Materials used to prepare the microcapsules containing the dye aqueous solution were as follows.

Methylene Blue (MB: Wako Pure Chemical Ind., Ltd., Japan) was used as a dye of core material. Styrene monomer (St: Wako Pure Chemical Ind., Ltd., Japan) was used as a polymerazable monomer to form the microcapsule shell at the suspension polymerization process, where 2,2’-Azobis, (2,4-dimethylvale- ronitrile) (V-65: Wako Pure Chemical Ind., Ltd., Japan) was dissolved as an initiator.

Methylene diphenyl 4,4’-diisocyanate (MDI: Tokyo Kasei Kogyo Ind., Ltd., Japan) and polyethylene glycol (PEG: Wako Pure Chemical Ind., Ltd., Japan) were used as an oil soluble monomer and a water soluble monomer at the interfacial polycondensation reaction process, respectively.

Polyglycerol polyricinolate (POEM: Riken Vitamin Ind., Ltd., Japan) and Soybean lechitin (SBL: Wako Pure Chemical Ind., Ltd., Japan) were used as oil soluble surfactants.

Sodium dodecylbenzenesulphonate (DBS: Wako Pure Chemical Ind., Ltd., Japan) and Tricalcium phosphate (TCP: Wako Pure Chemical Ind., Ltd., Japan) were used as a water soluble surfactant and a particulate stabilizer, respectively.

Corn oil (Wako Pure Chemical Ind., Ltd., Japan) was used as the continuous phase at the inverse interfacial polycondensation method.

The experimental apparatus used to prepare the microcapsules is the same as the previous one [21] .

Figure 1 shows the flow sheets for preparing the microcapsules containing the dye aqueous solution with the suspension polymerization method (Figure 1(a)), with the inverse interfacial polycondensation reaction method (Figure 1(b)) and with the suspension polymerization method in parallel with the interfacial polymerization method (Figure 1(c)).

First, the preparation of microcapsules with the suspension polymerization method was as follows.

The dye aqueous solution of the given volume was added into styrene monomer (St) and stirred with homogenizer to form the (W/O) emulsion. In styrene monomer, V-65 and POEM or SBL were dissolved beforehand as an initiator and an oil-soluble surfactant, respectively.

Then, prebulk polymerization was performed in the (W/O) emulsion under the conditions such as T = 70˚C, t = 30 min and Nr = 200 rpm in order to increase the viscosity of styrene monomer and to stabilize the (W/O) emulsion. After this operation, the (W/O) emulsion was added in the continuous water phase and stirred with the six-bladed impeller to form the (W/O)/W emulsion. Then, suspension polymerization was conducted under the conditions such as Nr = 300 rpm and T = 70˚C for 8 h. The model microcapsule prepared thus was shown in Figure 1(a). Hereafter, the suspension polymerization method and the microcapsules prepared were called Process A and MCS, respectively.

Second, the preparation of microcapsules with the inverse interfacial polycondensation reaction method was as follows. The dye aqueous solution dissolving PEG was added into the corn oil of the continuous phase and stirred to form the (W/O) emulsion under the conditions such as Nr = 300 rpm and T = 70˚C for 10 min. Then, the corn oil of 10 cc dissolving MDI was added to the (W/O) emulsion and the interfacial polycondensation reaction was conducted under the conditions such as Nr = 300 rpm and T = 70˚C for 24 h. The model

microcapsule prepared thus was shown in Figure 1(b). Hereafter, the inverse interfacial polycondensation reaction method and the microcapsules prepared were called Process B and MCI, respectively.

Third, the preparation of microcapsules with suspension polymerization in parallel with interfacial polycondensation reaction was as follows.

The dye aqueous solution dissolving PEG was added in styrene monomer and stirred to form the (W/O) emulsion. Then, St dissolving MDI of a given amount was added into the (W/O) emulsion and the interfacial polycondensation reaction was started in parallel with bulk polymerization under the conditions such as Nr = 200 rpm, t = 30 min and T = 70˚C to form the polyurethane shell on the interface between the inner water droplet and styrene monomer.

After bulk polymerization was conducted for 30 min, the (W/O) emulsion was added into the continuous water phase, stirred to form the (W/O)/W emulsion and then, suspension polymerization was conducted for 7 h under the conditions such as Nr = 300 rpm and T = 70˚C. In this microencapsulation method, the polyurethane shell may be formed on the surface of microcapsule by adding PEG into the continuous water phase.

The model microcapsule prepared thus was shown in Figure 1(c).

Hereafter, the suspension polymerization method in parallel with interfacial polycondensation reaction and the microcapsules prepared were called Process C and MCSI (1), respectively.

The experimental conditions are shown in detail in Table 1.

Figure 2 shows the SEM photographs of microcapsules prepared with each method.

The microcapsules (MCS) prepared with Process A (Figure 2(a) and Figure 2(b)) are found to be the spherical particles with the diameter of ca. 450 µm and to be the multi core type. Furthermore, the microcapsule prepared with POEM seems to contain more water (Figure 2(b)) compared with the microcapsule prepared without POEM (Figure 2(a)).

The microcapsule (MCI) prepared with the Process B (Figure 2(c)) is found to be the mono core type.

While, the microcapsules (MCSI) prepared with Process C (Figure 2(d) and Figure 2(e)) are found to be the multi core type. Also, it is found that the diameters of inner water droplets were different due to the oil soluble surfactant species.

Anyway, the microcapsules containing the dye aqueous solution could be prepared with the preparation methods adopted here.

Figure 3 shows the microencapsulation efficiency (λ) of microcapsules prepared by each preparation method, where the mean diameters (Dp) of microcapsules are shown, too.

The microencapsulation efficiency of microcapsules prepared with each preparation method was 8.8% for MCS, 100% for MCI, 96% for MCSI, respectively.

While, the mean diameter of each microcapsule was 480 µm for MCS, 180 µm for MCI, 480 µm for MCSI, respectively.

In the case of Process A, as the microcapsules were prepared by using the (W/O)/W emulsion, the dye aqueous solution may be easily released on breaking the (W/O) emulsion into the continuous water phase and on forming the (W/O) droplets [22] . As a result, the microencapsulation efficiency may become low (λ = ca. 8.8%).

In the case of Process B, as the microcapsules were prepared by using the (W/O) emulsion and by performing the inverse interfacial polycondensation reaction, the dye aqueous solution was never released into the oil phase at the microencapsulation process. As a result, the microencapsulation efficiency must become 100% just after preparation.

In the case of Process C, as the inner dye aqueous droplets could be stabilized with the polyurethane resin shell and the double shells were formed, the microencapsulation efficiency may become high (λ = ca. 96%).

It was investigated how the release feature for each microcapsule was depending on the preparation method.

Figure 4 shows the optical microscopic photographs of microcapsules used to estimate the release feature.

As MCI could not be dried as solid powder, the photograph for MCI was the microcapsule slurry. The microcapsules became blue in color due to the dye (methylene blue) aqueous solution. A few tiny holes are observed on the surface of microcapsules (MCS, MCSI).

Figure 5 shows the transient release features for the microcapsules prepared with each preparation method. In the case of MCI prepared with Process B, the dye aqueous solution was rapidly released. This may be due to the porous shell as shown in Figure 6.

It is well known that the porous shell is formed for the microcapsules prepared with the interfacial polycondensation reaction method which is suitable to microencapsulate the liquid core material [7] [12] . Accordingly, the tiny holes may be easily formed on the polyurethane shell. In the case of MCS prepared with Process A, the dye aqueous solution was released relatively slow because of the denser shell. While, in the case of MCSI prepared with Process C, the dye

aqueous solution was released remarkably slow. Especially, when POEM was used as an oil soluble surfactant added to stabilize the (W/O) emulsion, the release of the dye aqueous solution was prevented to a certain degree.

From these results, MCSI prepared with Process C was the most suitable to the loading and releasing capability and the microencapsulation efficiency.

From the results obtained above, it was found that the release velocity of the dye aqueous solution from the microcapsules was considerably different depending on the preparation method.

So, the release feature for MCSI was investigated in detail changing the conditions of the interfacial polycondensation reaction, namely, the concentrations of MDI and PEG.

Figure 7 shows the transient feature for MCSI prepared changing the concentrations of MDI and PEG.

The release velocity was decreased with the concentrations of MDI and PEG, where the microcapsules without MDI and PEG were MCS. The values of permeability coefficient were estimated from Equation (2) by obtaining the initial values of (C/t) as shown in Figure 7. Here, it was investigated how permeability of dye aqueous solution was affected by the formation of polyurethane shell.

The values of permeability coefficient for each microcapsule are shown in Table 2 together with the concentration of PEG [Cp: g/cm²] per unit interfacial area of the (W/O) emulsion.

It was found that the release velocity could be delicately controlled by changing the concentration (Cp) of PEG.

Furthermore, if PEG is added in the continuous water phase at the suspension polymerization process, the release of the dye aqueous solution could be more minutely controlled.