2, an EO6 mole adduct of n-dodecyl alcohol (A '-4) was obtained {(A'-4) is a compound in which R ¹ in the general formula (1) is an n-dodecyl group, AO is an ethyleneoxy group, m is 6, and c is 0.86}.

<Comparative Production Example 5> [Synthesis of 3,5,5-trimethyl-1-hexanol EO12 mol / BO2 mol adduct (A′-5)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 144 parts (3 mole parts) of 3,5,5-trimethyl-1-hexanol and 1 part (0.009 mole parts) of potassium hydroxide are charged. The mixture was purged with nitrogen, sealed, heated to 70 ° C., and dehydrated under reduced pressure for 1 hour. The temperature was raised to 140 ° C., 528 parts (14 moles) of EO was added dropwise over 8 hours while adjusting the pressure to be 0.5 MPaG or less, and then 144 parts (2 moles) of BO was charged at 160 ° C. Aged for 5 hours. After cooling to 70 ° C., 10 parts of an adsorption treatment agent [KYOWARD 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added, and the mixture is stirred at 70 ° C. for 1 hour and treated. , 5-trimethyl-1-hexanol EO12 mol / BO2 mol adduct (A′-5) was obtained {(A′-5) is R ¹ in the general formula (1) is 3,5,5-trimethyl. A compound in which -1-hexyl group, AO is ethyleneoxy group and 1,2-butyleneoxy group, m is 14, and c is 1.38. }

<Production Example 10> [Preparation of pigment dispersion]
30 parts of carbon black (B-1), 6 parts of β-naphthol EO 40 mol adduct, and 164 parts of distilled water are mixed and dispersed for 1 hour using an ultrasonic disperser. A pigment dispersion containing 15% carbon black (P -1) was obtained. The resulting average particle size of the carbon black particles in the pigment dispersion liquid _{(D 50)} was measured, was 162.1Nm. The average particle size (D ₅₀ ) was measured using a laser diffraction / scattering particle size distribution measuring device (LA-750, manufactured by Horiba, Ltd.).

<Examples 1-9 and Comparative Examples 1-5>
<Creation of ink composition>
Each ink composition is in accordance with Table 1, (A) or (A ′) obtained in Production Examples 1 to 9 or Comparative Production Examples 1 to 5, and the pigment dispersion (P-1) obtained in Production Example 10. It was produced by stirring a water-soluble organic solvent and water and mixing them uniformly.

Table 1 shows the Weibull distribution constant c of the surfactant used in each example, and the dynamic surface tension of the obtained ink composition. The measurement conditions for the dynamic surface tension are as follows.
<Dynamic surface tension measurement>
Each ink composition was measured for the dynamic surface tension when the surface life at 25 ° C. was 100 ms and 1000 ms using a bubble pressure type dynamic surface tension meter BP-2 manufactured by KRUSS.

As is apparent from Table 1, the ink compositions of Examples 1 to 9 exhibited a very low surface tension at 100 ms with a short surface life.
For the ink composition of Comparative Example 1, unreacted alcohol was not detected, and the Weibull distribution constant c could not be calculated. Since the ink composition of Comparative Example 2 was poorly soluble in water, the dynamic surface tension could not be measured. In addition, the ink compositions of Comparative Examples 3 to 5 exhibited a wide dynamic molecular weight with a short surface life because they had a wide molecular weight distribution and did not exhibit sufficient surface activity.

  The ink composition comprising the alkylene oxide adduct and the colorant of the present invention has a low dynamic surface tension over a wide surface life, and therefore can be used in fields such as printing and coating. In particular, it can be suitably used for inkjet inks in the printing field, and can be particularly suitably used in aqueous inks.

Claims (5)

An alkylene oxide adduct represented by the following general formula (1), wherein the alkyleneoxy group has an addition molar distribution, and the distribution constant c obtained from the following mathematical formula (1) derived from the Weibull distribution rule is: An ink composition comprising, as essential components, an alkylene oxide adduct (A) and a colorant (B) which are 1.0 or less.
R ¹ O (AO) _m H (1)
[Wherein, R ¹ is an aliphatic hydrocarbon group having 6 to 10 carbon atoms; AO is an alkyleneoxy group having 2 to 4 carbon atoms; m is a number of 3 to 14 representing the average number of added moles of alkylene oxide. ]

[Wherein Ln (n ₀₀ / n ₀ ) means the natural logarithm of (n ₀₀ / n ₀ ), v represents the average number of moles of alkylene oxide added per mole of aliphatic alcohol, and n ₀₀ Represents the number of moles of the aliphatic alcohol used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol. ] The ink composition according to claim 1, wherein the alkylene oxide adduct (A) is an alkylene oxide adduct represented by the following general formula (2).

[Wherein R ² is an aliphatic hydrocarbon group having 6 to 10 carbon atoms; n is a number of 3 to 10 representing the average number of added moles of propylene oxide, k is 0 to 4 representing the average number of added moles of ethylene oxide. And a number satisfying 3 ≦ n + k ≦ 14. ] The ink composition according to claim 1, wherein the aliphatic hydrocarbon group is a hydrocarbon group having a branched chain.   The ink composition according to any one of claims 1 to 3, wherein the aliphatic hydrocarbon group is a branched hydrocarbon group having 1 to 6 branched chains having 1 to 3 carbon atoms.   The ink composition according to any one of claims 1 to 4, wherein a dynamic surface tension at a surface lifetime of 100 ms is 35 mN / m or less.