JP3229589B2 - Dispersant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel novel dispersant used as a pigment dispersant for printing inks, toners for copying machines, ink ribbons, paints and the like.

[0002]

2. Description of the Related Art Compounds obtained by reacting polyamines or polyethyleneimines with polyesters, or
Polyalkylene polyamine / alkanoic acid or alkenoic acid polycondensate or meta-xylene diamine-epichlorohydrin polycondensate and various polyesters as reactants are used for printing ink, copier toner, ink ribbon,
It has been conventionally known to be useful as a pigment dispersant for paints and the like.

For example, Japanese Patent Application Laid-Open No. 9-313917 discloses a dispersant synthesized from various polyesters using polyalkylene polyamine / alkanoic acid or alkenoic acid polycondensate or metaxylene diamine-epichlorohydrin polycondensate as a raw material. It has been reported. Further, Japanese Unexamined Patent Publication No.
JP-A-177123 discloses a dispersant synthesized by condensation of polyethyleneimine and a polyester having a free carboxyl group. Also, JP-B 63-30
No. 057 discloses a dispersant synthesized by condensation of polyethyleneimine and a polyester having a free carboxyl group synthesized from 12-hydroxystearic acid.

According to the study by the present inventors, the effect of the dispersant is that the amine in the polyamine moiety is a pigment adsorbing group,
It was presumed that the polarity of the polyester portion contributed to the action portion of solubility in the solvent, that is, to the dispersion performance. It was also found that the molecular weight of the polyamine part and the molecular weight of the polyester part and their ratio were also related to the dispersing performance. Furthermore, it has been found that a densely packed chain such as polyester near the amino group is disadvantageous for adsorbing the pigment due to steric hindrance.

In the technique disclosed in JP-A-9-313917, the polyamine molecular weight is small, the interaction with the pigment is not sufficient, and the dispersion performance cannot be said to be sufficient.
No. 3, JP-B-63-30057 is a technique in which the polyester portion is a polymer of a single monomer and is produced by reacting a polyester with a polyalkylene polyamine.
The steric hindrance was large and the adsorption of the pigment was not sufficient. Furthermore, since a single monomer polymer is used, the solvent to be solubilized is limited, and the versatility is poor. JP-A-9-313917
Although the solubility is improved, the dispersing power cannot be said to be sufficient for the above-mentioned reasons, and the solubility in various solvents tends to deteriorate when the molecular weight of the polyamine is increased to increase the adsorptivity to the pigment. Not something.

Therefore, these conventional dispersants cannot provide a sufficient dispersing and thinning effect when the pigment concentration is high, and furthermore, it is difficult to improve the glossiness of a coating film of ink or paint, and the aggregation and viscosity of the pigment increase. There was such a problem.

[0007]

An object of the present invention [0005] to be Solved, even when the pigment concentration is high, sufficient dispersibility, viscosity-reducing effect, improvement of gloss obtained at wide temperature range Solvent The purpose is to provide a dispersant that dissolves.

[0008]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polyalkynepolyamine derivative having a specific structure can solve these problems. Completed the invention.

That is, after capping the reaction points of the polyalkylene polyamine with a fatty acid at a specific ratio,
Polycarbonylalkyleneoxy as lipophilic polymer chain
By introducing the chains in a specific ratio, the dispersing ability was high and it became possible to dissolve in various solvents by changing the introduction ratio.

That is, the present invention provides a compound represented by the general formula (1):

[0011]

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(Where k is an integer of 10 to 230, m is 2 to 2)
Indicates an integer of 6. A) a polyalkylenepolyamide
Formula (1-1)

[0013]

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(Where R ₁  Is a hydrogen atom or a carbon number of 8 to
22 carboxylic acids or branched hydroxy Carboxylic acid residue
Shown, p is an integer of 2 to 11, q is an integer of 2 to 1000
Show. ) And the general formula (1-2)

[0015]

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(Wherein YCO is a carboxylic acid having 8 to 22 carbon atoms)
Indicates an acid residue. ) Is added to 1 part by weight of the general formula (1).
Then, 1 to 50 parts by weight of the general formula (1-1) and the general formula (1-
Compound or its compound in which 0.01 to 1.6 parts by weight of 2) is introduced.
Pertaining to a dispersant, characterized by comprising a salt of
It is.

Further, the present invention provides a compound represented by the following general formula (1):

[0018]

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(Where k is an integer of 10 to 230, m is 2 to 2)
Indicates an integer of 6. A) a polyalkylenepolyamide
General formula (2-1)

[0020]

Embedded image (R is an integer of 1 to 25, s is an integer of 0 to 20, t is 2 to
Indicates an integer of 100. ) And the general formula (1-2)

[0021]

Embedded image

(Wherein YCO is a carboxylic acid having 8 to 22 carbon atoms)
Indicates an acid residue. ) Is added to 1 part by weight of the general formula (1).
Then, 1 to 50 parts by weight of the general formula (2-1) and the general formula (1-
2) a compound in which 0.01 to 1.6 parts by weight is introduced, or
It relates to a dispersant characterized by consisting of its salt
is there.

[0023]

Dispersant of the present invention DETAILED DESCRIPTION OF THE INVENTION, partially capping of reactive sites of the polyalkylene polyamine represented by the following following general formula (1) by the general formula (1-2), the remaining reactive sites The general formula (1-1) or the general formula (2-
It is the one into which the polyester of 1) is introduced.

The fatty acid content of the fatty acid capping is 0.05 to 1 part by weight of the raw material polyalkylene polyamine.
Capping is performed in a range of from 1 part by weight to 1.6 parts by weight. The raw material polyalkylene polyamine has the general formula (1)

[0025]

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( Where k is an integer of 10 to 230 , m is 2 to 2)
Indicates an integer of 6. ).

If the amount of the fatty acid group of the general formula (1-2) to be capped is less than 0.05 part by weight, the polyester groups are densely packed and the area around the amino group of the polyamine becomes sterically bulky, and the adsorbability of the pigment is reduced. Degenerate. Polyester that exhibits a dispersing effect when capping exceeds 1.6 parts by weight
And the dispersing effect is degraded.

The polyester group of the general formula (1-1) is a substituent which affects the dispersing effect. number of amine significantly reduced adsorption of the dispersant to the pigment may turn poor.

In the dispersant compound of the present invention, the alkylene chain represented by the repeating unit m has 2 to 2 carbon atoms.
6. In the general formula (1-1), p is 2 to 11, preferably 3, 5 which is industrially easily available. Further, q is from 2 to 1000, and if it is out of this range, the balance of the molecular weight with the polyalkylene polyamine becomes poor, and as a result, the solubility in the solvent becomes poor and the dispersion becomes poor, which is not preferable.

In the formula (1-2), the carboxylic acid is a carboxylic acid having 8 to 22 carbon atoms, preferably having 12, 14, 16, 18, 18F1, or 12-hydroxystearic acid, which is industrially easily available. It is . Claim 2
The average molecular weight of the hydroxycarboxylic acid condensed portion in the formula is in the range of 100 to 8000, and is preferably a 12-hydroxystearic acid condensate having an average molecular weight of 1500. The average molecular weight of the hydroxycarboxylic acid condensate in the dispersant compound according to claim 2 is 10
Outside the range of 0 to 8000, the performance as a dispersant, that is, dispersibility and solubility in a solvent are deteriorated, which is not preferable.

The average molecular weight of the dispersant compound according to claim 1 or 2 is 2100 to 500,000, and if the average molecular weight is out of this range, the performance as a dispersant and the solubility in a solvent are unfavorably deteriorated.

The dispersant compound of the present invention may be in a free form or a salt. Salts can be formed by reacting the dispersant compound with an acid or by quaternizing the amino group.
The acids that can be used are sulfuric acid, acetic acid, hydrochloric acid, phosphoric acid,
Alkyl sulfonic acid and aryl sulfonic acid. The quaternizing agent is dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, methyl halide, and ethyl halide.

The method for producing the dispersant compound of the present invention is not particularly limited, but includes, for example, the following method.

The dispersant compound according to claim 1 has the general formula (1)

[0035]

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(Wherein k and m are the same as defined above), and a polyalkylene polyamine which may have a branched form in which a nitrogen atom is present as a primary, secondary or tertiary amino group, and Equation (5)

[0037]

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(Wherein Y CO represents a carboxylic acid residue having 8 to 22 carbon atoms), or a carboxylic acid which may contain a hydroxy group, or sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid,
40 to 2 in the presence of an acid catalyst such as p-toluenesulfonic acid
The reaction can be performed at 10 ° C, preferably 50 to 150 ° C, for 2 to 7 hours.

Further, the general formula (6)

[0040]

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(Where A is a hydroxyl group or chlorine, R ₁ ,
p and q are the same as defined above) and a polycarbonylalkyleneoxy acid of 40 to 230 ° C, preferably 100 ° C.
The reaction can be performed at ~ 150 ° C for 2 to 16 hours .

Alternatively, the general formula (1)

[0043]

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(Wherein k and m are the same as defined above), and a polyalkylene polyamine which may contain a branched form in which a nitrogen atom is present as a primary, secondary or tertiary amino group, and Equation (5)

[0045]

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[0046] (wherein Y CO represents a carboxylic acid acid residues having 8 to 22 carbon atoms.) Only good acid contains hydroxy groups represented by or, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, p- toluene 40 in the presence of an acid catalyst such as sulfonic acid
The reaction can be carried out at a temperature of up to 210 ° C, preferably 50 to 150 ° C, for 2 to 7 hours. Further, general formula (8)

[0047]

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A lactone represented by the formula (where u represents an integer of 2 to 11) is added with 12-hydroxystearic acid as needed, and the mixture is added at 40 to 230 ° C., preferably 100 to 1
Tetrabutyl titanate at 50 ° C., zirconium naphthenate, can be produced by multiple match Rukoto using a catalyst such as zinc acetate or toluene sulphonic acid.

Further, the dispersant compound according to claim 2 has the general formula (1)

[0050]

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(Wherein k and m are the same as defined above) and a general formula (4)

[0052]

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(Wherein YCO represents a carboxylic acid residue having 8 to 22 carbon atoms) only a carboxylic acid which may contain a hydroxy group, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, p
40-21 in the presence of an acid catalyst such as toluenesulfonic acid
The reaction can be performed at 0 ° C, preferably 50 to 150 ° C, for 2 to 7 hours. After this reaction, general formula (9)

[0054]

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(B is a hydroxyl group or chlorine, r is 1 to 25
, S is an integer of 0 to 20, and t is an integer of 2 to 100. A) a branched polyester group represented by
0-230 ° C, preferably 100-150 ° C, 2-1
The reaction can be performed for 6 hours .

The reaction may be carried out under normal pressure or under pressure. The reaction is preferably performed in a nitrogen atmosphere in order to prevent decomposition of organic substances by oxygen.

The dispersant of the present invention includes, as inorganic pigments, titanium dioxide, cadmium sulfide, zinc oxide, chromate, carbon black, talc, barium carbonate, calcium carbonate, iron oxide, Prussian blue, ultramarine, etc.
In addition, azo, diazo, thioindigo, indanthrone, phthalocyanine, anthraquinone, isobenzanthrone, etc. can be dispersed well as organic pigments, and printing inks, paints, magnetic recording media, toners for copying, color plastic molded products, rubber magnets, sealing It can be used for the production of agents and the like.

Next, the present invention will be specifically described with reference to examples.

[0059]

[Production Example] Intermediate product 1: polycarbonylalkyleneoxy acid (PCAO acid) 1 To 684.8 g of ε-caprolactone and 300.5 g of 12-hydroxystearic acid, 0.68 g of tetrabutyl titanate was added, and 140 ° C. in a nitrogen atmosphere. And stirred for 7 hours. The product was a waxy material at room temperature with an acid number of 38.0 mg KOH / g.

Intermediate product 2: polycarbonylalkyleneoxy acid (PCAO acid) 2 To 1483.8 g of ε-caprolactone and 300.5 g of 12-hydroxystearic acid, 1.48 g of tetrabutyl titanate was added, and the mixture was heated at 140 ° C. in a nitrogen atmosphere. Stir for 9 hours. The product was a waxy material at room temperature with an acid number of 28.0 mg KOH / g.

Intermediate product 3: polycarbonylalkyleneoxy acid (PCAO acid) 3 To 2054.5 g of ε-caprolactone and 300.5 g of 12-hydroxystearic acid, 2.05 g of tetrabutyl titanate was added, and 140 ° C. in a nitrogen atmosphere. Stir for 11 hours. The product was a waxy material at room temperature with an acid number of 20.0 mg KOH / g.

[0062]

Example 1 12-Polyethyleneimine having a molecular weight of 1800 (trade name: Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd.) was added to 22.4 g.
Hydroxystearic acid (12.0 g) was added, and the mixture was stirred and reacted at 140 ° C for 5 hours in a nitrogen atmosphere. The product has an acid value of 1.
1.9 mg KOH / g, amine value 611.1 mg KOH
/ G. 1,578.9 g of the intermediate product was added thereto, and the mixture was stirred at 120 ° C. for 7 hours in a nitrogen atmosphere. The product had an acid value of 20.4 mg KOH / g and an amine value of 18.0 mg.
It was a waxy material at room temperature with KOH / g.

Example 2 After reacting polyethyleneimine with 12-hydroxystearic acid as in Example 1 above, the intermediate products 2,12
2.6 g was added and reacted at 120 ° C. for 5 hours in a nitrogen atmosphere. The product was a waxy substance at room temperature with an acid number of 25.6 mg KOH / g and an amine number of 24.8 mg KOH / g.

Example 3 In Example 1, 11.4 g of stearic acid was added in place of 12-hydroxystearic acid and reacted in the same manner. Acid value 21.0mgKOH / g, amine value 16.0mgKOH
/ G at room temperature to give a waxy material.

Example 4 In the above Example 1, 8.0 g of lauric acid was added in place of 12-hydroxystearic acid and reacted in the same manner. Acid value 2
1.8 mg KOH / g, amine value 17.1 mg KOH /
g of a waxy substance was obtained at room temperature.

EXAMPLE 5 Instead of 12-hydroxystearic acid, 12.0 g of a mixture of 85% of 12-hydroxystearic acid and 15% of stearic acid was added in the same manner as in Example 1 described above, and the mixture was reacted in the same manner to give an acid value of 1
8.0 mgKOH / g, amine value 15.0 mgKOH / g
g of a waxy substance at room temperature was obtained.

Example 6 12-Polyethyleneimine having a molecular weight of 10,000 (trade name: Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.) was added to 6.5 g.
3.5 g of hydroxystearic acid was added, and the mixture was stirred and reacted at 140 ° C. for 5 hours in a nitrogen atmosphere. The product has an acid value of 7.1 m
gKOH / g, an amine value of 951.0 mgKOH / g, and further, an intermediate product 3, 325.0 g were added, and the mixture was stirred and reacted at 120 ° C. for 5 hours in a nitrogen atmosphere. The product has an acid value of 14.7 mgKOH / g and an amine value of 14.0 mgKO.
H / g and was a waxy substance.

Example 7 9.6 g of 12-hydroxystearic acid was added to 6.0 g of polyethyleneimine having a molecular weight of 1800 (trade name: Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd.), and the mixture was added under nitrogen atmosphere.
The mixture was stirred and reacted at 40 ° C. for 5 hours. The product has an acid value of 9.5 mg.
KOH / g, an amine value of 300.3 mg KOH / g, and 272.0 g of an intermediate product 3 were further added thereto, and the mixture was stirred and reacted at 120 ° C. for 5 hours in a nitrogen atmosphere. The product has an acid value of 15.1 mg KOH / g and an amine value of 11.0 mg KOH.
/ G and a waxy substance.

Example 8 After reacting polyethyleneimine with 12-hydroxystearic acid as in Example 1, 550.1 g of 12-hydroxystearic acid condensate (trade name KF-1000, manufactured by Kawaken Fine Chemical Co., Ltd.) was obtained. Add in nitrogen atmosphere 1
The reaction was stirred at 20 ° C. for 5 hours. The product has an acid value of 22.0 m
It was a wax-like substance having gKOH / g and an amine value of 14.9 mgKOH / g.

Example 9 A mixture of 150 g of the reaction product of Example 4 and 3.7 g of dimethyl sulfate was reacted in a nitrogen atmosphere at 100 ° C. for 1 hour. The product was a waxy material at room temperature with an amine number of 0.0 mg KOH / g.

Example 10 Polyethyleneimine reacted with 12-
To 15.0 g of the hydroxystearic acid reactant, 255.0 g of ε-caprolactone and 0.1 g of tetrabutyl titanate were added.
25 g of the mixture was stirred and reacted in a nitrogen atmosphere at 150 ° C. for 2 hours. The reaction product was a wax-like substance having an acid value of 3.7 mgKOH / g and an amine value of 16.3 mgKOH / g.

The dispersing ability test of the compounds of Examples 1 to 10 was performed. Dispersibility was evaluated by a sedimentation stability test. Furthermore, after the ink was formed, the viscosity and glossiness were measured. The solubility in organic solvents was also investigated. The results are shown below.

The sedimentation stability test was carried out by using carbon (Columbian Carbon Japan Co., Ltd.) as a pigment in a test tube.
200 mg of Raven 780), 10 mg of a dispersant, and 10 ml of xylene were added, and after 30 times of inverting stirring, the mixture was allowed to stand and measured for the thickness of the dispersion layer after a certain period of time. Example 2 described in JP-A-9-313917 as a comparative example
(Comparative Example 1). The following is a description of Japanese Patent Application Laid-Open
Reference is made to the production method of Example 2 described in JP-A-313917.

Comparative Example 1 Intermediate product polycarbonylalkylene oxyacid (PCAO acid) ε-caprolactone 684.8 g, 12-hydroxystearic acid 300.4 g and tetrabutyl titanate 0.1.
68 g was added and the mixture was stirred at 140 ° C. for 9 hours in a nitrogen atmosphere. A PCAO acid having an acid value of 28.0 mg KOH / g gave a solid reaction at room temperature. 125.0 of this intermediate product
g and 10.0 g of a polyalkylenepolyamine-alkanoic acid or alkenoic acid polycondensate (trade name “76T”, manufactured by Sanwa Chemical Industry Co., Ltd.) at 150 ° C. in a nitrogen atmosphere.
For 3 hours. The product has an amine value of 14.8 mgK
The reaction product was a solid at room temperature having OH / g, and was soluble in toluene, MEK, and the like.

As a comparative example, Japanese Patent Publication No. Sho 63-3005
Example 2 described in the specification of No. 7 and Dispersant C (Comparative Example 2) were also performed. In the following,
Reference is made to the production method of Example 2 described in the specification of No. 7.

Preparation of Polyester A A mixture consisting of 348 parts by weight of xylene and 3350 parts by weight of commercial grade 12-hydroxystearic acid (having an acid number and a hydroxyl number of 182 mg KOH / g and 160 mg KOH / g, respectively) is treated for 22 hours 190
The mixture is stirred at ２００200 ° C. to separate the water formed during the reaction from the xylene in the distillate, which is then returned to the reaction medium. After collecting 152 parts by weight of water, xylene was added to 200 parts by weight.
Removed by heating in a stream of nitrogen at 0 ° C. The resulting pale yellow liquid has an acid value of 35.0 mg KOH / g.

Comparative Example 2 Dispersant C Highly branched polyethyleneimine having a molecular weight of about 5000 (trade name "PEI600" by Dow Chemical Company)
A mixture consisting of 75 parts by weight of toluene and 21.6 parts by weight of toluene was stirred and boiled under nitrogen, water was removed from the distillate using a separator, and toluene was added to the reaction mixture. To return. 500 parts by weight of polyester A and further 21.6 parts by weight of toluene are added and the mixture is stirred while distilling off the toluene until the temperature reaches 150 ° C. 150 ° C after 1 hour
The mixture becomes too viscous to stir, but the mixture is maintained at 150 ° C. for an additional 2 hours. Upon cooling, a brown gum is produced that is soluble in hydrocarbon solvents. The acid value is 16.8 mg KOH / g.

[0078]

[Table 1]

The measurement of the viscosity after the formation of the ink was performed as follows.

30 g of carbon (Raven 780, manufactured by Columbian Carbon Japan Co., Ltd.), 60 g of acrylic resin
(Acrydic A- manufactured by Dainippon Ink and Chemicals, Inc.)
801, non-volatile content 50%), toluene 7g, dispersant 3g
, And the viscosity was measured with a B-type viscometer (rotor No. 3, 60 rpm, 25 ° C). The results are shown in Table 2.

[0081]

[Table 2]

After the ink was formed in the same manner as in Table 2, the color was drawn on a PET film using a bar coder (No. 5, 5 μm), and the gloss at 60 ° incident angle was measured with a gloss meter after color development. Table 3 shows the results.

[0083]

[Table 3]

Further, the solubility of the dispersant in various organic solvents was also investigated. Tables 4 and 5 show the results.

[0085]

[Table 4]

[0086]

[Table 5]

As is clear from the results shown in Examples 1 to 10 and Tables 1 to 5, the novel dispersant of the present invention has superior dispersing ability, viscosity reducing effect and performance of improving glossiness more than conventional products. have.

[0088]

Industrial Applicability The novel polymer dispersant of the present invention has excellent dispersing ability, viscosity reducing effect, and gloss improvement performance more than conventional products, and is useful for printing inks, toners for copying machines, It is useful as a pigment dispersant for ink ribbons and paints.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 7/02 C09D 7/02 11/02 11/02 (72) Inventor Masahiro Yasaka 1-3-34 Kitafu, Takefu City, Fukui Prefecture Takeo Inside Fine Chemical Co., Ltd. (72) Inventor Gozo Matsuda 1-3-34, Kitafu, Takefu-shi, Fukui Prefecture Inside Takefu Fine Chemical Co., Ltd. (56) References JP-A-9-313917 (JP, A) JP-A-2 −48029 (JP, A) JP 6-44985 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01F 17/52 B01F 17/16 B01F 17/34

Claims (5)

(57) [Claims] 1. A general formula (1) ## STR1 ## (Where k represents an integer of 10 to 230, and m represents an integer of 2 to 6)
You. The polyalkylene polyamine represented by the general formula
(1-1) ## STR2 ## (Wherein R ₁ is a hydrogen atom or a carbohydrate having 8 to 22 carbon atoms)
Acid or branched hydroxycarboxylic acid residue, p is 2
An integer of 1 to 11, and q represents an integer of 2 to 1000. ) And
Fine the general formula (1-2) ## STR3 ## (Wherein YCO represents a carboxylic acid residue having 8 to 22 carbon atoms)
You. ) Is substituted with 1 part by weight of the general formula (1).
(1-1) is 1 to 50 parts by weight, and the general formula (1-2) is 0.1% by weight.
From 0.1 to 1.6 parts by weight of a compound or a salt thereof.
A dispersant, characterized in that: Wherein general formula (1) embedded image (Where k represents an integer of 10 to 230, and m represents an integer of 2 to 6)
You. The polyalkylene polyamine represented by the general formula
(2-1) [of 5] (R is an integer of 1 to 25, s is an integer of 0 to 20, t is 2 to
Indicates an integer of 100. ) And the general formula (1-2) [of 6] (Wherein YCO represents a carboxylic acid residue having 8 to 22 carbon atoms)
You. ) Is substituted with 1 part by weight of the general formula (1).
(2-1) is 1 to 50 parts by weight, and the general formula (1-2) 0.0
1 to 1.6 parts by weight of a compound or a salt thereof
A dispersant characterized by comprising: 3. The dispersant according to claim 1, wherein the substituent represented by the general formula (1-2) is a branched hydroxycarboxylic acid or a hydroxycarboxylic acid residue. 4. The dispersant compound having an average molecular weight of 2100
The dispersant according to any one of claims 1 to 3, wherein the dispersant is 500,000. 5. A salt with an acid selected from sulfuric acid, acetic acid, hydrochloric acid, phosphoric acid, alkylsulfonic acid and arylsulfonic acid, or dimethyl sulfate, diethyl sulfate, dimethyl carbonate, methyl halide, and halogenated salt. a salt of selected from ethyl quaternizing agent, claims 1
The dispersant according to claim 4 .