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    available online @ Prog. Color Colorants Coat. 10 (2017), 51-65

    Synthesis and Surface Modification of Pigment Red 3 by Sulfonation

    Method for Improving Properties in Waterborne Ink

    M. Rostami *1

    , A. Khosravi 2 , M. M. Attar


    1. Department of Nano Materials and Coatings, Institute for Color Science Technology. P.O. Box 16765-654, Tehran-


    2. Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box:

    15875-4413, Tehran, Iran


    Article history:

    Received: 26 July 2016

    Final Revised: 20 Dec 2016

    Accepted: 2 Jan 2017

    Available online: 17 Jan 2017


    Pigment Red 3

    Surface treatment


    Water born flexographic inks

    igment Red 3 was synthesized and chemically treated by sulfonation. The

    treatment, affected the surface chemistry and the shape of pigments. The

    effects of reaction time, temperature, solvent/pigment ratio and

    acid/pigment ratio were examined on the treated pigment. The investigation of

    experimental design was carried out based on Taguchi method. UV-Visible

    spectroscopy, densitometry, turbidimetry, pH and Scanning Electron Microscopy

    were used to assess the treated particles. The effects of surface modification on

    properties of water born flexographic ink were studied using dispersion rate,

    gloss, chroma, hue, lightness and K/S of ink coating. Optimum samples were

    selected according to the results of the analyses as well as the Variance Analysis

    and by considering the effect of each independent parameter. Prog. Color

    Colorants Coat. 10 (2017), 51-65© Institute for Color Science and Technology.

    1. Introduction Since pigment manufacturers should produce pigments

    which possess acceptable wettability in different

    media, surface treatment of organic and inorganic

    pigments has become one of the most important goals.

    The shape and surface chemistry of synthesized

    pigments should be modified before applying in the

    final product. The final properties of the pigments are

    not only dependant on their chemical structure but also

    on factors such as particle shape, particle size, type of

    crystal and surface chemistry of pigment particles. For

    example, final properties like tinting strength, opacity

    and transparency depend on the type of crystal [1-3].

    Methods such as resination [4], treating with

    surfactants [5, 6], acid- base (alkali) treatment [7],

    solvent treatment [8], treatment with pigment

    derivative [9], inorganic materials [10], gases [11],

    silane coupling agent [12, 13], polymers [14-16] and

    finally, treatment with sulfonating agents [17, 18] are

    applied in order to produce surface treated pigment

    particles. It should be noted that the final application

    and also the pigment structure will decide what method

    should be carried out. Organic pigments have low

    surface energy and their wettability in polar media is

    low. With sulfonating method, the surface energy of

    the pigments increases. On the other hand, the surface

    treated organic pigment with sulfonating agent has

    excellent dispersibility and long-term dispersion

    stability in water and organic polar solvent. In

    sulfonating method, reaction of a sulfonating agent

    with a dispersed organic pigment occurred in a solvent

    in which the organic pigment is insoluble or sparingly

    soluble, and thereby it results in the introduction of a

    sulfonic group to the surface of each particle of organic

    pigment [19].

    After surface modification of pigments, this work


  • M. Rostami et al

    52 Prog. Color Colorants Coat. 10 (2017), 51-65

    aims to surface modification of pigment Red 3 by

    different sulfonating agents. Analytical techniques

    including UV-Visible spectroscopy, densitometry,

    turbidimetry, pH value and Scanning Electron

    Microscope were performed. Dispersion rate, fineness,

    gloss, K/S, chroma, hue, lightness and tinting strength

    are measured to evaluate the effects of the surface

    modification of Pigment red-3 on properties of the ink


    2. Experimental

    2.1. Materials

    Nitro benzene and sulfuric acid were provided from

    Merck. In this study, surface modification of the

    toluidine red 3 was done by sulfonating agent in order

    to enhance its compatibility with water based

    flexographic inks. Toluidine red 3 with the chemical

    structure given in Figure 1 was synthesis. Water based

    flexographic inks were prepared using acrylic resins

    (R94, R95) from Neo Resin and a Dispersing agent

    BYK184, anti-foam BYK023 from BYK Co.

    2.2. Synthesis of Pigment Red 3

    At first, Pigment Red 3 was synthesized as follows.

    16.5 g amine (Meta nitro para toluidine prepared from

    Merck Co.) and 60.25 g hydrochloric acid (5N) were

    mixed. Then the mixture was charged into the reactor.

    The temperature of the reactor was kept between -2 to

    5 °C. Then the NaNO3 olution was gradually (16

    mL/min) added to the reactor. After the reaction was

    completed, the final product of the reaction was

    filtered. The diazotization yield was at 98%, and then

    the diazotization solution was gradually (2 mL/min)

    added to the β-naphthol solution (20 g β-naphthol

    dissolve in 643 mL distillated water with 4.43 g

    NaOH). After the completion of the reaction, the

    temperature of the reactor was 37 0 C. The product was

    filtered and then washed using hot distilled water. The

    reaction yield was 94.7%. The efficiency was

    calculated according to Eq. 1. The structure of Pigment

    Red 3 is shown in Figure 1.


    2.3. Treatment of Pigment Red 3

    2.3.1. Method of treatment

    In this process, four independent factors were selected,

    including temperature, time, solvent/pigment ratio and

    acid/pigment ratio. For each independent factor, four

    levels were considered. Based on Taguchi method, for

    4 levels and 4 factors, 16 arrays are investigated (L 16).

    It should be noted that if we didn’t use Taguchi

    method, we had to do 256 (44) experiments. The values

    corresponding to the independent factors and their

    levels are shown in Table 1.


    CH 3


    NO 2

    Figure 1: The chemical Structure of Pigment Red 3.

    Table 1: Independent Factors.

    4 3 2 1 Independent Factors 150 100 50 25 A Solvent/Pigment

    2 1.5 1 0.5 B Acid / Pigment

    4 3 2 1 C Time (hr)

    80 60 40 20 D Temperature (C)

  • Synthesis and Surface Modification of Pigment Red 3

    Prog. Color Colorants Coat. 10 (2017), 51-65 53

    In Table 2, the first column corresponds to the

    number of treatments. The values of independent

    factors of each treatment reaction are selected. For

    example, in Treatment No 9, the parameter A

    corresponds to solvent/pigment ratio, which its value

    corresponds to the third column of Table 1 which is

    equal to 100. The parameter B corresponds to

    acid/pigment ratio, which its value corresponds to the

    first column of Table 1 which is equal to 0.5. The

    parameter C corresponds to reaction time, which

    corresponds to the third column of Table 1 which is

    equal to 3 and parameter D is the temperature of

    reaction which corresponds to the fourth column of

    Table 1 which is equal to 80 °C.

    Independent parameters for each treatment are

    selected according to Table 2. The nitrobenzene was

    poured into the reactor as a solvent and then Pigment

    Red 3 was added to it. The homogenizer was adjusted

    to 13000 rpm in order to disperse the pigment, and the

    temperature was adjusted to the corresponding

    temperature. When the homogenizer was at 16000 rpm,

    sulfonating agent was added to the reactor. When the

    reaction time was completed, the slurry was poured in

    water and filtered. The treated pigment was

    characterized, using UV-Visible spectroscope,

    scanning electron microscope, densitometer, and

    turbidimeter and pH value.

    2.4. Preparation of flexographic ink

    Different weight loadings (1, 2 and 3 wt.%) of

    modified and unmodified nanoparticles were dispersed

    in acrylic polyol resin using zirconia pearls (Spherical

    Beads). Then, isocyanate was added to the dispersions

    prepared at weight ratio of 1:4 (isocyanate: acrylic).

    The nanocomposites prepared were applied on the

    clean glass sheets using film applicator. Finally,

    coatings were cured at 70 °C for 4 h. The dry thickness

    of the coating was 45±5 µm.

    Table 2: 16 arrays for independent Factors.

    A B C D Treatment. No

    1 1 1 1 1

    1 2 2 2 2

    1 3 3 3 3

    1 4 4 4 4

    2 2 2 3 5

    2 2 1 4 6

    2 3 4 1 7

    2 4 3 2 8

    2 1 3 4 9

    3 2 4 3 10

    3 3 1 2 11