JP2013221088A - Dispersant for carbon black - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant for carbon black, capable of dispersing carbon black to various mediums such as solvent, resin and rubber.SOLUTION: A dispersant for carbon black contains a polyoxyalkylene amine compound (A) represented by general formula (1). A carbon black dispersion containing the dispersant, carbon black and a dispersion medium; and a method for producing the dispersant are also provided. [In the formula, Z is a residue obtained by removing p primary amino groups and n active hydrogens from an amine compound (a), AO is 2-4C alkylene oxy, m, which shows the average addition mole number of the alkylene oxy, is a number of 1-100, n is an integer of 1-5, and p is an integer of 1-3].

Description

  The present invention relates to a dispersant for carbon black. More specifically, the present invention relates to a dispersant for carbon black having high dispersibility.

  Carbon black is widely used in fields such as printing inks, paints, and plastic forming materials as color pigments and light shielding materials. In order to improve colorability and light absorption performance in these products, carbon black must be uniformly dispersed in a solvent or resin, and usually a method of adding various dispersants (for example, Patent Document 1).

Japanese Patent Laid-Open No. 11-256068

However, even if the method of Patent Document 1 is used, there is a drawback that a sufficiently satisfactory dispersion performance cannot be obtained, and versatility is poor from the viewpoint of the selectivity of the dispersion medium.
An object of this invention is to provide the dispersing agent for carbon black which can disperse | distribute carbon black to various media, such as a solvent, resin, or rubber | gum.

［式中、Ｚはアミン化合物（ａ）からｐ個の１級アミノ基の他、更にｎ個の活性水素を除いた残基、ＡＯは炭素数２〜４のアルキレンオキシ基、ｍはアルキレンオキシ基の平均付加モル数であって１〜１００の数、ｎは１〜５の整数、ｐは１〜３の整数である。］ As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention is selected from the group consisting of a dispersant for carbon black containing the polyoxyalkyleneamine compound (A) represented by the general formula (1); the dispersant, carbon black, a solvent, a resin, and rubber. A carbon black dispersion containing one type of dispersion medium; and a method for producing the dispersant.

[Wherein Z is a residue obtained by removing n active hydrogens in addition to p primary amino groups from amine compound (a), AO is an alkyleneoxy group having 2 to 4 carbon atoms, and m is alkyleneoxy. Average number of added moles of group, 1 to 100, n is an integer of 1 to 5, and p is an integer of 1 to 3. ]

  The dispersant for carbon black of the present invention can disperse carbon black in various media such as solvents, resins and rubbers, and the obtained dispersion has high dispersibility and excellent dispersion stability over time. There is an effect.

  The dispersant of the present invention is a dispersant for carbon black containing the polyoxyalkyleneamine compound (A) represented by the general formula (1).

Z in the general formula (1) represents a residue obtained by removing n active hydrogens in addition to p primary amino groups from the amine compound (a), n is an integer of 1 to 5, p is 1 to It is an integer of 3.
The amine compound (a) has n active hydrogens in addition to p primary amino groups, and 1 to 3 primary amino groups and 1 to 1 in addition to the active hydrogens of the primary amino group. It is preferred to have 5 active hydrogens.
Specific examples of the amine compound (a) include monoalcoholamines such as monoethanolamine and monopropanolamine; aminoethylethanolamine, aminoethylpropanolamine, aminoethylbutanolamine, aminopropylethanolamine, aminopropylpropanolamine, amino Aminoalkylalkanolamines such as propylbutanolamine; polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine; aminoethylpiperazine, aminopropylpiperazine, aminobutylpiperazine N-aminoethyl-N′-hydroxyethylpiperazine, N-aminopropyl-N′-hydro Xylethylpiperazine, N-aminobutyl-N'-hydroxyethylpiperazine, N-aminoethyl-N'-hydroxypropylpiperazine, N-aminopropyl-N'-hydroxypropylpiperazine, N-aminobutyl-N'-hydroxypropyl And piperazine derivatives such as piperazine. In addition, as (a), you may use 2 or more types of these together.
Of the amine compounds (a), aminoalkylalkanolamines, polyalkylenepolyamines and piperazine derivatives are preferred from the viewpoint of dispersibility, and polyalkylenepolyamines are particularly preferred.

AO in the general formula (1) is an alkyleneoxy group having 2 to 4 carbon atoms. Examples of the alkyleneoxy group having 2 to 4 carbon atoms include an ethyleneoxy group, a 1,2-propyleneoxy group, and 1,2-, A 1,3-, 2,3- or 1,4-butyleneoxy group may be mentioned.
M in the general formula (1) is an average added mole number of an alkyleneoxy group and is a number of 1 to 100, preferably 10 to 100, and more preferably 15 to 60. When m exceeds 100, it is not preferable from the viewpoint of dispersibility of carbon black.
(AO) m in the general formula (1) may be a combination of two or more alkyleneoxy groups having 2 to 4 carbon atoms, and the two or more addition forms may be block or random.

  As the polyoxyalkyleneamine compound (A), an amine oxide (a) 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) adduct, EO and PO random adduct, EO / PO block adduct, PO / EO Block adducts, random adducts of EO and BO, EO / BO block adducts, and BO / EO block adducts. Of these, from the viewpoint of dispersibility, EO and PO adducts and PO adducts, EO and BO adducts, PO and BO adducts, and BO adducts are preferred, and PO adducts and EO / PO block adduct.

Said (A) can be manufactured by a well-known method etc., However, It is preferable to manufacture by hydrolyzing the polyoxyalkylene ketimine compound (B) represented by following General formula (2).

In the formula, Z is a residue obtained by removing n active hydrogens in addition to p ketimine groups from the amine compound (a), AO is an alkyleneoxy group having 2 to 4 carbon atoms, and m is an average of alkyleneoxy groups. The number of moles added is 1 to 100, n is an integer of 1 to 5, p is an integer of 1 to 3, and R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms.

R ₁ and R ₂ in the general formula (2) are each independently an alkyl group having 1 to 6 carbon atoms, and may be a linear or branched alkyl group or a saturated or unsaturated alkyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, propenyl group, allyl group, n-butyl group, isobutyl group, t-butyl group and butenyl group, Examples include n-pentyl group, isopentyl group, n-hexyl group, and isohexyl group.

Said (B) is obtained by adding an alkylene oxide to the ketimine compound (C) obtained by making amine compound (a) and ketone (b) react.
As ketone (b), acetone, methyl ethyl ketone, methyl butyl ketone, methyl pentyl ketone, methyl hexyl ketone, diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, ethyl pentyl ketone, ethyl hexyl ketone, dipropyl ketone, propyl butyl ketone, propyl Examples include pentyl ketone and propyl hexyl ketone. From the viewpoint of removability after hydrolysis, methyl ethyl ketone and methyl butyl ketone are preferred.

  The ketimine compound (C) includes an amine compound (a) and an acetone ketimine compound, an amine compound (a) and a methyl ethyl ketone ketimine compound, an amine compound (a) and a methyl butyl ketone ketimine compound, an amine compound (a) and methyl Ketimine compound of isobutyl ketone, ketimine compound of amine compound (a) and methylhexyl ketone, ketimine compound of amine compound (a) and diethyl ketone, ketimine compound of amine compound (a) and ethyl propyl ketone, amine compound (a) Examples thereof include ketimine compounds of ethyl butyl ketone. From the viewpoint of removability after hydrolysis, an amine compound (a) and a ketimine compound of methyl ethyl ketone, and an amine compound (a) and a ketimine compound of methyl isobutyl ketone are preferred.

  As polyoxyalkylene ketimine compound (B) obtained by adding alkylene oxide to ketimine compound (C), EO adduct, PO adduct, BO addition of ketimine compound of amine compound (a) and ketone (b) EO and PO random adduct, EO / PO block adduct, PO / EO block adduct, EO and BO random adduct, EO / BO block adduct and BO / EO block adduct. Of these, from the viewpoint of dispersibility, EO and PO adducts and PO adducts, EO and BO adducts, PO and BO adducts, and BO adducts are preferred, and PO adducts and EO / PO block adduct.

The polyoxyalkyleneamine compound (A) in the present invention is produced by the following method.
An amine compound (a) and a ketone (b) are put into a reaction vessel, and heated and stirred. The reaction temperature is 50 to 150 ° C, preferably 60 to 90 ° C. The reaction time is 2 to 5 hours, and the reaction pressure is -0.1 MPaG to 0 MPaG. After the reaction, the ketimine compound (C) can be obtained by removing the produced water and excess ketone under reduced pressure of 80 to 150 ° C.
The obtained ketimine compound (C) is charged into a pressurized reaction vessel, and an alkylene oxide having 2 to 4 carbon atoms is blown in the absence of a catalyst or in the presence of a catalyst, and the reaction is carried out at normal pressure or under pressure. Examples of the catalyst include alkali catalysts [eg, hydroxides of alkali metals (lithium, sodium, potassium, cesium, etc.) and alkoxides (methoxide, ethoxide, propoxide, butoxide, etc.) The reaction temperature is usually 50 to 200 ° C. Yes, the reaction time is usually 2 to 20 hours, and the polyoxyalkylene ketimine compound (B) can be obtained.
Next, the polyoxyalkyleneamine compound (A) can be obtained by adding water, removing the ketone produced by hydrolysis and excess water while heating and stirring. The hydrolysis temperature is usually 50 to 150 ° C., and the amount of water used for the hydrolysis under a reaction pressure of −0.1 MPaG to 0 MPaG is usually preferably 2 to 100 equivalents relative to the polyoxyalkylene ketimine compound. If necessary, after completion of the addition reaction of alkylene oxide or after hydrolysis of the ketimine compound, the catalyst can be neutralized and treated with an adsorbent to remove and purify the catalyst.
The dispersant in the present invention may be used in combination with a known surfactant in order to further improve dispersibility and the like. Specifically, an alkylene oxide addition-type nonionic surfactant containing no polyoxyalkyleneamine compound (A) of the present invention; a polyhydric alcohol type nonionic surfactant such as a fatty acid alkanolamide; a sulfonic acid (salt) group And high molecular type and low molecular type anionic surfactants having a sulfate ester (salt) group, a phosphate ester (salt) group, a phosphonic acid (salt) group, and a carboxylic acid (salt) group.

  By using the dispersant of the present invention, a dispersion in which carbon black is dispersed in a dispersion medium such as a solvent, a resin, or rubber can be obtained.

  The solvent used in the present invention refers to water, an organic solvent and a mixture thereof, and is not particularly limited as long as it dissolves the dispersant. Specific examples include water, xylene, ethyl acetate, toluene, tetrahydrofuran, methyl ethyl ketone, acetone, butyl cellosolve, dimethylformamide, n-propanol, ethanol, dimethyl sulfoxide, n-butanol and methanol.

The resin used in the present invention can be used without any particular limitation. Specific examples include acrylic resins, polyester resins, alkyd resins, urethane resins, silicone resins, fluororesins, polycarbonate resins, and polyvinyl chloride resins, which can be used alone or in admixture of two or more. . Among these, a urethane resin or a silicone resin is preferable.
Examples of rubber include natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, isoprene rubber, butadiene rubber and other diene rubbers, halogen rubber such as chloroprene rubber, acrylic rubber, silicone rubber, and fluorine rubber. It is done. Among these, natural rubber, styrene butadiene rubber, isoprene rubber or butadiene rubber is preferable.

  The carbon black of the present invention is not particularly limited by the type and production history, and various types such as commercially available oil furnace black, gas furnace black, thermal furnace black, acetylene black, and channel black can be used. Ordinarily performed ozone treatment, plasma treatment, or liquid phase oxidation treatment carbon black may be used.

The contents of the dispersant, carbon black and dispersion medium in the dispersion of the present invention are as follows.
The dispersant is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, from the viewpoint of dispersibility, based on the weight of the dispersion.
Carbon black is preferably 3 to 50% by weight, more preferably 5 to 30% by weight, from the viewpoint of dispersibility, based on the weight of the dispersion.
The dispersion medium is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, from the viewpoint of stability, based on the weight of the dispersion.

  The weight of the dispersant in the dispersion is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the weight of carbon black. If it is less than 1% by weight, sufficient dispersibility cannot be obtained, and if it exceeds 40% by weight, the ratio of the dispersant becomes too high and the performance of the dispersion itself is undesirably lowered.

  Among the methods for producing a carbon black dispersion of the present invention, the method for dispersing in a solvent is obtained by mixing and stirring carbon black and a medium such as a dispersant and a solvent. There are no particular restrictions on the mixing and stirring method, but the pulverizer or disperser may be a three-roll mill or two-roll mill that finely disperses carbon black particles by shear stress, or carbon by the impact force of media such as glass beads or zirconia beads. Ball mills, attritors, sand mills, coball mills, basket mills, vibration mills, paint conditioners, etc. that disperse black, dispersers, homogenizers, etc. that finely disperse by rotating blades that generate shear stress, cavitation, collision force, potential core, etc. Also, kneaders, extruders, jet mills, etc. that finely disperse by carbon black particles or between carbon black particles and vehicle or disperser wall surface or shear force, ultrasonic waves that are finely dispersed by ultrasonic waves Such as dispersion machine can be mentioned. Furthermore, you may heat-process before and behind a dispersion | distribution process.

  As a method of dispersing in resin or rubber, the surface of carbon black is pretreated with a dispersant and then added to the resin or rubber. The carbon black or other compounding agent is added to the resin or rubber together. There are methods to do this, but any of them can be handled. Although there is no restriction | limiting in particular in the method of mixing and stirring, Well-known various apparatuses, such as a kneader, a pressure kneader, a Banbury mixer, a 2 roll, an intensive mixer, can be used.

  The field of use of the dispersion is not particularly limited, but is a field that requires light-shielding properties, conductivity, durability, jetness, etc., such as gravure ink, offset ink, back coat for magnetic recording media, electrostatic toner In addition, it is possible to provide a stable and uniform dispersion in ink jet, automobile paints, tires, fiber / plastic forming materials, and the like.

  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”.

<Example 1> [Synthesis of diethylenetriamine PO 40 mol adduct (A-1)]
Diethylenetriamine 103 parts (1 mol part) and methyl isobutyl ketone 400 parts (4 mol part) were put into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, and stirred at 90 ° C. for 2 hours under a nitrogen stream. Later, by removing unreacted methyl isobutyl ketone and produced water at −0.1 MPaG, the ketimination reaction was completed. Next, after raising the temperature to 140 ° C., 58 parts (1 mole part) of PO was added dropwise with stirring so that the pressure was adjusted to 0.5 MPaG or less, followed by aging at the same temperature for 3 hours. After aging, the mixture was cooled to 90 ° C., 5 parts of potassium hydroxide was added, and dehydration was performed at 90 ° C. for 1 hour. After the temperature was raised to 140 ° C., PO2622 parts (39 mol parts) were added dropwise over 8 hours while adjusting the pressure to be 0.5 MPaG or less with stirring, and the mixture was aged at the same temperature for 6 hours. After cooling to 90 ° C., 4.5 parts of acetic acid and 150 parts of water were added, and after stirring at 90 ° C. for 2 hours, methyl isobutyl ketone and excess water produced at −0.1 MPaG were removed, and diethylenetriamine PO 40 mol adduct was obtained. (A-1) was obtained. {(A-1) is a residue obtained by removing two primary amines and one active hydrogen from diethylenetriamine in general formula (1), AO is a propyleneoxy group, Compound in which m is 40, n is 1, and p is 2.}

<Example 2> [Synthesis of triethylenetetramine PO 80 mol adduct (A-2)]
The same procedure as in Example 1 was repeated except that 103 parts of diethylenetriamine was changed to 146 parts (1 mole part) of triethylenetetramine, 116 parts (2 mole parts) of PO58, and PO2622 part (78 mole parts) of PO2262 part. Ethylenetetramine PO 80 mol adduct (A-2) {(A-2) is a residue obtained by removing two primary amines and two active hydrogens from triethylenetetramine in the general formula (1), AO Is a propyleneoxy group, m is 40, n is 2, and p is 2.}

<Example 3> [Synthesis of diethylenetriamine BO 40 mol adduct (A-3)]
Diethylenetriamine BO40 mol adduct (A-3) {(A-3) in the same manner as in Example 1 except that 58 parts of PO were changed to 140 parts (2 parts by mole) of BO and 2626 parts of PO (39 parts by mole) were changed to BO2730 parts. In general formula (1), Z is a residue obtained by removing two primary amines and one active hydrogen from diethylenetriamine, AO is a butyleneoxy group, m is 40, n is 1, and p is 2. }.

<Example 4> [Synthesis of diethylenetriamine EO20 / PO20 molar random adduct (A-4)]
Diethylenetriamine EO20 / PO20 molar random adduct (A-4) {(A−) in the same manner as in Example 1 except that PO2262 part was changed to a mixture of PO1102 part (19 molar part) and EO880 part (20 molar part). 4) is a residue obtained by removing two primary amines and one active hydrogen from diethylenetriamine, AO is a propyleneoxy group and an ethyleneoxy group, m is 40, n is 1, Compound in which p is 2}.

<Comparative Example 1> [Synthesis of diethylenetriamine PO 40 mol adduct (A′-1)]
Into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, 103 parts (1 mole part) of diethylenetriamine was charged, and after replacing with reduced-pressure nitrogen, the temperature was raised to 140 ° C., and PO290 part (5 mole part) with stirring. Was added dropwise over 4 hours while adjusting the pressure to 0.5 MPaG or less, and aged at the same temperature for 5 hours. After aging, the mixture was cooled to 90 ° C., 5 parts of potassium hydroxide was added, and dehydration was performed at 90 ° C. for 1 hour. After the temperature was raised to 140 ° C., 2030 parts (35 mole parts) of PO was added dropwise with stirring so that the pressure was adjusted to 0.5 MPaG or less, and the mixture was aged at the same temperature for 6 hours. After cooling to 50 ° C., the mixture was neutralized with 4.5 parts of acetic acid to obtain diethylenetriamine PO 40 mol adduct (A′-1).

  About the dispersing agent of Examples 1-4 and Comparative Examples 1-2, carbon black dispersibility was evaluated with the following method. The results are shown in Table 1. The carbon black dispersibility evaluation method is as follows.

The abbreviations in Table 1 have the following meanings.
DETA: Diethylenetriamine

<Dispersibility of carbon black in toluene and stability over time>
Examples 1 to 4, 1 g of dispersants of Comparative Examples 1 and 2, 4 g of carbon black (“Mitsubishi Carbon Black MA100” [Mitsubishi Chemical Corporation]), 25 g of toluene, 50 g of glass beads (2.5 to 3.5 mm) Was put into a 100 ml plastic container with a lid and mixed and dispersed for 120 minutes with a paint conditioner (manufactured by Red Devil) to obtain a carbon black dispersion. The obtained carbon black dispersion was applied to a PET film using an applicator and dried so that the film thickness was 125 μm, and then dried. Then, a specular gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.) was used. The 60 degree gloss value was measured. A higher 60 degree gloss value means higher carbon black dispersibility. The obtained dispersion was allowed to stand at 25 ° C. for 1 month, and the 60 ° gloss value was measured in the same manner to evaluate the temporal stability.
[Evaluation criteria for carbon black dispersibility]
A: Excellent dispersibility (60 degree gloss value = 75 to −100)
○: Excellent dispersibility (60 degree gloss value = 50 or more and less than −75)
Δ: Dispersibility is slightly inferior (60 ° gloss value = 30 or more and less than −50)
X: Dispersibility is poor (60 degree gloss value = less than 30 or viscosity increases so that a coating film cannot be formed)

<Dispersibility and processability of carbon black in rubber>
140 g of styrene butadiene rubber (“Nipol 1712” [Nippon Zeon Co., Ltd.]) was placed in a Banbury mixer and kneaded for 1 minute, and then 80 g of carbon black (“Seast KH” [Tokai Carbon Co., Ltd.]), 3 g of zinc oxide, 2 g of stearic acid and 3 g of the dispersants of Examples 1 to 4 and Comparative Examples 1 and 2 were added all at once, and further kneading was continued and the rubber temperature was taken out at 150 ° C. Then, the rubber was allowed to cool, and 1.5 g of sulfur, 1 g of N-oxydiethyl-2-benzothiozolsulfenamide and 1 g of dibenzothiazyl disulfide were added and kneaded at 70 to 80 ° C. for 10 minutes using an 8-inch roll. An unvulcanized rubber composition was obtained. The Mooney viscosity of the obtained unvulcanized rubber composition was measured according to JIS K-6300, and the carbon black dispersibility and processability were evaluated. A lower Mooney viscosity means better processability and better carbon black dispersibility.
[Evaluation criteria for carbon black dispersibility and processability]
○: Excellent dispersibility and processability (Mooney viscosity = 80 or less)
Δ: Dispersibility and processability are slightly inferior (Mooney viscosity = 80 or more and less than −85)
X: Dispersibility and processability are poor (Mooney viscosity = 85 or more)

  As can be seen from Table 1, the dispersibility of carbon black can be greatly improved by using the dispersant of the present invention. In Comparative Example 1, the viscosity of the dispersion after mixing and dispersing by the paint conditioner was high, and a coating could not be formed.

  Since the carbon black dispersant of the present invention can stably and highly disperse carbon black in a solvent, resin, or rubber, it is used when blending carbon black as a black pigment, reinforcing agent, filler, or conductive agent. Suitable as a dispersant.

Claims (6)

A dispersant for carbon black containing a polyoxyalkyleneamine compound (A) represented by the following general formula (1).

[Wherein Z is a residue obtained by removing n active hydrogens in addition to p primary amino groups from amine compound (a), AO is an alkyleneoxy group having 2 to 4 carbon atoms, and m is alkyleneoxy. Average number of added moles of group, 1 to 100, n is an integer of 1 to 5, and p is an integer of 1 to 3. ] The amine compound (a) is aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N ′-(2-hydroxy The dispersant according to claim 1, which is an amine compound selected from the group consisting of (ethyl) piperazine. The dispersant according to claim 1 or 2, wherein the polyoxyalkyleneamine compound (A) is represented by the following general formula (2).

[Wherein, AO is an alkyleneoxy group having 2 to 4 carbon atoms, m is an average added mole number of the alkyleneoxy group, and is a number of 1 to 100, and n is an integer of 1 to 5. ] A carbon black dispersion containing a dispersion medium selected from the group consisting of the dispersant according to any one of claims 1 to 3, carbon black, a solvent, a resin, and rubber. The carbon black dispersion according to claim 4, wherein the weight of the dispersant is 1 to 40% by weight based on the weight of the carbon black. The manufacturing method of the dispersing agent of any one of Claims 1-3 obtained by hydrolyzing the polyoxyalkylene ketimine compound (B) represented by following General formula (3).

[In the formula, Z is a residue obtained by removing p ketimine groups and n active hydrogens from an amine compound (a), AO is an alkyleneoxy group having 2 to 4 carbon atoms, and m is an average addition mole of an alkyleneoxy group. A number of 1 to 100, n is an integer of 1 to 5, p is an integer of 1 to 3, and R ₁ and R ₂ are each independently an alkyl group of 1 to 6 carbon atoms. ]