Process for production of vinyl polymer

A process for production of a vinyl polymer by suspension polymerization or emulsion polymerization of at least one kind of vinyl monomer in an aqueous medium is disclosed. In this process, the polymerization is carried out in a polymerizer, the inner wall surface and portions of the auxiliary equipment thereof which may come into contact with the monomer during polymerization having a surface roughness of not greater than 5 .mu.m and being previously coated with a scaling preventive comprising at least one selected from dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated .pi. bonds. According to this process, scaling on the inner wall surface of a polymerizer, etc. during polymerization can be prevented effectively and surely.

The present invention is described in more detail below with reference to 
the following Examples, by which the scope of the present invention is not 
limited. In the following, all parts are by weight unless otherwise noted. 
(Note: In the following Examples, Experiment Nos. 277 to 300 are skipped.) 
EXAMPLE 1 
As shown in Table 1, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 1, a dye or a pigment was 
dissolved or dispersed in a solvent, optionally with the addition of an 
inorganic compound or a polymeric compound as shown in the Table to 
prepare a coating solution. The formulation ratio of the inorganic 
compound or the polymeric compound and the concentration of the dye or 
pigment in the coating solution are also shown in Table 1. The coating 
solution was applied on the inner wall surface of the polymerizer, etc. 
treated as mentioned above, dried at 80.degree. C. for 10 minutes and then 
thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of vinyl 
chloride monomer, 200 parts of deionized water, 0.022 part of partially 
saponified polyvinyl alcohol, 0.028 part of hydroxymethyl cellulose and 
0.03 part of t-butyl peroxyneodecanate, and polymerization was carried out 
at 52.degree. C. for 7 hours. After completion of polymerization, the 
polymer was taken out and the polymerizer was washed with water at a flow 
rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 1. 
The above operations from coating and charging to washing with water were 
conducted for each batch and this was repeated for a maximum of 200 
batches. 
Also, scaling after completion of each of the 10th, 30th, 50th, 100th, 
150th and 200th batches was evaluated visually according to the standards 
shown below, and the amount of scales adhering (g/m.sup.2) was also 
measured after completion of the final batch. The results are also shown 
in Table 1. 
A: no sticking of scale 
B: several percent sticking of sandy scales 
C: scales sticking thinly over part of the surface (about 10% of surface) 
D: scales sticking thickly over part of the surface (about 10% of surface) 
E: scales sticking thinly over part of the surface (about 50% of surface) 
F: scales sticking thickly over part of the surface (about 50% of surface) 
G: scales sticking thinly over the entire surface 
H: scales sticking thickly over the entire surface 
In Table 1, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 1 to 6 are examples 
in which the inner wall surface of the polymerizer was subjected to no 
treatment with any compound. Also, the coating solution employed in 
Experiment Nos. 23 and 57 was prepared by dissolving one part of sodium 
sulfide in 100 parts of water and adding 0.5 part of a dye to the 
resultant solution, followed by heating at 80.degree. C. for 30 minutes. 
TABLE 1 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Dye or pigment (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. 
(Mixing ratio) (b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
1* 
-- -- -- -- 
2* 
-- -- -- -- 
3* 
-- -- -- -- 
4* 
-- -- -- -- 
5* 
-- -- -- -- 
6* 
-- -- -- -- 
7* 
Solvent Black 5 -- -- 0.5 
Methanol 
8* 
" Colloidal silica 
100/100 
-- 0.5 
" 
9* 
-- " 0/100 
-- 0.4 
" 
10* 
Solvent Black 5 -- Atactic polypropylene 
100/70 
0.7 
Acetone 
11* 
-- -- " 0/100 
0.5 
" 
12 Solvent Black 5 -- -- 0.5 
Methanol 
13 Solvent Black 5 Colloidal silica 
100/100 
-- 0.6 
" 
14 " Fe(OH).sub.3 sol 
100/5 
-- 0.6 
" 
15 Acid Blue 82 -- -- 0.5 
Water/Methanol 
(90/10) 
16 " Water glass 
100/100 
-- 0.7 
Water/Methanol 
(90/10) 
17 " Colloid of sulfur 
100/5 
-- 0.6 
Water/Methanol 
(90/10) 
18 " CuCl.sub.2 
100/2 
-- 0.5 
Water/Methanol 
(90/10) 
19 Acid Violet 47 -- -- 0.8 
Water 
20 Acid Red 83 -- -- 0.5 
" 
21 Acid Blue 102 -- -- 0.7 
" 
22 Direct Blue 199 -- -- 0.7 
" 
23 Food Blue 2 -- -- 2.0 
" 
24 Food Green 2/Acid Red 52 
Colloidal silica 
100/50 
-- 0.8 
Water/Isobutyl 
(90/10) alcohol (90/10) 
25 Direct Blue 108 -- -- 0.9 
Water 
26 Acid Brown 165 -- -- 1.0 
" 
27 Acid Yellow 7 Zn(CH.sub.3 COO).sub.2 
100/5 
-- 0.5 
" 
28 Sulfur Blue 2 -- -- 0.9 
" 
29 Fluorescent Brightening 
-- -- 0.8 
" 
Agent 56 
30 Reactive Yellow 2 
-- -- 0.9 
" 
31 Reactive Green 7 
-- -- 0.7 
" 
32 Basic Red 2 Metasilicic acid 
-- 0.8 
" 
(100/80) 
33 Reactive Blue 7 -- -- 0.5 
" 
34 Reactive Black 8 
-- -- 0.8 
" 
35 Azoic Brown 2 -- Polystyrene 100/30 
0.7 
Toluene 
36 Azoic Orange 7 -- -- 0.9 
Water 
37 Basic Yellow 34 -- -- 0.5 
" 
38 Basic Orange 2 -- -- 0.8 
" 
39 Basic Red 17 -- -- 1.0 
" 
40 Basic Violet 26 -- -- 0.5 
" 
41 Basic Orange 14/Disperse Blue 
Colloid of lithium 
100/150 
-- 1.0 
Water/Acetone 
66 (50/50) silicate (50/50) 
42 Disperse Brown 3 
-- -- 0.7 
Acetone 
43 Pigment Blue 25/Solvent Black 5 
-- Polystyrene 100/20 
0.7 
Toluene 
(20/80) 
44 Solvent Red 21 Sodium metasilicate 
100/60 
-- 0.9 
Methanol 
45 Basic Blue 21 -- -- 0.6 
Water 
46 Vat Yellow 10 -- -- 0.4 
Xylene 
47 Vat Red 16/Vat Brown 44 
-- -- 0.5 
" 
48 Solvent Black 7 Colloidal silica 
100/100 
-- 0.4 
Water/Methanol 
(30/70) 
49 Disperse Blue 104 
-- Polyindene 100/50 
0.7 
Trichloroethylene 
50 Vat Yellow 4 -- -- 0.9 
Xylene 
51 Vat Orange 4 -- -- 0.5 
Methanol 
52 Pigment Violet 122 
-- Poly(4-chlorostyrene) 
100/100 
1.0 
MEK 
53 Vat Red 1 -- -- 0.8 
Xylene 
54 Pigment Green 38 
-- Poly(4-methoxystyrene) 
100/10 
0.9 
MEK 
55 Acid Black 2/Basic Red 9 
-- -- 0.5 
Water/n-Amyl 
alcohol (80/20) 
56 Basic Green 1 -- -- 0.6 
Water 
57 Pigment Blue 1 -- Poly(vinyl methyl 
100/40 
0.9 
Acetone 
ketone) 
58 Pigment Violet 23 
-- Atactic polypropylene 
100/70 
0.7 
Toluene 
59 Solvent Black 3/Basic Blue 24 
-- -- 0.6 
Methanol 
60 Basic Orange 22 Water glass -- 0.8 
Water 
(100/50) 
61 Disperse Yellow 33 
-- -- 1.5 
Xylene 
62 Vat Orange 7 -- -- 0.7 
Pyridine 
63 Sulfur Blue 4 Fe(OH).sub.3 sol 
100/5 
-- 0.6 
Water 
64 Fluorescent Brightening 
-- -- 0.7 
Pyridine 
Agent 174 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount attached 
g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. 
Polymerizer 
.mu.m min. 10 30 50 100 150 
200 
__________________________________________________________________________ 
1* 
100 l 10-13 60 H (1200) 
2* 
40 m.sup.3 
7-8 " H (1100) 
3* 
100 l 0.8-1 30 H (900) 
4* 
130 m.sup.3 
0.4-0.7 " E H (900) 
5* 
1 m.sup.3 
0.2-0.3 " E H (800) 
6* 
2 m.sup.3 
0.05-0.1 " B E H (700) 
7* 
40 m.sup.3 
7-8 " B E H (400) 
8* 
" " " B C F H (300) 
9* 
1 m.sup.3 
0.2-0.3 " H (800) 
10* 
40 m.sup.3 
7-8 " B C F H (450) 
11* 
1 m.sup.3 
0.2-0.3 60 H (1100) 
12 130 m.sup.3 
0.4-0.7 10 A A A A A B (3) 
13 " 0.4-0.7 " A A A A A A (0.2) 
14 " " " A A A A A A (0.5) 
15 2 m.sup.3 
0.05-0.1 " A A A B C D (20) 
16 " " " A A A A A A (0.9) 
17 " " " A A A A A A (0.7) 
18 " " " A A A A A A (0.8) 
19 " " " A A A B C D (21) 
20 " " " A A A B C D (18) 
21 " " " A A A B C D (19) 
22 " " " A A A B C D (15) 
23 " " " A A A B C D (20) 
24 " " " A A A A A A (0.5) 
25 1 m.sup.3 
0.2-0.3 " A A A B C D (16) 
26 " " " A A A B C D (18) 
27 " " " A A A A A A (0.9) 
28 " " " A A A B C D (20) 
29 " " " A A A B C D (22) 
30 " " " A A A B C D (19) 
31 " " " A A A A B C (10) 
32 130 m.sup.3 
0.4-0.7 " A A A A A A (0.8) 
33 1 m.sup.3 
0.2-0.3 " A A A B C D (18) 
34 " " " A A A A B C (8) 
35 " " " A A A A A B (3) 
36 " " " A A A A B C (10) 
37 " " " A A A B C D (20) 
38 " " " A A A A B C (9) 
39 " " " A A A B C D (18) 
40 100 l 0.8-1 " A A A B C D (17) 
41 " " " A A A A A A (0.7) 
42 " " " A A A A A B (3) 
43 " " " A A A A A B (2.5) 
44 " " " A A A A A A (0.4) 
45 " " " A A A B C D (19) 
46 " " " A A A A A B (4) 
47 " " " A A A A B C (9) 
48 " " 15 A A A A A A (0.2) 
49 2 m.sup.3 
0.05-0.1 " A A A A A B (2.5) 
50 " " " A A A A B C (7) 
51 " " " A A A A B C (9) 
52 " " " A A A A B C (10) 
53 " " " A A A B C D (19) 
54 " " " A A A A A B (2.3) 
55 " " " A A A A A A (0.9) 
56 " " " A A A A B C (8) 
57 " " " A A A B C D (18) 
58 1 m.sup.3 
0.2-0.3 " A A A A A B (2.1) 
59 " " " A A A A A A (0.7) 
60 " " " A A A A A B (1.8) 
61 " " " A A A A B C (10) 
62 " " " A A A A B C (9) 
63 " " " A A A A A A (0.6) 
64 " " " A A A B C D 
__________________________________________________________________________ 
(7) 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 2 
As shown in Table 2, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 2, a dye or a pigment was 
dissolved or dispersed in a solvent, optionally with the addition of an 
inorganic compound or a polymeric compound as shown in the Table to 
prepare a coating solution. The formulation ratio of the inorganic 
compound and the polymeric compound and the concentration of dye or 
pigment in the coating solution are also shown in Table 2. The coating 
solution was applied on the inner wall surface of the polymerizer, etc. 
treated as mentioned above, dried at 80.degree. C. for 10 minutes and then 
thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of vinyl 
chloride monomer, 200 parts of deionized water, 0.125 part of 
hydroxypropylmethyl cellulose, 0.125 part of sorbitan monolaurate and 
0.025 part of .alpha.,.alpha.'-azobis-2,4-dimethylvaleronitrile, and 
polymerization was carried out at 52.degree. C. for 10 hours. After 
completion of polymerization, the polymer was taken out and the 
polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 
hr for the period of time shown in Table 2. The above operations from 
coating and charging to washing with water were conducted for each batch 
and this was repeated for a maximum of 200 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. The results are also shown in Table 2. 
In Table 2, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 65 and 66 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. Also, the coating solution employed in 
Experiment Nos. 105 and 133 was prepared by dissolving one part of sodium 
sulfide in 100 parts of water and adding 0.5 part of a dye to the 
resultant solution, followed by heating at 80.degree. C. for 30 minutes. 
TABLE 2 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Dye or pigment (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. (Mixing ratio) (b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
65* 
-- -- -- -- 
66* 
-- -- -- -- 
67* 
Basic Black 2 -- -- 0.8 Water/n-Butyl 
alcohol (80/20) 
68* 
" Colloidal silica 
100/80 
-- 0.8 Water/n-Butyl 
alcohol (80/20) 
69* 
-- " 0/100 
-- 0.8 Water 
70* 
-- -- Polyindene 0/100 
0.5 Dioxane 
71* 
Basic Red 2 ZnCl.sub.2 
100/5 
-- 0.8 Water/n-Amyl 
alcohol (80/20) 
72* 
Acid Blue 59 Water glass 
100/80 
-- 0.5 Water/Isobutyl 
alcohol (90/10) 
73* 
Basic Orange 14 Mesotrisilicic acid 
100/50 
-- 0.7 Water 
74* 
Acid Black 2 Manganese dioxide 
100/5 
-- Water/Butyl 
alcohol (85/15) 
75 Basic Orange 14 -- -- 0.6 Water 
76 " ZnCl.sub.2 -- " " 
77 Basic Orange 14 Colloidal silica 
-- 0.6 " 
78 " Colloid of sulfur 
-- " " 
79 Direct Brown 44 -- -- 0.9 " 
80 Acid Orange 33 -- -- 0.8 " 
81 Basic Red 2 ZnCl.sub.2 
100/5 
-- 0.8 Water/n-Amyl 
alcohol (80/20) 
82 Mordant Red 21 -- -- 0.5 Water 
83 Solvent Red 30 -- -- 0.7 Methanol 
84 Acid Black 110 -- -- 0.4 Water 
85 Direct Blue 108 Mesotetrasilicic acid 
100/40 
-- 0.7 " 
86 Acid Blue 59 Water glass 
100/80 
-- 0.5 Water/Isobutyl 
alcohol (90/10) 
87 Solvent Orange 44 
-- -- 0.9 Methanol 
88 Solvent Black 5 -- -- 1.0 " 
89 Basic Orange 14 Mesotrisilicic acid 
100/50 
-- 0.7 Water 
90 Solvent Red 100 -- -- 0.6 Methanol 
91 Basic Blue 22 Al(OH).sub.3 sol 
100/2 
-- 0.5 Water 
92 Vat Yellow 20 -- -- 0.8 " 
93 Vat Orange 13 -- -- 0.4 " 
94 Disperse Violet 23 
-- -- 0.9 Acetone 
95 Solvent Black 3 -- -- 0.7 " 
96 Pigment Red 35 -- Poly(vinyl n-butyl 
100/80 
1.0 Methylene 
ether) chloride 
97 Vat Green 2 -- -- 0.5 -- 
98 Pigment Red 88 -- Polyvinyl methyl 
100/70 
0.8 Dioxane 
ketone 
99 Pigment Blue 16 -- Polyvinyl sulfonic 
100/100 
0.7 Water 
acid 
100 Basic Blue 19 Ce(NO.sub.3).sub.3 
100/10 
-- 0.7 " 
101 Solvent Blue 73/Pigment Blue 2 
-- Polyindene 100/50 
0.5 Dioxane 
(50/50) 
102 Solvent Black 49 
Ni(NO.sub.3).sub.2 
100/20 
-- 1.0 Water 
103 Basic Black 2 Colloidal silica 
100/80 
-- 1.0 Water/n-Butyl 
alcohol (80/20) 
104 Disperse Violet 42 
-- -- 0.7 Acetone 
105 Sulfur Blue 6 -- -- 0.9 Water 
106 Solubilized Sulfur Brown 1 
-- -- 0.6 " 
107 Fluorescent Brightening 
-- -- 0.4 " 
Agent 22 
108 Disperse Red 113 
-- -- 0.8 Acetone 
109 Pigment Red 2/Pigment 
-- Polyacenaphthylene 
100/100 
0.8 Toluene 
Green 10 
110 Pigment Yellow 13 
-- Poly(4-vinylbiphenyl) 
100/30 
0.6 Benzene 
111 Basic Orange 2 MgCl.sub.2 
100/15 
-- 0.9 Water 
112 Basic Orange 33 -- -- 0.6 " 
113 Basic Yellow 36 -- -- 0.7 " 
114 Direct Violet 90 
-- -- 0.5 " 
115 Direct Blue 168 -- -- 0.6 " 
116 Direct Black 22 Water glass 
100/50 
-- 0.6 Water/Isobutyl 
alcohol (90/10) 
117 Acid Yellow 42 -- -- 1.0 Water 
118 Acid Red 77/Food Yellow 4 
-- -- 0.5 " 
(40/60) 
119 Pigment Brown 5 -- Polyacrylomorpholide 
100/50 
1.0 DMF 
120 Acid Black 115 Colloid of sulfur 
100/20 
-- 0.9 Water 
121 Direct Red 11 -- -- 0.6 " 
122 Mordant Blue 8 -- -- 0.8 " 
123 Pigment Violet 5 
-- Polyacrolein 
100/40 
0.9 DMF 
124 Food Blue 1/Food Green 2 
-- -- 0.7 Water 
125 Pigment Red 90 -- Poly(1,5-hexadiene- 
100/80 
0.8 Acetophenone 
sulfone) 
126 Acid Black 2 Colloid of manganese 
100/5 
-- 0.6 Water/n-Butyl 
dioxide alcohol (85/15) 
127 Acid Brown 103 -- -- 0.5 Water 
128 Acid Yellow 7/Solvent Back 7 
CoCl.sub.2 
100/2 
-- 0.7 Water/Methanol 
(90/10) (30/70) 
129 Sulfur Green 2 -- -- 0.9 Water 
130 Fluorescent Brightening 
-- -- 0.4 " 
Agent 87 
131 Reactive Orange 20 
-- -- 0.5 " 
132 Reactive Brown 7 
-- -- 0.8 " 
133 Reactive Black 12 
Sodium metasilicate 
100/30 
-- 1.0 Water/Amyl 
alcohol (80/20) 
134 Azoic Component 17 
-- -- 0.6 Water 
135 Azoic Green 1 -- -- 0.8 " 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. 
Polymerizer 
.mu.m min. 10 30 50 100 150 
200 
__________________________________________________________________________ 
65* 
100 l 10-13 60 H(1500) 
66* 
2 m.sup.3 
0.05-0.1 45 H(1200) 
67* 
100 l 10-13 " G H(400) 
68* 
" " " B C F H(300) 
69* 
1 m.sub.3 
0.2-0.3 " H(700) 
70* 
" " " H(800) 
71* 
100 l 10-13 " B C F H(350) 
72* 
" " " B C F H(320) 
73* 
" " " B C F H(300) 
74* 
" " " B C F H(280) 
75 
1 m.sup.3 
0.2-0.3 10 A A A B C D(20) 
76 
" " " A A A A A B(3) 
77 
1 m.sup.3 
0.2-0.3 10 A A A A A B(2.5) 
78 
" " " A A A A A B(2.3) 
79 
2 m.sup.3 
0.05-0.1 " A A B C D F(60) 
80 
" " " A A B C D F(58) 
81 
" " " A A A A A B(3) 
82 
" " " A A B C D F(57) 
83 
" " " A A B C D F(61) 
84 
" " " A A B C D F(55) 
85 
" " " A A A A A B(2.5) 
86 
100 l 0.3-0.5 20 A A A A A B(2.0) 
87 
" " " A A B C D F(61) 
88 
" " " A A A A B C(9) 
89 
100 l 0.3-0.5 20 A A A A A B(2.1) 
90 
" " " A A B C D F(60) 
91 
" " " A A A A A B(59) 
92 
" " " A A B C D F(60) 
93 
" " 15 A A B C D F(80) 
94 
1 m.sup.3 
0.2-0.3 " A A B C D F(62) 
95 
" " " A A B C D F(57) 
96 
" " " A A A B C D(58) 
97 
" " " A A B C D F(59) 
98 
" " " A A A B C D(18) 
99 
" " " A A A B C D(20) 
100 
" " " A A A A A B(1.9) 
101 
1 m.sup.3 
0.2-0.3 15 A A B C D F(60) 
102 
" " 10 A A A A A B(2.5) 
103 
" " " A A A A A B(2.0) 
104 
" " " A A B C D F(56) 
105 
100 l 0.3-0.5 " A A B C D F(57) 
106 
" " " A A B C D F(59) 
107 
" " " A A B C D F(60) 
108 
" " " A A B C D F(57) 
109 
" " " A A A B C D(20) 
110 
" " " A A A A B C(11) 
111 
" 0.8-1 15 A A A A A B(3) 
112 
" " " A A B C D F(60) 
113 
100 l 0.8-1 15 A A B C D F(58) 
114 
" " " A A B C D F(57) 
115 
" " " A A B C D F(58) 
116 
" " " A A A A A B(2) 
117 
" " " A A B C D F(60) 
118 
" " " A A B C D F(56) 
119 
" " " A A A B C D(20) 
120 
" " " A A A A A B(1.9) 
121 
1 m.sup.3 
0.2-0.3 " A A B C D F(57) 
122 
" " " A A B C D F(58) 
123 
" " " A A A B C D(20) 
124 
" " " A A B C D F(59) 
125 
1 m.sup.3 
0.2-0.3 15 A A A B C D(20) 
126 
" " 10 A A A A A B(3) 
127 
" " " A A B C D F(57) 
128 
" " " A A A A A B(1.8) 
129 
" " " A A A B C D(21) 
130 
" " " A A B C D F(59) 
131 
2 m.sup.3 
0.05-0.1 " A A B C D F(60) 
132 
" " " A A B C D F(62) 
133 
" " " A A A A A B(3) 
134 
" " " A A B C D F(60) 
135 
" " " A A B C D F(59) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 3 
As shown in Table 3, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as the stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 3, a dye or a pigment was 
dissolved or dispersed in a solvent, optionally with the addition of an 
inorganic compound or a polymeric compound as shown in the Table to 
prepare a coating solution. The formulation ratio of the inorganic 
compound and the polymeric compound and the concentration of dye or 
pigment in the coating solution are also shown in Table 3. The coating 
solution was applied on the inner wall surface of the polymerizer, etc. 
treated as mentioned above, dried at 80.degree. C. for 10 minutes and then 
thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 80 parts of vinyl 
chloride monomer, 20 parts of vinyl acetate monomer, 200 parts of 
deionized water, 0.3 part of gelatin, 1 part of trichlene and 0.175 part 
of lauroyl peroxide, and polymerization was carried out at 70.degree. C. 
for 6 hours. After completion of polymerization, the polymer was taken out 
and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 
/m.sup.2 hr for the period of time shown in Table 3. The above operations 
from coating and charging to washing with water were conducted for each 
batch and this was repeated for a maximum of 200 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. The results are also shown in Table 3. 
In Table 3, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 136 and 137 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. Also, the coating solution employed in 
Experiment Nos. 177 and 178 was prepared by dissolving one part of sodium 
sulfide in 100 parts of water and adding 0.5 part of a dye to the 
resultant solution, followed by heating at 80.degree. C. for 30 minutes. 
TABLE 3 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic 
(a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Dye or pigment (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. (Mixing ratio) (b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
136* 
-- -- -- -- 
137* 
-- -- -- -- 
138* 
Solvent Black 5 
-- -- 0.5 
Methanol 
139* 
" Colloidal silica 
100/50 
-- 0.8 
" 
140* 
-- " 0/100 
-- 1.0 
Water 
141* 
Solvent Black 5 
-- Polystyrene 100/50 
0.7 
Toluene 
142* 
Basic Black 2 Water glass 
100/50 
-- 0.9 
Water/Isobutyl 
alcohol (90/10) 
143* 
Disperse Blue 98 
BaCl.sub.2 
100/5 
-- 0.8 
Water/Acetone 
(50/50) 
144* 
Basic Blue 65/Basic Red 34 
CuSO.sub.4 
100/20 
-- 0.9 
Water 
(70/30) 
145 Acid Violet 41 -- -- 0.5 
Methanol 
146 " Colloidal silica 
100/150 
-- 0.8 
" 
147 " Al(OH).sub.3 sol 
100/2 
-- 0.5 
" 
148 Acid Violet 41 FeCl.sub.2 
100/5 
-- 0.5 
Methanol 
149 Direct Red 13 -- -- " Water 
150 Direct Green 31 
NiCl.sub.2 
100/3 
-- 0.8 
" 
151 Basic Black 2 Water glass 
100/50 
-- 0.9 
Water/Isobutyl 
alcohol (90/10) 
152 Basic Red 18 -- -- 0.5 
Water 
153 Basic Red 22 -- -- 0.4 
" 
154 Basic Red 24 -- -- 0.7 
" 
155 Basic Blue 65/Basic Red 34 
CuSO.sub.4 
100/20 
-- 0.9 
" 
(70/30) 
156 Azoic Diazo Component 21 
-- -- 0.6 
Methanol 
157 Azoic Diazo Component 27 
-- -- 0.6 
Ethanol 
158 Disperse Yellow 8 
-- Polyglutardialdehyde 
100/100 
0.8 
Ethyl ether 
159 Disperse Orange 45 
-- -- 0.6 
Acetone 
160 Disperse Red 58 
-- -- 0.4 
Acetone 
161 Disperse Violet 24 
Colloidal silica 
100/40 
-- 1.0 
Water/Acetone 
(50/50) 
162 Disperse Yellow 23 
-- -- 0.8 
Acetone 
163 Disperse Red 74 
-- -- 0.9 
" 
164 Solvent Orange 31 
-- -- 0.7 
Methanol 
165 Solvent Orange 16 
-- -- 0.8 
" 
166 Solvent Brown 5 
Colloid of lithium 
100/10 
-- 0.8 
Water/Methanol 
silicate (30/70) 
167 Solvent Black 3 
Colloidal silica 
100/50 
-- 1.0 
Water/Acetone 
(50/50) 
168 Disperse Black 10 
-- -- 0.5 
Acetone 
169 Solvent Yellow 16/Solvent 
-- -- 0.7 
Methanol 
Orange 45 (60/40) 
170 Pigment Brown 2 
-- Polyvinyl n-butyl 
100/40 
2.0 
Methylene 
ether chloride 
171 Pigment Black 1 
-- Polycyclopentene 
100/70 
1.0 
Toluene 
172 Vat Green 8 -- -- 0.5 
Xylene 
173 Disperse Blue 98 
BaCl.sub.2 
100/5 
-- 0.8 
Water/Acetone 
(40/60) 
174 Vat Violet 10 -- -- 0.7 
Xylene 
175 Vat Red 2/Basic Blue 26 
-- -- 0.9 
Water/n-Amyl 
alcohol (90/10) 
176 Basic Violet 7 -- -- 0.6 
Water 
177 Sulfur Black 6 -- -- 0.8 
" 
178 Sulfur Black 11 
-- -- 0.5 
" 
179 Azoic Diazo Component 47 
-- -- 0.8 
" 
180 Basic Red 40 -- -- 0.7 
" 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. Polymerizer 
.mu.m min. 10 30 
50 100 150 
200 
__________________________________________________________________________ 
136* 
100 l 10-13 60 H(1200) 
137* 
1 m.sup.3 
0.2-0.3 " H(800) 
138* 
40 m.sup.3 
7-8 45 B F H(400) 
139* 
" " " B C F H(300) 
140* 
2 m.sup.3 
0.05-0.1 " H(600) 
141* 
100 l 10-13 " B C F H(400) 
142* 
" " " B C F H(280) 
143* 
" " " B C F H(250) 
144* 
" " " B C F H(310) 
145 1 m.sup.3 
0.2-0.3 10 A A A B C D(20) 
146 " " " A A A A A A(0.5) 
147 " " " A A A A A A(0.7) 
148 1 m.sup.3 
0.2-0.3 10 A A A A A A(0.9) 
149 2 m.sup.3 
0.05-0.1 15 A A A A B C(10) 
150 " " " A A A A A A(0.5) 
151 " " " A A A A A A(0.6) 
152 " " " A A A A B C(12) 
153 " " " A A A B C D(20) 
154 " " " A A A B C D(25) 
155 " " " A A A A A A(0.5) 
156 " " " A A A B C D(19) 
157 " " " A A A B C D(20) 
158 " " " A A A A B C(10) 
159 1 m.sup.3 
0.2-0.4 10 A A A B C D(18) 
160 1 m.sup.3 
0.2-0.4 10 A A A B C D(17) 
161 " " " A A A A A A(0.7) 
162 " " " A A A B C D(18) 
163 " " " A A A B C D(17) 
164 " " " A A A B C D(18) 
165 " " " A A A B C D(19) 
166 130 m.sup.3 
0.4-0.7 20 A A A A A A(0.5) 
167 " " " A A A A A A(0.6) 
168 1 m.sup.3 
0.2-0.4 " A A A B C D(20) 
169 " " " A A A A A B(3) 
170 100 l 0.8-1.0 10 A A A A A B(2.8) 
171 " " " A A A A A B(2.9) 
172 100 l 0.8-1.0 10 A A A B C D(21) 
173 " " " A A A A A A(0.8) 
174 " " " A A A B C D(21) 
175 " " " A A A B C D(15) 
176 " " " A A A B C D(18) 
177 " " " A A A A B C(17) 
178 " " " A A A B C D(20) 
179 " " " A A A B C D(21) 
180 " " " A A A B C D(18) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 4 
As shown in Table 4, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as the stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 4, a dye or a pigment was 
dissolved or dispersed in a solvent, optionally with the addition of an 
inorganic compound or a polymeric compound as shown in the Table to 
prepare a coating solution. The formulation ratio of the inorganic 
compound and the polymeric compound and the concentration of dye or 
pigment in the coating solution are also shown in Table 4. The coating 
solution was applied on the inner wall surface of the polymerizer, etc. 
treated as mentioned above, dried at 80.degree. C. for 10 minutes and then 
thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of vinyl 
chloride monomer, 200 parts of deionized water, 0.02 part of partially 
saponified polyvinyl alcohol, 0.03 part of hydroxymethyl cellulose and 
0.04 part of di-2-ethylhexyl peroxydicarbonate, and polymerization was 
carried out at 57.degree. C. for 7 hours. After completion of 
polymerization, the polymer was taken out and the polymerizer was washed 
with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of 
time shown in Table 4. The above operations from coating and charging to 
washing with water were conducted for each batch and this was repeated for 
a maximum of 200 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. 
The numbers of fish eyes in the products obtained from the polymers 
produced in the 10th, 30th, 50th, 100th, 150th and 200th batches in each 
experiment were measured as follows. A mixture of 100 parts by weight of a 
polymer obtained by dehydrating and drying the slurry after 
polymerization, 50 parts by weight of DOP, 1 part by weight of dibutyltin 
laurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of 
titanium oxide and 0.05 part by weight of carbon black was kneaded between 
two rolls at 150.degree. C. for 7 minutes and then formed into a sheet 
with a thickness of 0.2 mm. The number of fish eyes per 100 cm.sup.2 
contained in the sheet was examined according to the light transmission 
method. The results are shown in Table 4. 
In Table 4, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 181 and 182 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 4 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric 
(a)/(c) 
(2) 
Exp. Dye or pigment (a) 
compound weight 
compound 
weight 
conc. 
Solvent 
No. (Mixing ratio) (b) ratio (c) ratio % (Mixing 
__________________________________________________________________________ 
ratio) 
181* -- -- -- -- 
182* -- -- -- -- 
183 Solvent Yellow 16/Solvent 
Colloidal silica 
100/100 0.5 Methanol 
Orange 45 (50/50) 
184 Solvent Brown 5 Fe(OH).sub.3 sol 
100/10 
-- 0.9 Acetone 
185 Acid Yellow 7/Solvent Black 
Colloidal silica 
100/40 
-- 1.0 Methanol 
7 (20/80) 
186 Solvent Black 3 Colloid of sulfur 
100/20 
-- 0.4 " 
187 Solvent Black 5 CaCl.sub.2 
100/5 -- 0.9 " 
188 Solvent Black 7 Al(OH).sub.3 sol 
100/10 
-- 0.8 " 
189 " -- -- 0.8 " 
__________________________________________________________________________ 
(3) Surface 
(4) 
roughness of 
Time for washing 
Scaling 
(1) 
Capacity 
inner wall 
with water after 
Visual evaluation (Amount attached 
Fish eyes (number) 
Exp. 
of Poly- 
surface, etc. 
completion 
Batch No. Batch No. 
No. 
merizer 
(Rmax) .mu.m 
min. 10 30 
50 100 150 
200 10 30 
50 100 
150 
200 
__________________________________________________________________________ 
181* 
100 l 
10-13 60 H(1100) 350 
182* 
1 m.sup.3 
0.2-0.3 " C D F H(950) 20 50 
100 
320 
183 
2 m.sup.3 
0.05-0.1 
10 A A A A A B(1.5) 
0 0 0 0 7 10 
184 
100 l 
0.8-1 " A A A A A B(2.0) 
0 0 0 0 9 15 
185 
1 m.sup.3 
0.2-0.3 " A A A A A A(0.3) 
0 0 0 0 0 2 
186 
" " " A A A A A B(2.0) 
0 0 0 0 6 11 
187 
130 m.sup.3 
0.4-0.7 " A A A A A A(0.5) 
0 0 0 0 3 5 
188 
" " " A A A A A A(0.5) 
0 0 0 0 2 3 
189 
" " " A A A A A B(3.0) 
0 0 0 0 5 10 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 5 
As shown in Table 5, for each experiment, a 5-l, 20-l, or 100-l stainless 
steel polymerizer was selected, and the inner wall surface of the 
polymerizer and the portions of the auxiliary equipment such as the 
stirrers which may come into contact with monomer were treated to have the 
surface roughness (Rmax) shown in the Table. For each experiment, as shown 
in Table 5, a dye or a pigment was dissolved or dispersed in a solvent, 
optionally with the addition of an inorganic compound or a polymeric 
compound as shown in the Table to prepare a coating solution. The 
formulation ratio of the inorganic compound and the polymeric compound and 
the concentration of dye or pigment in the coating solution are also shown 
in Table 5. The coating solution was applied on the inner wall surface of 
the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. 
for 10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 75 parts of styrene, 25 
parts of acrylonitrile, 120 parts of deionized water, 0.5 part of 
tricalcium phosphate, 0.01 part of sodium dodecylbenzenesulfonate and 0.4 
part of lauroyl peroxide, and polymerization was carried out at 90.degree. 
C. for 8 hours. After completion of polymerization, the polymer was taken 
out and the polymerizer was washed with water at a flow rate of 0.1 
m.sup.3 /m.sup.2 hr for the period of time shown in Table 5. The above 
operations from coating and charging to washing with water were conducted 
for each batch and this was repeated for a maximum of 10 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount 
of scales adhering (g/m.sup.2) was also measured after completion of the 
final batch. The results are also shown in Table 5. 
In Table 5, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 190 and 191 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. Also, the coating solution employed in 
Experiment No. 215 was prepared by dissolving one part of sodium sulfide 
in 100 parts of water and adding 0.5 part of a dye to the resultant 
solution, followed by heating at 80.degree. C. for 30 minutes. 
TABLE 5 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic 
(a)/(b) 
Polymeric 
(a)/(c) 
(2) 
Exp. 
Dye or pigment (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. 
(Mixing ratio) (b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
190* 
-- -- -- -- 
191* 
-- -- -- -- 
192* 
Direct Black 51 
-- -- -- 
193* 
" Cu(NO.sub.3).sub.2 
100/10 
-- 0.5 
Water 
194* 
-- " 0/100 
-- 0.5 
" 
195* 
Solvent Black 5 
Fe(OH).sub.3 sol 
100/20 
-- 0.5 
Water/Methanol 
(30/70) 
196* 
Basic Red 37 CuCl.sub.2 
100/5 
-- 0.8 
Water 
197* 
Direct Black 51 
-- -- 0.5 
" 
198* 
" Cu(NO.sub.3).sub.2 
100/10 
-- 0.5 
" 
199* 
" Colloidal silica 
100/200 
-- 0.8 
" 
200 
" Colloid of sulfur 
100/20 
-- 0.5 
" 
201 
" Metadisilicic acid 
100/100 
-- 0.7 
" 
202 
Basic Violet 28 
-- -- 0.4 
Water 
203 
Basic Blue 67 -- -- 0.9 
" 
204 
Disperse Violet 41 
-- -- 0.8 
Acetone 
205 
Disperse Red 82 
-- -- 0.6 
" 
206 
Pigment Red 10 -- Polyacetaldehyde 
100/30 
0.8 
Methanol 
207 
Solvent Black 5 
Fe(OH).sub.3 sol 
100/20 
-- 0.5 
Water/Methanol 
(30/70) 
208 
Solvent Red 83 -- -- 1.0 
Methanol 
209 
Direct Black 112 
Cu(NO.sub.3).sub.2 
100/10 
-- 0.5 
Water 
210 
Vat Black 29 -- Polyvinyl alcohol 
100/20 
0.8 
" 
211 
Basic Violet 14 
-- -- 0.5 
" 
212 
Basic Blue 41/Solvent Blue 2 
Colloidal silica 
100/50 
-- 0.9 
Water/Methanol 
(40/60) (50/50) 
213 
Acid Orange 19 -- -- 0.4 
Water 
214 
Basic Red 37 CuCl.sub.2 
100/5 
-- 0.6 
Water 
215 
Sulfur Brown 12 
-- -- 0.8 
Water/Isobutyl 
alcohol (80/20) 
216 
Fluorescent Brightening 
-- -- 0.6 
Water 
Agent 121 
217 
Azoic Diazo Component 14 
-- -- 0.7 
" 
218 
Acid Blue 59 Metadisilicic acid 
100/100 
-- 0.5 
Water/n-Amyl 
alcohol 
__________________________________________________________________________ 
(90/10) 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount attached 
g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. Polymerizer 
.mu.m min. 1 2 3 5 7 10 
__________________________________________________________________________ 
190* 
5 l 10-13 20 H(2000) 
191* 
20 l 0.1-0.3 " H(1900) 
192* 
5 l 10-13 " G H(500) 
193* 
" " " B E H(200) 
194* 
" 0.05-0.1 " H(1800) 
195* 
" 10-13 " B E H(210) 
196* 
" " " B E H(250) 
197* 
100 l 0.8-1.0 5 A A A B C D(20) 
198* 
" " " A A A A A A(0.9) 
199* 
" " " A A A A A A(0.8) 
200 " " " A A A A A A(0.5) 
201 " " " A A A A A A(0.4) 
202 5 l 0.05-0.1 " A A A B C D(21) 
203 " " " A A A B C D(19) 
204 " " " A A A B C D(18) 
205 " " " A A A B C D(17) 
206 " " " A A A A A B(3) 
207 " " " A A A A A A(0.4) 
208 " 0.4-0.7 " A A A B C D(20) 
209 " " 10 A A A A A A(0.9) 
210 " " " A A A A B C(12) 
211 " " " A A A B C D(20) 
212 " " " A A A A A A(0.5) 
213 20 l 0.1-0.3 " A A A B C D(20) 
214 " " " A A A A A A(0.8) 
215 " " " A A A B C D(21) 
216 " " " A A A B C D(17) 
217 " " " A A A B C D(18) 
218 " " " A A A A A A(25) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 6 
As shown in Table 6, for each experiment, a 5-l, 20-l, or 100-l stainless 
steel polymerizer was selected, and the inner wall surface of the 
polymerizer and the portions of the auxiliary equipment such as the 
stirrers which may come into contact with monomer were treated to have the 
surface roughness (Rmax) shown in the Table. For each experiment, as shown 
in Table 6, a dye or a pigment was dissolved or dispersed in a solvent, 
optionally with the addition of an inorganic compound or a polymeric 
compound as shown in the Table to prepare a coating solution. The 
formulation ratio of the inorganic compound and the polymeric compound and 
the concentration of dye or pigment in the coating solution are also shown 
in Table 6. The coating solution was applied on the inner wall surface of 
the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. 
for 10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of styrene 
monomer, 250 parts of deionized water, 0.2 part of polyvinyl alcohol, 0.75 
part of t-dodecyl mercaptan and 0.5 part of lauroyl peroxide, and 
polymerization was carried out under stirring at 70.degree. C. for 5 
hours. Thereafter, the reaction mixture was heated from 70.degree. C. to 
80.degree. C. over 2 hours, and polymerization was further conducted at 
80.degree. C. for 1 hour. After completion of polymerization, the polymer 
was taken out and the polymerizer was washed with water at a flow rate of 
0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 6. The above 
operations from coating and charging to washing with water were conducted 
for each batch and this was repeated for a maximum of 10 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount 
of scales adhering (g/m.sup.2) was also measured after completion of the 
final batch. The results are also shown in Table 6. 
In Table 6, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 219 and 220 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 6 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Dye or pigment (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. (Mixing ratio) (b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
219* 
-- -- -- -- 
220* 
-- -- -- -- 
221* 
-- Colloidal silica 
0/100 
-- 0.5 Water 
222* 
-- -- Polyvinyl alcohol 
0/100 
0.8 " 
223* 
Basic Blue 25 Colloidal silica 
100/20 
-- 0.6 Water/n-Amyl 
alcohol (80/20) 
224* 
Solvent Black 5 
CoCl.sub.3 
100/10 
-- 0.7 Water/Methanol 
(50/50) 
225 Disperse Yellow 7 
-- -- 0.8 Acetone 
226 Solvent Black 5 
CoCl.sub.3 
100/10 
-- 0.7 Water/Methanol 
(50/50) 
227 Solvent Black 5 
-- -- 0.5 Methanol 
228 Solvent Blue 35 
-- -- 0.5 " 
229 Disperse Violet 1 
-- -- 0.6 Acetone 
230 Direct Black 113/Acid Brown 
Orthosilicic acid 
100/50 
-- 1.0 Water/Isobutyl 
14 (60/40) alcohol (90/10) 
231 Pigment Blue 3 -- Polyvinyl alcohol 
100/50 
0.7 Water 
232 Pigment Violet 3 
-- Polyphenylacetylene 
100/80 
0.8 Methanol 
233 Basic Orange 2 Water glass 
100/100 
-- 0.8 Water 
234 Basic Blue 25 Colloidal silica 
100/20 
-- 0.6 Water/n-Amyl 
alcohol (80/20) 
235 Disperse Orange 20 
-- -- 0.5 Acetone 
236 Solvent Red 24 -- -- 0.5 Methanol 
237 Basic Blue 54 -- -- 0.7 Water 
238 Disperse Red 65 
-- -- 1.0 Acetone 
239 Disperse Blue 91 
-- -- 0.6 " 
240 Vat Green 9 -- -- 0.5 Xylene 
241 Basic Blue 5 Fe(OH).sub.3 sol 
100/5 
-- 0.8 Water 
242 Acid Black 2 Sodium metasilicate 
100/60 
-- 0.6 Water/n-Butyl 
alcohol (85/15) 
243 Basic Red 12 -- -- 0.4 Water 
244 Fluorescent Brightening 
-- -- 0.7 " 
Agent 175 
245 Disperse Orange 30 
-- -- 0.9 Acetone 
246 Pigment Red 7 -- Polyvinyl butyral 
100/100 
1.0 Ethanol 
247 Basic Red 38 -- -- 0.5 Water 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached 
Exp. 
Capacity of 
(Rmax) completion 
g/m.sup.2) Batch No. 
No. Polymerizer 
.mu.m min. 1 2 3 5 7 10 
__________________________________________________________________________ 
219* 
5 l 10-13 30 H(800) 
220* 
20 l 0.1-0.3 " G H(750) 
221* 
5 l 0.05-0.1 " G H(780) 
222* 
" " " G H(800) 
223* 
" 10-13 " B E H(300) 
224* 
" " " B E H(280) 
225 100 l 0.8-1.0 15 A A A B C D(20) 
226 " " " A A A A A A(0.3) 
227 " " " A A A A A B(3) 
228 " " " A A A B C D(18) 
229 " " " A A A B C D(17) 
230 " " 10 A A A A A A(0.5) 
231 5 l 0.05-0.1 10 A A A A A B(3) 
232 " " " A A A A A B(3.5) 
233 " " " A A A A A A(0.7) 
234 " " " A A A A A A(0.6) 
235 " " " A A A B C D(20) 
236 " " " A A A B C D(18) 
237 " " " A A A B C D(19) 
238 20 l 0.1-0.3 " A A A B C D(21) 
239 " " " A A A B C D(18) 
240 " " 15 A A A B C D(19) 
241 " " " A A A A A A(0.9) 
242 " " " A A A A A A(0.5) 
243 5 l 0.4-0.7 15 A A A B C D(20) 
244 " " " A A A B C D(25) 
245 " " " A A A B C D(20) 
246 " " " A A A A A B(4) 
247 " " " A A A B C D(18) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 7 
As shown in Table 7, for each experiment, a 5-l, 20-l, or 100-l stainless 
steel polymerizer was selected, and the inner wall surface of the 
polymerizer and the portions of the auxiliary equipment such as the 
stirrers which may come into contact with monomer were treated to have the 
surface roughness (Rmax) shown in the Table. For each experiment, as shown 
in Table 7, a dye or a pigment was dissolved or dispersed in a solvent, 
optionally with the addition of an inorganic compound or a polymeric 
compound as shown in the Table to prepare a coating solution. The 
formulation ratio of the inorganic compound and the polymeric compound and 
the concentration of dye or pigment in the coating solution are also shown 
in Table 7. The coating solution was applied on the inner wall surface of 
the polymerizer, etc. treated as mentioned above, dried at 90.degree. C. 
for 10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 148 parts of water, 1.85 
parts of sodium oleate, 48 parts of polybutadiene latex (solid content: 
45%), 33 parts of styrene monomer, 19 parts of acrylonitrile monomer, 0.15 
part of t-dodecyl mercaptan and 0.5 part of cumene hydroperoxide. After 
the temperature of the mixture was raised to 65.degree. C., the 
polymerizer was further charged with 0.74 part of glucose, 0.0074 part of 
ferrous sulfate and 0.37 part of sodium pyrophosphate, and polymerization 
was carried out under stirring at 65.degree. C. for 5 hours. After 
completion of polymerization, the polymer was taken out and the 
polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 
hr for the period of time shown in Table 7. The above operations from 
coating and charging to washing with water were conducted for each batch 
and this was repeated for a maximum of 10 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount 
of scales adhering (g/m.sup.2) was also measured after completion of the 
final batch. The results are also shown in Table 7. 
In Table 7, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 248 and 249 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 7 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Dye or pigment (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. (Mixing ratio) 
(b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
248* 
-- -- -- -- 
249* 
-- -- -- -- 
250* 
-- Sodium metasilicate 
-- 0.5 Water 
251* -- Polyvinyl sulfonic acid 
0.7 " 
252* 
Solvent Black 5 
Colloidal silica 
100/50 
-- 0.7 Water/Methanol 
(30/70) 
253* 
Basic Orange 2 
Sodium metasilicate 
100/100 
-- 0.8 Water 
254 Solvent Red 23 
-- -- 0.4 Methanol 
255 Solvent Yellow 6/Direct 
-- -- 1.0 Water/Methanol 
Black 107 (40/60) (50/50) 
256 Disperse Blue 7 
-- -- 0.5 Acetone 
257 Disperse Violet 37 
-- -- 0.8 " 
258 Acid Black 2/Solvent 
-- -- 0.6 Water/Methanol 
Yellow 14 (90/10) (60/40) 
259 Pigment Red 14 
-- Polyvinyl acetate 
100/100 
0.8 Toluene 
260 Pigment Brown 1 
-- Polyvinyl ethyl ether 
100/30 
0.9 Methylene 
chloride 
261 Solvent Black 5 
Colloidal silica 
100/50 
-- 0.7 Water/Methanol 
(30/70) 
262 Basic Blue 45 
-- -- 0.5 Water 
263 Vat Brown 25 -- Polyvinyl sulfonic 
100/50 
0.6 " 
acid 
264 Disperse Blue 79 
-- -- 0.3 Acetone 
265 Acid Yellow 29 
-- -- 0.5 Water 
266 Basic Orange 2 
Sodium metasilicate 
100/100 
-- 0.8 " 
267 Disperse Blue 90 
Lithium orthosilicate 
100/40 
-- 0.8 Water/Acetone 
(40/60) 
268 Basic Violet 1 
-- -- 0.7 Water 
269 Disperse Yellow 4 
-- -- 0.5 Acetone 
270 Disperse Red 52 
-- -- 0.6 " 
271 Solvent Black 3 
-- -- 0.5 " 
272 Acid Red 303 Colloidal silica 
100/60 
-- 0.6 Water 
273 Fluorescent Brightening 
-- -- 0.4 " 
Agent 153 
274 Disperse Red 17 
-- -- 0.5 Acetone 
275 Basic Red 2 ZnCl.sub.3 100/10 
-- 0.8 Water/Isobutyl 
alcohol (80/20) 
276 Disperse Yellow 3 
-- -- 0.5 Acetone 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. Polymerizer 
.mu.m min. 1 2 3 5 7 10 
__________________________________________________________________________ 
248* 
5 l 10- 13 45 H(1500) 
249* 
20 l 0.1-0.3 " G H(800) 
250* 
" " " G H(1100) 
251* 
" " " G H(1200) 
252* 
5 l 0.05-0.1 " B E H(700) 
253* 
" " 15 B E H(650) 
254 " 0.4-0.7 " A A B C D H(200) 
255 " " " A A A B C D(20) 
256 " " " A A A B C D(25) 
257 " " " A A A B C D(18) 
258 " " " A A A A A A(0.5) 
259 " " " A A A A A B(3) 
260 100 l 0.8-1.0 10 A A A A A B(4) 
261 " " " A A A A A A(0.4) 
262 " " " A A A B C D(19) 
263 " " " A A A A A B(2.5) 
264 5 l 0.05-0.1 " A A A B C D(18) 
265 " " " A A B C D H(100) 
266 " " " A A A A A A(0.9) 
267 " " " A A A A A A(0.7) 
268 " " " A A A B C D(20) 
269 " " " A A A B C D(21) 
270 " " " A A A B C D(19) 
271 20 l 0.1-0.3 " A A A A A B(3) 
272 20 l 0.1-0.3 10 A A A A A A(0.9) 
273 " " " A A A B C D(20) 
274 " " " A A A B C D(21) 
275 " " " A A A A A A(0.5) 
276 " " " A A A B C D(20) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Dye or pigment concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 8 
As shown in Table 8, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as the stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 8, a conjugated .pi. bond 
compound was dissolved or dispersed in a solvent, optionally with the 
addition of an inorganic compound or a polymeric compound as shown in the 
Table to prepare a coating solution. The formulation ratio of the 
inorganic compound or the polymeric compound and the concentration of the 
conjugated .pi. bond compound in the coating solution are also shown in 
Table 8. The coating solution was applied on the inner wall surface of the 
polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 
10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of vinyl 
chloride monomer, 200 parts of deionized water, 0.022 part of partially 
saponified polyvinyl alcohol, 0.028 part of hydroxyethyl cellulose and 
0.03 part of t-butyl peroxyneodecanate, and polymerization was carried out 
at 52.degree. C. for 7 hours. After completion of polymerization, the 
polymer was taken out and the polymerizer was washed with water at a flow 
rate of 0.1 m.sup.3 /m.sup.2 hr for the period of time shown in Table 8. 
The above operations from coating and charging to washing with water were 
conducted for each batch and this was repeated for a maximum of 200 
batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. The results are also shown in Table 8. 
In Table 8, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 301 to 306 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 8 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. 
Kind (Mixing ratio) 
(b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
301* -- -- -- 
302* -- -- -- 
303* 
Quinalizarin -- -- 0.5 
Methanol 
304* 
Quinalizarin Colloidal silica 
100/50 0.8 
" 
305* -- " 0/100 
-- 0.5 
Water 
306* 
Aurine Colloid of sulfur 
100/30 
-- 0.8 
Water/Methanol 
(30/70) 
307* 
Azotoluene/ -- Poly(N--vinylbenzo- 
100/30 
0.6 
DMF 
Phenazoxide triazole) 
(60/40) 
308* 
1,2-Dichloro- Metasilicic acid 
100/50 
-- 0.6 
Water/Methanol 
naphthalene (30/70) 
309* 
Azoxyanthraquinone 
Colloid of sulfur 
100/10 
-- 0.7 
Water/Methanol 
(50/50) 
310 
Quinalizarin Fe(OH).sub.3 sol 
100/5 
-- 0.5 
Water/Methanol 
(50/50) 
311 " Al(OH).sub.3 sol 
100/2 
-- 0.4 
Water/Methanol 
(50/50) 
312 " CuCl.sub.2 
100/10 
-- 0.6 
Water/Methanol 
(50/50) 
313 
Quinalizarin FeCl.sub.3 
100/15 
-- 0.5 
Water/Methanol 
(50/50) 
314 
Phenylazo-2- Fe(OH).sub.3 sol 
100/5 
-- 0.5 
Water/Methanol 
naphthol (50/50) 
315 
Succinic acid -- -- 0.7 
Methanol 
bis(.beta.-phenyl- 
hydrazine) 
316 
Bisphenylhydrazone 
-- -- 0.6 
" 
317 
Benzophenone -- -- 0.5 
" 
potassium 
318 
Disalicylaldehyde Colloidal silica 
100/30 
-- 0.8 
Water/Methanol 
(80/20) 
319 
Aurin Colloid of sulfur 
100/20 
-- 0.8 
Water/Methanol 
(30/70) 
320 
Fluorene -- -- 0.6 
Methanol 
321 
Chlorobenzophenone 
-- -- 0.8 
" 
322 
6-Chloro-3- -- -- 0.5 
" 
benzoylflavone 
323 
Azotoluene/ 
(60/40) 
-- Poly(N-vinylbenzo- 
100/30 
0.6 
DMF 
Phenazoxide triazole) 
324 
2-Aminostilbene -- -- 0.9 
Methanol 
325 
2-Aminostilbene Al(OH).sub.3 sol 
100/10 
-- 0.8 
Water/Methanol 
(20/80) 
326 
Terphenyl -- -- 0.5 
Methanol 
327 
N--Methylnaph- -- -- 0.5 
" 
thylamine 
328 
1,2-Dichloro- -- -- 0.7 
Water/Methanol 
naphthalene (30/70) 
329 
1,2-Dichloro- Metasilicic acid 
100/50 
-- 0.6 
Water/Methanol 
naphthalene (30/70) 
330 
1-Phenoxynaph- -- -- 0.8 
Methanol 
thalene 
331 
Dinaphthoquinone -- -- 0.5 
" 
332 
Imide chloride -- -- 0.5 
" 
333 
4-Oxybenzanthrone -- -- 0.6 
" 
334 
1-Aminoanthracene Orthosilicic acid 
100/30 
-- 0.8 
Water/Methanol 
(50/50) 
335 
1,4-Diamino- Metasilicic acid 
100/50 
-- 0.8 
Water/Methanol 
anthracene (20/80) 
336 
1,1'-Bianthryl -- -- 0.5 
Methanol 
337 
Estrone/3- (50/50) 
-- -- 0.5 
" 
Acetylretene 
338 
2,7-Dibromophenan- 
-- -- 0.8 
" 
threnequinone 
339 
2-Oxyretenequinone 
-- -- 0.9 
" 
340 
Benzo[a]pyrene- -- -- 0.6 
" 
1,6-quinone 
341 
1,4-naphthoquinone 
-- -- 0.6 
" 
phenoxathine 
342 
2-Methyl-3-phytil-1,4- 
-- Polyacetaldehyde 
100/30 
1.0 
" 
naphthoquinone 
343 
Di-(3-oxy-1,4- -- 0.7 
" 
naphthoquinonyl- 
2-)methane 
344 
Quinalizarin -- -- 0.5 
" 
345 
Azoxyanthraquinone 
-- -- 0.7 
Water/Methanol 
(50/50) 
346 
Azoxyanthraquinone 
Colloid of sulfur 
100/10 
-- 0.7 
Water/Methanol 
(50/50) 
347 
Benzopyran/6- 
(40/60) 
-- -- 0.7 
Methanol 
Phenylcumalin 
348 
Dracorhodin/ 
(50/50) 
-- -- 0.6 
" 
Petunidin 
349 
Fukugetin -- -- 0.8 
" 
350 
Xanthotoxin -- -- 0.9 
" 
351 
Bilirubin -- -- 0.7 
" 
352 
3-Triphenyl- -- -- 0.7 
" 
methylindole 
353 
Tryptophan/ -- -- 0.5 
" 
Violasein (70/30) 
354 
2,2'-Diaminodiphenyl 
Colloidal silica 
100/100 
-- 0.8 
Water/Methanol 
(40/60) 
355 
5-Amino-3-methyl-4- -- 0.7 
Methanol 
phenylisoxazole 
356 
2-Phenylimidazole -- Poly(1,5-hexane- 
100/50 
1.0 
Acetophenone 
dienesulfone) 
357 
5-Amino-3- -- -- 0.7 
Methanol 
phenylpyrazole 
358 
3,4-Diphenylfurazane 
-- -- 0.6 
" 
359 
Quinaldine/ 
(0/60) 
-- -- 0.9 
" 
Naphthocyanol 
360 
6-Aminomethyl- -- -- 0.4 
" 
phenanthridine 
361 
Quinazoline/ 
(50/50) 
-- -- 0.5 
" 
2,3-Dimethyl- 
quinoxaline 
362 
Quinazoline 
(50/50) 
Fe(OH).sub.3 sol 
100/5 
-- 0.9 
" 
2,3-Dimethyl- 
quinoxaline 
363 
.alpha.-Sexithienyl 
-- -- 0.6 
" 
364 
2,3-Thiophan- -- -- 0.8 
" 
thraquinone 
365 
8,9-Benzothio- -- -- 0.8 
" 
phanthrene 
366 
Thiaxanthone -- -- 0.6 
" 
367 
Thianthrene -- -- 0.9 
" 
368 
3-Ethyl-2-phenyl- Colloidal silica 
100/200 
-- 0.5 
Water/Methanol 
pyrrocoline (50/50) 
369 
Canadine methiodide 
-- -- 0.7 
Methanol 
370 
Codamine -- -- 1.0 
" 
371 
Flindersine -- -- 0.7 
" 
372 
Laudanine/ (50/50) 
Colloid of vanadium 
100/50 
-- 1.0 
Water/Methanol 
Corpaverine pentoxide (20/80) 
373 
o-Methylberbamine -- -- 0.5 
Methanol 
374 
Angelicin -- -- 0.5 
" 
375 
Pimpinellin -- -- 0.3 
" 
376 
Medakenine -- -- 0.5 
" 
377 
Xanthoxylene -- -- 0.6 
" 
378 
Nodakenetin -- Polyethylene 
100/50 
0.8 
" 
terephthalate 
379 
Seselin -- -- 0.7 
" 
380 
Oroselole -- -- 0.6 
" 
381 
Psoralen -- -- 0.5 
" 
382 
Dixanthylene -- -- 0.5 
" 
383 
9,9-Diphenylxanthene 
-- -- 0.7 
" 
384 
2,5-Diphenylisoindole 
-- -- 0.4 
" 
385 
Naphtho[1,2] CuCl.sub.2 
100/10 
-- 0.8 
Water/Methanol 
thiazole (30/70) 
386 
2-Fluoroquinoline/ 
Al(OH).sub.3 sol 
100/20 
-- 0.7 
Water/Methanol 
Quinoxaline (50/50) 
387 
1,5-Diphenyltetrazole 
-- -- 0.5 
Methanol 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. 
Polymerizer 
.mu.m min. 10 30 50 100 
150 
200 
__________________________________________________________________________ 
301* 
100 l 10-13 60 H (1200) 
302* 
1 m.sup.3 
0.2-0.3 " E H (800) 
303* 
40 m.sup.3 
7-8 " E H (700) 
304* 
" " " B E H (250) 
305* 
1 m.sup.3 
0.2-0.3 " H (800) 
306* 
100 l 10-13 " B E H (400) 
307* 
" " " E H (400) 
308* 
" " " B E H (300) 
309* 
" " " B E H (280) 
310 
2 m.sup.3 
0.05-0.1 15 A A A A A B (2.1) 
311 
" " " A (1.8) 
A A A A B (1.8) 
312 
" " " A A A A A B (2.0) 
313 
" " " A A A A A B (2.5) 
314 
" " " A A A A A B (3) 
315 
" " " A A A B C D (20) 
316 
" " " A A A B C D (15) 
317 
" " " A A A B C D (18) 
318 
" " " A A A A A B (1.8) 
319 
" " " A A A A A B (3) 
320 
" " " A A A B C D (20) 
321 
" " " A A B C D F (60) 
322 
100 l 0.8-1.0 " A A A B C D (21) 
323 
" " 10 A A A A B B (2.6) 
324 
" " " A A A B C D (21) 
325 
" " " A A A A A B (2.8) 
326 
" " " A A A B C D (20) 
327 
" " " A A A B C D (23) 
328 
" " " A A A B C D (19) 
329 
" " " A A A A A B (3) 
330 
" " " A A A B C D (18) 
331 
" " " A A B C D F (60) 
332 
" " " A A B C D F (59) 
333 
" " 15 A A A B C D (20) 
334 
130 m.sup.3 
0.4-0.7 20 A A A A A B (3) 
335 
" " " A A A A A B (2.5) 
336 
1 m.sup.3 
0.2-0.3 " A A A B C D (21) 
337 
" " " A A B C D F (55) 
338 
" " " A A A B C D (15) 
339 
" " " A A A B C D (17) 
340 
" " " A A B C D F (58) 
341 
" " " A A A B C D (15) 
342 
" " " A A A B B C (8) 
343 
" " " A A A B C D (14) 
344 
" " " A A A B C D (17) 
345 
" " " A A A B C D (19) 
346 
" " " A A A A A B (2.2) 
347 
" " " A A A B C D (18) 
348 
" " " A A A B C D (13) 
349 
" " " A A A B C D (19) 
350 
" " " A A A B C D (20) 
351 
" " " A A B C D F (60) 
352 
" " " A A A B C D (20) 
353 
130 m.sup.3 
0.4-0.7 15 A A A B C D (18) 
354 
100 l 0.8-1.0 " A A A A A B (2.6) 
355 
" " " A A A B C D (19) 
356 
" " " A A A B B C (5) 
357 
" " " A A A B C D (13) 
358 
" " " A A A B C D (19) 
359 
" " " A A A B C D (16) 
360 
" " " A A A B C D (18) 
361 
" " " A A A B C D (15) 
362 
" " " A A A A A B (1.9) 
363 
" " " A A B C D F (60) 
364 
" " " A A A B C D (20) 
365 
2 m.sup.3 
0.05-0.1 10 A A A B C D (20) 
366 
" " " A A B C D F (60) 
367 
" " " A A A B C D (21) 
368 
" " " A A A A A B (2) 
369 
" " " A A A B C D (18) 
370 
" " " A A A B C D (17) 
371 
" " " A A A B C D (20) 
372 
" " " A A A A A B (1.9) 
373 
" " " A A B C D F (61) 
374 
" " " A A B C D F (60) 
375 
100 l 0.8-1.0 " A A A B C D (18) 
376 
" " " A A A B C D (17) 
377 
" " " A A A B C D (15) 
378 
" " " A A A A B C (8) 
379 
" " " A A B C D F (60) 
380 
" " " A A B C D F (58) 
381 
" " " A A B C D F (57) 
382 
100 l " " A A B C D F (60) 
383 
" " " A A A B C D (20) 
384 
130 m.sup.3 
0.4-0.7 15 A A A B C D (20) 
385 
" " " A A A A A B (2.7) 
386 
1 m.sup.3 
0.2-0.3 " A A A A A B (2.5) 
387 
" " " A A A B C D 
__________________________________________________________________________ 
(18) 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surfacce of the polymerizer and 
the portions of the equipment therof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 9 
As shown in Table 9, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as the stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 9, a conjugated .pi. bond 
compound was dissolved or dispersed in a solvent, optionally with the 
addition of an inorganic compound or a polymeric compound as shown in the 
Table to prepare a coating solution. The formulation ratio of the 
inorganic compound or the polymeric compound and the concentration of the 
conjugated .pi. bond compound in the coating solution are also shown in 
Table 9. The coating solution was applied on the inner wall surface of the 
polymerizer, etc. treated as mentioned above, dried at 80.degree. C. for 
10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of vinyl 
chloride monomer, 200 parts of deionized water, 0.125 part of 
hydroxypropylmethyl cellulose, 0.125 part of sorbitan monolaurate and 
0.025 part of a .alpha.,.alpha.'-azobis-2,4-dimethylvalelonitrile, and 
polymerization was carried out at 52.degree. C. for 10 hours. After 
completion of polymerization, the polymer was taken out and the 
polymerizer was washed with water at a flow rate of 0.1 m.sup.3 /m.sup.2 
hr for the period of time shown in Table 9. The above operations from 
coating and charging to washing with water were conducted for each batch 
and this was repeated for a maximum of 200 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. The results are also shown in Table 9. 
In Table 9, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 388 and 389 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 9 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. 
Kind (Mixing ratio) 
(b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
388* 
-- -- -- 
389* 
-- -- -- 
390* 
2,4-Dinitrophenoxazine 
-- -- 0.5 
Methanol 
391* 
" Silicomolybdic acid 
100/50 
-- 1.0 
Water/Methanol 
(30/70) 
392* 
-- Silicomolybdic acid 
0/100 
-- 0.5 
Water 
393* 
1-Aminoacetylnaphthalene 
Fe(OH).sub.3 sol 
100/20 
-- 0.8 
Water/Methanol 
(10/90) 
394 
2,4-Dinitrophenoxazine 
-- -- 0.5 
Water/Methanol 
(30/70) 
395 
2,4-Dinitrophenoxazine 
Silicomolybdic acid 
100/50 
-- 1.0 
Water/Methanol 
(30/70) 
396 
Triphenylenedioxazine 
-- -- 0.6 
Methanol 
397 
Bis(4-nitrophenylhydrazine) 
-- -- 0.5 
" 
398 
Dinitrobenzyl -- -- 0.7 
" 
399 
Phlorchinyl -- -- 0.8 
" 
400 
2-Oxy-4-methylquinone 
-- -- 0.6 
Methanol 
401 
2,2'-Diaminostilbene 
-- -- 0.5 
" 
402 
Di-.alpha.-naphthylmethane 
-- Polyindene 100/50 
0.8 
Benzene 
403 
Naphthazarin/Perimidone 
-- -- 1.0 
Methanol 
(70/30) 
404 
Diaminotetralin Colloidal silica 
100/100 
-- 0.7 
Water/Methanol 
(50/50) 
405 
2,3-Dihydrazinonaphthalene 
-- Polyvinyl ethyl ether 
100/100 
0.9 
Chloroform 
406 
3-Acetyl-6,7-benzocumarin 
-- -- 0.6 
Methanol 
407 
1,2-Benzoxanthone 
-- -- 0.5 
" 
408 
1-Aminoacetylnaphthalene 
Fe(OH).sub.3 sol 
100/20 0.8 
Water/Methanol 
(10/90) 
409 
9-Isopropylanthracene 
-- -- 0.6 
Methanol 
410 
Anthrone/6-Acylaminoretene 
-- -- 0.9 
" 
(50/50) 
411 
2,7-Diaminophenanthrenequinone 
ZnCl.sub.2 
100/5 
-- 0.7 
Water/Methanol 
(20/80) 
412 
Nitrosaminonaphthoquinone 
-- -- 0.6 
Water/Methanol 
(50/50) 
413 
Nitrosaminonaphthoquinone 
Orthosilicic acid 
100/100 
-- 0.7 
Water/Methanol 
(50/50) 
414 
Azoxyanthraquinone 
Mesotrisilicic acid 
100/50 
-- 0.4 
Water/Methanol 
(40/60) 
415 
Alizarinquinone/Pyridoxine 
-- -- 0.9 
Methanol 
(80/20) 
416 
Stercobilin -- -- 0.6 
" 
417 
2-Methyl[1,2]thiazole 
-- -- 0.4 
" 
418 
Azacyanine -- -- 0.9 
" 
419 
Acriflavine -- -- 0.6 
" 
__________________________________________________________________________ 
(3) (4) Scaling 
(1) Surface roughness of 
Time for washing 
Visual evaluation (Amount attached 
g/m.sup.2) 
Exp. 
Capacity of 
inner wall surface, etc. 
with water after 
Batch No. 
No. 
Polymerizer 
(Rmax) .mu.m 
completion min. 
10 30 50 100 150 
200 
__________________________________________________________________________ 
388* 
100 l 10-13 45 H(1500) 
389* 
2 m.sup.3 
0.05-0.1 " H(1200) 
390* 
40 m.sup.3 
7-8 " G H(700) 
391* 
" " 30 B E H(500) 
392* 
2 m.sup.3 
0.05-0.1 " H(900) 
393* 
100 l 10-13 " B C F H(400) 
394 
2 m.sup.3 
0.05-0.1 " A A B C D F(60) 
395 
" " " A A A A B C(10) 
396 
" " " A A B C D F(59) 
397 
" " " A A B B C D(20) 
398 
" " " A A B C D E(31) 
399 
" " " A A B C D F(61) 
400 
" " " A A B C D E(29) 
401 
" " " A A B C D F(60) 
402 
" " " A A A B C D(23) 
403 
" " " A A B C D E(30) 
404 
" " " A A A A B C(10) 
405 
" " " A A A B C D(21) 
406 
" " " A A B C D F(60) 
407 
1 m.sup.3 
0.2-0.3 " A A B C D F(58) 
408 
" " " A A A A B C(9) 
409 
" " " A A B C D F(60) 
410 
" " " A B B C D F(65) 
411 
" " " A A A A B C(8) 
412 
" " " A A B C D F(60) 
413 
" " " A A A A B C(20) 
414 
" " " A A A A B C(21) 
415 
" " " A A B C D E(30) 
416 
" " " A B B C D F(62) 
417 
" " " A A B C D F(60) 
418 
" " " A A B C D E(30) 
419 
" " " A A B C D E(29) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 10 
As shown in Table 10, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as the stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table 10, a conjugated .pi. bond 
compound was dissolved or dispersed in a solvent, optionally with the 
addition of an inorganic compound or a polymeric compound as shown in the 
Table to prepare a coating solution. The formulation ratio of the 
inorganic compound or the polymeric compound and the concentration of the 
conjugated .pi. bond compound in the coating solution are also shown in 
Table 10. The coating solution was applied on the inner wall surface of 
the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. 
for 10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 80 parts of vinyl 
chloride monomer, 20 parts of vinyl acetate monomer, 200 parts of 
deionized water, 0.3 part of gelatin, 1 part of trichlene and 0.175 part 
of lauroyl peroxide, and polymerization was carried out at 70.degree. C. 
for 6 hours. After completion of polymerization, the polymer was taken out 
and the polymerizer was washed with water at a flow rate of 0.1 m.sup.3 
/m.sup.2 hr for the period of time shown in Table 10. The above operations 
from coating and charging to washing with water were conducted for each 
batch and this was repeated for a maximum of 200 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. The results are also shown in Table 10. 
In Table 10, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 420 and 421 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 10 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic 
(a)/(b) 
Polymeric 
(a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. 
Kind (Mixing ratio) 
(b) ratio (c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
420* 
-- -- -- 
421* 
-- -- -- 
422* 
9,9-Azoxyphenanthrene 
-- -- Methanol 
423* 
" Fe(OH).sub.3 sol 
100/5 -- 0.8 
" 
424* 
-- Fe(OH).sub.3 sol 
0/100 
-- 0.5 
Water 
425* 
4-Aminoacridine Water glass 
100/50 
-- 0.6 
Water/Methanol 
(80/20) 
426 
Egonol -- -- 1.0 
Methanol 
427 
Dibenzofuran -- -- 0.9 
" 
428 
Euparin -- -- 0.5 
" 
429 
Dracorubin/Pelargonidin 
-- -- 1.0 
" 
(50/50) 
430 
Isopimpinellin Colloidal silica 
100/200 
-- 1.0 
Water/Methanol 
(20/80) 
431 
2,3,4,5-Tetraphenylpyrrole 
-- -- 0.5 
Methanol 
432 
1,3-Diphenylpyrazole 
-- -- 0.7 
Methanol 
433 
4-Aminoacridine -- -- 0.6 
Water/Methanol 
(80/20) 
434 
4-Aminoacridine Water glass 
100/50 
-- 0.6 
Water Methanol 
(80/20) 
435 
3-Bromocinnoline -- -- 0.7 
Methanol 
436 
Cyclo[3.2.2]azine MgCl.sub.2 
100/10 
-- 0.7 
Water/Methanol 
437 
Heteroquinine/Quinotoxine 
-- -- 0.9 
Methanol 
(70/30) 
438 
Naphthotropone Colloid of lithium 
100/50 
-- 1.0 
Water/Methanol 
silicate (50/50) 
439 
N--Naphthylglycine 
-- Polycyclohexane 
100/70 
1.5 
Benzene 
oxide 
440 
.alpha.-Naphthylhydrazine 
-- -- 0.7 
Methanol 
441 
4-Amino-1-naphthaldehyde 
-- -- 0.6 
" 
442 
4-Amino-1-naphthaldehyde 
Orthosilicic acid 
100/30 
-- 0.8 
Water/Methanol 
(70/30) 
443 
2-Aminobenzoylnaphthalene 
-- -- 0.7 
Water/Methanol 
(10/90) 
444 
9,9'-Azoxyphenanthrene 
Fe(OH).sub.3 sol 
100/5 -- 0.8 
Methanol 
445 
Mesonaphthodianthrene 
-- -- 0.4 
" 
446 
Triphthaloylbenzene 
-- -- 0.7 
" 
447 
Anthraquinoneacridone 
-- -- 0.6 
" 
448 
Anthraquinoneacridone 
CaCl.sub.2 
100/5 -- 0.6 
" 
449 
Mesonaphthodianthrone 
-- -- 0.8 
" 
450 
Phenazine -- -- 0.4 
" 
451 
2-Methylquinazoline 
-- -- 0.9 
" 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. 
Polymerizer 
.mu.m min. 10 30 
50 100 150 
200 
__________________________________________________________________________ 
420* 
100 l 10-13 45 H(1100) 
421* 
2 m.sup.3 
0.05-0.1 " H(700) 
422* 
40 m.sup.3 
7-8 " B E H(500) 
423* 
" " " B C F H(400) 
424* 
2 m.sup.3 
0.05-0.1 " H(800) 
425* 
100 l 10-13 " B C F H(500) 
426 
1 m.sup.3 
0.2-0.3 15 A A A B C D(20) 
427 
" " " A A B C D F(60) 
428 
" " " A A B C D F(61) 
429 
" " " A A B C D F(58) 
430 
" " " A A A A A B(2.5) 
431 
" " " A A B C D F(58) 
432 
1 m.sup.3 
0.2-0.3 15 A A A B C D(20) 
433 
" " " A A A B C D(18) 
434 
" " " A A A A A B(2.3) 
435 
" " " A A B C D F(59) 
436 
" " " A A A A B C(10) 
437 
100 l 0.8-1.0 10 A A A B C D(21) 
438 
" " " A A A A B C(9) 
439 
" " " A A A B B C(8) 
440 
" " " A A B C D F(60) 
441 
" " " A A A B C D(21) 
442 
" " " A A A A B C(10) 
443 
" " " A A A B C D(23) 
444 
100 l 0.8-1.0 10 A A A A B C(9) 
445 
" " " A A A B C D(21) 
446 
" " " A A A B C D(20) 
447 
2 m.sup.3 
0.05-0.1 " A A A B C D(18) 
448 
" " " A A A A B C(9) 
449 
" " " A A B C D F(50) 
450 
" " " A A A B C D(21) 
451 
" " " A A A B C D(19) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 11 
As shown in Table 11, for each experiment, a 100-l, 1000-l, 2000-l, 
40-m.sup.3 or 130-m.sup.3 stainless steel polymerizer was selected, and 
the inner wall surface of the polymerizer and the portions of the 
auxiliary equipment such as the stirrers which may come into contact with 
monomer were treated to have the surface roughness (Rmax) shown in the 
Table. For each experiment, as shown in Table II, a conjugated .pi. bond 
compound was dissolved or dispersed in a solvent, optionally with the 
addition of an inorganic compound or a polymeric compound as shown in the 
Table to prepare a coating solution. The formulation ratio of the 
inorganic compound or the polymeric compound and the concentration of the 
conjugated .pi. bond compound in the coating solution are also shown in 
Table 11. The coating solution was applied on the inner wall surface of 
the polymerizer, etc. treated as mentioned above, dried at 80.degree. C. 
for 10 minutes and then thoroughly washed with water. 
Next, the thus coated polymerizer was charged with 100 part of vinyl 
chloride monomer, 200 parts of deionized water, 0.02 part of partially 
saponified polyvinyl alcohol, 0.03 part of hydroxymethyl cellulose and 
0.04 part of di-2-ethylhexyl peroxydicarbonate, and polymerization was 
carried out at 57.degree. C. for 7 hours After completion of 
polymerization, the polymer was taken out and the polymerizer was washed 
with water at a flow rate of 0.1 m.sup.3 /m.sup.2 hr for the period of 
time shown in Table 11. The above operations from coating and charging to 
washing with water were conducted for each batch and this was repeated for 
a maximum of 200 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
10th, 30th, 50th, 100th, 150th and 200th batches was evaluated visually, 
and the amount of scales adhering (g/m.sup.2) was also measured after 
completion of the final batch. 
The numbers of fish eyes in the products obtained from the polymers 
produced in the 10th, 30th, 50th, 100th, 150th and 200th batches in each 
experiment were measured in the same manner as in Example 4. The results 
are shown in Table 11. 
In Table 11, the Experimental numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 452 and 453 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 11 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric 
(a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound weight compound 
weight 
conc. 
Solvent 
No. Kind (Mixing ratio) 
(b) ratio (c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
452* 
-- -- -- 
453* 
-- -- -- 
454 Quinalizarin Colloidal silica 
100/100 
-- 0.8 Methanol 
455 Disalicylaldehyde Fe(OH).sub.3 sol 
100/10 -- 0.9 " 
456 1-Phenoxynaphthalene 
CaCl.sub.2 
100/5 -- 0.5 " 
457 Azoxyanthraquinone 
Colloid of sulfur 
100/40 -- 0.6 " 
458 Quinaldine/Naphthocyanol 
CuCl.sub.2 
100/20 -- 1.0 " 
(50/50) 
459 2,5-Diphenylisoindole 
Al(OH).sub.3 sol 
100/10 -- 0.7 " 
460 2,2'-Diaminostilbene 
Ni(NO.sub.3).sub.2 
100/5 -- 0.8 " 
461 Naphthazarin/Perimidone 
Fe(OH).sub.3 sol 
100/10 -- 0.7 " 
(60/40) 
462 Azacyanine Colloidal silica 
100/100 
-- 0.9 Methanol 
463 Azacyanine -- -- 0.9 " 
__________________________________________________________________________ 
(3) (4) 
Surface roughness 
Time for washing 
Scaling 
(1) of inner wall 
with water after 
Visual evaluation (Amount attached 
Fish eyes(number) 
Exp. 
Capacity of 
surface, etc. 
completion 
g/m.sup.2) Batch No. 
Batch No. 
No. 
Polymerizer 
(Rmax) .mu.m 
min. 10 30 
50 
100 
150 
200 10 30 
50 
100 
150 
200 
__________________________________________________________________________ 
452* 
100 l 10-13 60 H(1000) 300 
453* 
40 m.sup.3 
7-8 " H(950) 280 
454 
100 l 0.8-1.0 15 A A A A B C(10) 
0 0 0 0 30 55 
455 
" " " A A A A B C(9) 
0 0 0 0 25 50 
456 
" " " A A A A B C(7) 
0 0 0 0 13 30 
457 
" " " A A A A B C(9) 
0 0 0 0 15 35 
458 
130 m.sup.3 
0.4-0.7 " A A A A B C(8) 
0 0 0 0 20 40 
459 
1 m.sup.3 
0.2-0.3 " A A A A B C(10) 
0 0 0 0 35 70 
460 
" " " A A A A B C(7) 
0 0 0 0 12 20 
461 
" " " A A A A B C(8) 
0 0 0 0 21 40 
462 
1 m.sup.3 
0.2-0.3 15 A A A A B C(10) 
0 0 0 0 32 60 
463 
" " " A A A B C D(18) 
0 0 0 15 40 70 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 12 
As shown in Table 12, for each experiment, a 5-l, 20-l, or 100-l stainless 
steel polymerizer was selected, and the inner wall surface of the 
polymerizer and the portions of the auxiliary equipment such as the 
stirrers which may come into contact with monomer were treated to have the 
surface roughness (Rmax) shown in the Table. For each experiment, as shown 
in Table 12, a conjugated .pi. bond compound was dissolved or dispersed in 
a solvent, optionally with the addition of an inorganic compound or a 
polymeric compound as shown in the Table to prepare a coating solution. 
The formulation ratio of the inorganic compound or the polymeric compound 
and the concentration of the conjugated .pi. bond compound in the coating 
solution are also shown in Table 12. The coating solution was applied on 
the inner wall surface of the polymerizer, etc. treated as mentioned 
above, dried at 90.degree. C. for 10 minutes and then thoroughly washed 
with water. 
Next, the thus coated polymerizer was charged with 75 parts of styrene, 25 
parts of acrylonitrile, 120 parts of deionized water, 0.5 part of 
tricalcium phosphate, 0.01 part of sodium dodecylbenzenesulfonate and 0.4 
part of lauroyl peroxide, and polymerization was carried out at 90.degree. 
C. for 8 hours. After completion of polymerization, the polymer was taken 
out and the polymerizer was washed with water at a flow rate of 0.1 
m.sup.3 /m.sup.2 hr for the period of time shown in Table 12. The above 
operations from coating and charging to washing with water were conducted 
for each batch and this was repeated for a maximum of 10 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount 
of scales adhering (g/m.sup.2) was also measured after completion of the 
final batch. The results are also shown in Table 12. 
In Table 12, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 464 and 465 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 12 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic (a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. Kind (Mixing ratio) 
(b) ratio 
(c) ratio 
% (Mixing 
__________________________________________________________________________ 
ratio) 
464* 
-- -- -- 
465* 
-- -- -- 
466* 
Diaminonaphthalene 
-- -- 0.6 
Methanol 
467* 
" Colloidal silica 
100/50 
-- 0.6 
" 
468* 
-- Colloidal silica 
0/100 
-- 0.5 
Water 
469* 
N--Benzylnaphthylamine 
CaCl.sub.3 
100/5 
-- 0.7 
Methanol 
470* 
1-Benzoylphenanthrene 
Fe(OH).sub.3 sol 
100/20 
-- 0.5 
" 
471* 
Isoxazole Mesotetrasilicic acid 
100/100 
-- 0.6 
Water/Methanol 
(50/50) 
472 Diaminonaphthalene 
-- -- 0.6 
Methanol 
473 " Colloidal silica 
100/50 
-- 0.6 
" 
474 Tetraaminonaphthalene 
-- -- 0.8 
" 
475 N--Methylnaphthylamine 
-- -- 1.0 
" 
476 N--Benzylnaphthylamine 
CoCl.sub. 3 
100/5 
-- 0.7 
Methanol 
477 N--Phthaloylnaphthylamine 
-- Polyvinyl alcohol 
100/30 
0.6 
Water/Isobutyl 
alcohol (90/10) 
478 Aminotetralin -- -- 0.4 
Methanol 
479 Acenaphthene/Dinaphthopyran 
-- -- 0.7 
" 
480 1-Benzoylphenanthrene 
-- -- 0.5 
" 
481 1-Benzoylphenanthrene 
Fe(OH).sub.3 sol 
100/20 
-- 0.5 
" 
482 4,4'-Diphenoquinone 
-- Polypyridylacetylene 
100/80 
0.8 
" 
483 Phenanthrophenazine 
-- -- 0.6 
" 
484 Calchonphenylhydrazone 
-- -- 0.7 
" 
485 Apigeninidin -- -- 0.5 
" 
486 Apigeninidin Colloidal silica 
100/150 
-- 0.8 
Water/Methanol 
(30/70) 
487 Ostruthol/Bergapten 
-- -- 0.7 
Methanol 
488 Prodigiosin -- -- 0.5 
Methanol 
489 Isoxazole Mesotetrasilicic acid 
100/100 
-- 0.6 
Water/Methanol 
(50/50) 
490 2-Aminonaphtho[2,1]thiazole 
-- -- 0.6 
Methanol 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of (Rmax) completion 
Batch No. 
No. Polymerizer .mu.m min. 1 2 3 5 7 10 
__________________________________________________________________________ 
464* 
5 l 10-13 20 H(1200) 
465* 
20 l 0.1-0.3 " H(1950) 
466* 
5 l 10-13 " G H(700) 
467* 
" " " B E H(280) 
468* 
" 0.05-0.1 " G H(1000) 
469* 
" 10-13 " B E H(600) 
470* 
" " " B E H(400) 
471* 
" " " B E H(300) 
472 100 l 0.8-1.0 10 A A A B C D(20) 
473 " " " A A A A A B(3) 
474 " " " A A A B C D(21) 
475 " " " A A A B C D(18) 
476 20 l 0.1-0.3 10 A A A A A B(2.5) 
477 " " " A A A A B C(10) 
478 " " " A A A B C D(22) 
479 " " " A A A B C D(25) 
480 5 l 0.05-0.1 " A A A B C D(19) 
481 " " " A A A A A B(2.1) 
482 " " " A A A A B C(12) 
483 " " " A A A B C D(20) 
484 " " 5 A A A B C D(18) 
485 " " " A A A B C D(15) 
486 " 0.4-0.7 " A A A A A B(2.5) 
487 " " " A A A B C D(20) 
488 5 l 0.4-0.7 5 A A A B C D(17) 
489 " " " A A A A A B(2.8) 
490 " " " A A A B C D(25) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 13 
As shown in Table 13, for each experiment, a 5-l, 20-l, or 100-l stainless 
steel polymerizer was selected, and the inner wall surface of the 
polymerizer and the portions of the auxiliary equipment such as the 
stirrers which may come into contact with monomer were treated to have the 
surface roughness (Rmax) shown in the Table. For each experiment, as shown 
in Table 13, a conjugated .pi. bond compound was dissolved or dispersed in 
a solvent, optionally with the addition of an inorganic compound or a 
polymeric compound as shown in the Table to prepare a coating solution. 
The formulation ratio of the inorganic compound and the polymeric compound 
and the concentration of the conjugated .pi. bond compound in the coating 
solution are also shown in Table 13. The coating solution was applied on 
the polished inner wall surface of the polymerizer, etc. treated as 
mentioned above, dried at 90.degree. C. for 10 minutes and then thoroughly 
washed with water. 
Next, the thus coated polymerizer was charged with 100 parts of styrene 
monomer, 250 parts of deionized water, 0.2 part of polyvinyl alcohol, 0.75 
part of t-dodecyl mercaptan and 0.5 part of lauroyl peroxide, and 
polymerization was carried out at 70.degree. C. for 5 hours. Thereafter, 
the temperature of the mixture was raised from 70.degree. C. to 80.degree. 
C. over 2 hours, and polymerization was conducted at 80.degree. C. for 
another one hour. After completion of polymerization, the polymer was 
taken out and the polymerizer was washed with water at a flow rate of 0.1 
m.sup.3 /m.sup.2 hr for a period of time shown in Table 13. The above 
operations from coating and charging to washing with water were conducted 
for each batch and this was repeated for a maximum of 10 batches. 
In the same manner as in Example 1, scaling after completion of each of the 
1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount 
of scales adhering (g/m.sup.2) was also measured after completion of the 
final batch. The results are also shown in Table 13. 
In Table 13, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 491 and 492 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 13 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic 
(a)/(b) 
Polymeric (a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound weight 
compound weight 
conc. 
Solvent 
No. Kind (Mixing ratio) 
(b) ratio 
(c) ratio % (Mixing 
__________________________________________________________________________ 
ratio) 
491* 
-- -- -- 
492* 
-- -- -- 
493* 
-- Colloidal silica 
0/100 
-- 
494* 
-- -- Poly(3-phenoxylene) 
0/100 
0.5 
Methanol 
495* 
Pararosaniline Colloidal silica 
100/20 
-- Water/Methanol 
(40/60) 
496* 
3-Nitro-2-phenylindole/Acid 
Colloidal silica 
100/50 
-- 0.8 
Water/Methanol 
Red 274 (50/50) 
497 Benzoic acid toluidide 
-- -- 0.4 
Methanol 
498 2-Phenylbenzoxazole 
-- -- 0.8 
" 
499 3-Nitro-2-phenylindole 
-- -- 0.3 
" 
500 Pararosaniline Colloidal silica 
100/20 
-- 0.6 
Water/Methanol 
(40/60) 
501 Pyrrole-polymethine dye 
-- -- 0.4 
Methanol 
502 9-Benzylacridine -- Poly(3-phenoxylene) 
100/30 
0.5 
" 
503 5-Phenylthiazole -- -- 0.5 
Methanol 
504 2-(o-Aminophenyl)benzimidazole 
-- -- 0.3 
" 
505 Indigo/Carbazole Fe(OH).sub.3 sol 
100/10 
-- 0.5 
Water/Methanol 
(70/30) (10/90) 
506 3-Nitro-2-phenylindole/Acid 
Colloidal silica 
100/50 
-- 0.8 
Water/Methanol 
Red 274 (40/60) (50/50) 
507 1-Chloroisoquinoline 
-- -- 0.9 
Methanol 
508 1-Aminoacridine -- -- 0.5 
" 
509 8-Methyl-1,7-phenanthroline 
-- -- 0.4 
" 
510 5-Phenyltetrazole 
Colloidal silica 
100/100 
-- 0.7 
Water/Methanol 
(40/60) 
511 2-Methylquinoxaline 
-- -- 0.5 
Methanol 
512 1-Phenazinol -- -- 0.3 
" 
513 Bis(3-dibenzofuryl) 
Metasilicic acid 
100/20 
-- 0.5 
Water/Methanol 
(20/80) 
514 2-Iodobenzothiophene 
-- -- 0.9 
Methanol 
515 Naphtho[1,2-b]thiophene 
-- -- 0.8 
Methanol 
516 2,3-Diaminophenazine/Direct 
-- -- 0.8 
Water/Methanol 
Green 6 (50/50) (40/60) 
517 Benzo[b] quinolizinium salt 
Colloidal silica 
100/100 
-- 0.6 
Water 
518 Acronycidine -- -- 0.4 
Methanol 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. Polymerizer 
.mu.m min. 1 2 3 5 7 10 
__________________________________________________________________________ 
491* 
5 l 10-13 30 H(800) 
492* 
20 l 0.1-0.3 " G H(750) 
493* 
5 l 0.05-0.1 " G H(780) 
494* 
" " " G H(820) 
495* 
" 10-13 " B E H(400) 
496* 
" " 10 B E H(300) 
497 " 0.4-0.7 " A A A B C D(20) 
498 " " " A A B C D E(30) 
499 " " " A A B B C D(21) 
500 " " 15 A A A A A B(2.3) 
501 " " " A A A B C D(23) 
502 " " " A A A A A B(2.5) 
503 5 l 0.4-0.7 15 A A A B C D(19) 
504 " " " A A A B C D(20) 
505 100 l 0.8-1.0 " A A A A A B(2.0) 
506 " " " A A A A A A(0.9) 
507 " " 10 A A B C D E(30) 
508 5 l 0.05-0.1 " A A B C C D(21) 
509 " " " A A B B C D(17) 
510 " " " A A A A A B(2.8) 
511 " " " A A A B C D(22) 
512 " " " A A B C D E(29) 
513 " " " A A A A A B(2.8) 
514 20 l 0.1-0.3 " A A B B C D(20) 
515 20 l 0.1-0.3 10 A A B C D E(30) 
516 " " " A A A A A B(1.2) 
517 " " " A A A A A B(3) 
518 " " " A A A B C D(20) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h 
EXAMPLE 14 
As shown in Table 14, for each experiment, a 5-l, 20-l, or 100-l stainless 
steel polymerizer was selected, and the inner wall surface of the 
polymerizer and the portions of the auxiliary equipment such as the 
stirrers which may come into contact with monomer were treated to have the 
surface roughness (Rmax) shown in the Table. For each experiment, as shown 
in Table 14, a conjugated .pi. bond compound was dissolved or dispersed in 
a solvent, optionally with the addition of an inorganic compound or a 
polymeric compound as shown in the Table to prepare a coating solution. 
The formulation ratio of the inorganic compound and the polymeric compound 
and the concentration of the conjugated .pi. bond compound in the coating 
solution are also shown in Table 14. The coating solution was applied on 
the inner wall surface of the polymerizer, etc. treated as mentioned 
above, dried at 90.degree. C. for 10 minutes and then thoroughly washed 
with water. 
Next, the thus coated polymerizer was charged with 148 parts of water, 1.85 
parts of sodium oleate, 48 parts of polybutadiene latex (solid content: 
45%), 33 parts of styrene monomer, 19 parts of acrylonitrile monomer, 0.15 
part of t-dodecyl mercaptan and 0.5 part of cumene hydroperoxide. After 
the mixture was heated to 65.degree. C., the polymerizer was further 
charged with 0.74 part of glucose, 0.0074 part of ferrous sulfate and 0.37 
part of sodium pyrophosphate, and polymerization was carried out under 
stirring at 65.degree. C. for 5 hours. After completion of polymerization, 
the polymer was taken out and the polymerizer was washed with water at a 
flow rate of 0.1 m.sup.3 /m.sup.2 hr for a period of time shown in Table 
14. The above operations from coating and charging to washing with water 
were conducted for each batch and this was repeated for a maximum of 10 
batches. 
In the same manner as in Example 1, scaling after completion of each of the 
1st, 2nd, 3rd, 5th and 7th batches was evaluated visually, and the amount 
of scales adhering (g/m.sup.2) was also measured after completion of the 
final batch. The results are also shown in Table 14. 
In Table 14, the Experiment numbers marked with an asterisk (*) indicate 
Comparative examples. In particular, Experiment Nos. 519 and 520 are 
examples in which the inner wall surface of the polymerizer was subjected 
to no treatment with any compound. 
TABLE 14 
__________________________________________________________________________ 
Coating Solution 
(1) Inorganic 
(a)/(b) 
Polymeric 
(a)/(c) 
(2) 
Exp. 
Conjugated .pi. bond compound (a) 
compound 
weight 
compound weight 
conc. 
Solvent 
No. Kind (Mixing ratio) 
(b) ratio (c) ratio % (Mixing 
__________________________________________________________________________ 
ratio) 
519* 
-- -- -- 
520* 
-- -- -- 
521* 
-- Fe(OH).sub.3 sol 
0/100 
-- 0.5 Water 
522* 
-- -- Nitrocellulose 
0/100 
0.5 Methanol 
523* 
4,5'-Biquinoline Fe(OH).sub.3 sol 
100/2 -- 0.5 Water/Methanol 
(20/80) 
524* 
Naphthol[1,2]furazane 
Colloidal silica 
100/100 
-- 0.5 Water/Methanol 
(50/50) 
525 4,5'-Biquinoline Fe(OH).sub.3 sol 
100/2 -- 0.5 Water/Methanol 
(20/80) 
526 Aminocinnoline -- -- 0.5 Methanol 
527 2,3-Diphenyl-4-quinazoline 
-- -- 0.7 Methanol 
528 Meldola's Blue/Chloropromazine 
Colloidal silica 
100/30 
-- 0.8 Water/Methanol 
(30/70) (10/90) 
529 5,10-Dihydrophenazine 
-- -- 0.5 Methanol 
530 Chlorothen citrate 
-- -- 0.7 Methanol 
531 Acronycin -- -- 0.9 Methanol 
532 .alpha.-Hydridone/Disperse Red 5 
-- -- 0.4 Acetone 
(50/50) 
533 2,3-Diphenylindole 
-- -- 1.0 Methanol 
534 Resazurin/1,3-Dioxyacridine 
-- Nitrocellulose 
100/30 
0.6 Methanol 
(20/80) 
535 Phthalazine -- -- 0.7 Methanol 
536 2,3-Diaminoquinoxaline 
-- -- 0.4 Methanol 
537 2,4-Diphenylthiophene 
-- -- 0.5 Methanol 
538 10,10-Diphenylphenoxathine 
-- -- " 0.9 Methanol 
539 Dimethylimino-.beta.-isoindigo 
Colloidal silica 
100/100 
-- 1.0 Water/Methanol 
(50/50) 
540 Naphtho[1,2]furazane 
Colloidal silica 
100/200 
-- 0.5 Water/Methanol 
(20/80) 
541 3-Chloro-10-ethylphenothiazine 
Fe(OH).sub.3 sol 
100/50 
-- 0.8 Water/Methanol 
(5/95) 
542 Allomycin/Solvent Black 5 
-- Polyvinyl acetate 
100/50 
0.5 Ethanol 
(50/50) 
543 Naphtho[2,3-c]thiophene 
-- -- 0.5 Methanol 
544 4,5-Diphenyloxazole 
-- -- 0.4 Methanol 
__________________________________________________________________________ 
(3) (4) 
Surface roughness of 
Time for washing 
Scaling 
(1) inner wall surface, etc. 
with water after 
Visual evaluation (Amount 
attached g/m.sup.2) 
Exp. 
Capacity of 
(Rmax) completion 
Batch No. 
No. 
Polymerizer 
.mu.m min. 1 2 3 5 7 10 
__________________________________________________________________________ 
519* 
5 l 10-13 45 H(1500) 
520* 
" 0.1-0.3 " H(800) 
521* 
" " " H(780) 
522* 
" " " H(750) 
523* 
" 10-13 " B E H(750) 
524* 
" " " B E H(700) 
525 
100 l 0.8-1.0 10 A A A A A B(3) 
526 
" " " A A A B C D(20) 
527 
" " " A A B C D H(100) 
528 
" " " A A A A A B(3) 
529 
5 l 0.05-0.1 " A A B B C D(21) 
530 
" " " A A B C D H(120) 
531 
5 l " " A A B B C D(17) 
532 
" " " A A A A B C(10) 
533 
" " 15 A A B C D E(30) 
534 
" " " A A A A A B(2.5) 
535 
" 0.4-0.7 " A A A B C D(22) 
536 
" " " A A B C D H(100) 
537 
" " " A A A B C D(20) 
538 
" " " A A A B C D(19) 
539 
20 l 0.1-0.3 5 A A A A A B(2.8) 
540 
" " " A A A A A B(2.5) 
541 
" " " A A A A A B(2.1) 
542 
" " " A A A A A B(2.3) 
543 
" " " A A B C D H(150) 
544 
" " " A A B B C D(20) 
__________________________________________________________________________ 
Notes: 
(1) *comparative examples 
(2) Conjugated .pi. bond compound concentration in coating solution. 
(3) Surface roughness of the inner wall surface of the polymerizer and th 
portions of the equipment thereof which may come into contact with the 
monomer. 
(4) Flow rate of water 0.1 m.sup.3 /m.sup.2 h