JPH0236602B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a vinyl polymer, and particularly to an improvement in preventing scale from adhering to the inner wall surface of a polymerization vessel during the polymerization process of a vinyl monomer. [Prior art and its problems] For example, in a method in which vinyl monomers such as vinyl chloride are subjected to suspension or emulsion polymerization in an aqueous medium in the presence of a polymerization catalyst, the inner wall surface of the polymerization vessel or stirring There is a problem in that polymer scale adheres to the parts of equipment attached to the polymerizer such as machines that come into contact with the monomer. If this scale adheres to the inner walls of the polymerization vessel, it will not only reduce the polymer yield and cooling capacity of the polymerization vessel, but also cause the adhering scale to peel off from the polymerization vessel and mix into the product, causing so-called "fish eyes." reduce the quality of Furthermore, in order to remove this adhered scale, it not only takes excessive effort and time, but also unreacted monomers are adsorbed in this scale, which has recently become an extremely serious problem. The disadvantage is that there is a risk of injury to the human body due to the monomers (vinyl chloride, etc.) A known method for preventing the adhesion of such polymer scale is to apply a chemical (hereinafter referred to as a "scale adhesion preventive agent") to the inner wall surface of the polymerization vessel, and various scale adhesion preventive agents have been proposed. It's here. Among various known methods, a method using dyes and/or pigments as a scale adhesion inhibitor is known as a particularly excellent method (Japanese Patent Publication No. 45
−30835). However, this method cannot effectively and reliably prevent scale adhesion in all cases, and is not always satisfactory. [Object of the Invention] In view of the drawbacks of the prior art described above, the object of the present invention is to provide a vinyl polymer that can reliably prevent scale adhesion during the polymerization process of one or more vinyl monomers. Our goal is to provide a manufacturing method for The present inventors have attempted to improve the method disclosed in Japanese Patent Publication No. 45-30835, and as a result, the surface roughness of dyes and/or pigments can be controlled when they are applied to the inner wall surface of a polymerization vessel as a scale adhesion prevention agent. It has been found that by doing so, scale adhesion can be effectively and reliably prevented. [Structure of the present invention - Means for solving problems] That is, according to the present invention, in a method for suspension polymerization or emulsion polymerization of one or more vinyl monomers in an aqueous medium, the inner wall surface of a polymerization vessel , and the surface roughness of the part of the polymerization vessel accessory equipment that comes into contact with the monomer is 1 μm or less,
A method for producing vinyl polymers is provided, which comprises coating the surfaces of the vinyl polymers with dyes and/or pigments in advance. In the present invention, "surface roughness" refers to JIS
Rmax (maximum height) specified in B0601. This surface roughness Rmax is determined by the stylus method (JIS
B0651), optical measurement method (JIS B0652), etc. Although it is not necessarily clear why scale adhesion can be effectively prevented by reducing the surface roughness of the surface to which the dye and/or pigment is applied to 1 μm or less as in the present invention, the surface roughness If it is larger than 1 μm, even if the dye/pigment is applied to the inner wall surface of the polymerization vessel, it will not be sufficiently effective as a scale adhesion preventive agent, and it will not be possible to effectively prevent scale adhesion. The method of the present invention can be applied regardless of the material of the inner wall surface of the polymerization vessel and other parts of the equipment attached to the polymerization vessel that come into contact with monomers. Polymerization vessels and attached equipment are usually made of materials such as stainless steel, carbon steel, Monel, and titanium, and some have glass-lined interior walls, but in the case of any of these materials, the surface roughness must be kept to 1 μm or less. By applying dyes/pigments in advance, scale adhesion can be effectively prevented. If the surface roughness of the polymerization vessel inner wall remains as it is,
If the surface roughness exceeds 5 μm, polish the surface using an appropriate polishing method to reduce the surface roughness to 5 μm or less before applying the dye/pigment. There are no particular restrictions on the polishing methods that can be used, and examples include buffing, electrolytic polishing, emery paper polishing, and the like. Dyes and pigments used as scale adhesion inhibitors in the method of the present invention include, for example, azo dyes and pigments such as monoazo and polyazo dyes and pigments, metal complex azo dyes and pigments, stilbene azo dyes, and thiazole azo dyes; anthraquinone derivatives; , anthraquinone dyes and pigments such as anthrone derivatives; indigoid dyes and pigments such as indigo derivatives and thioindigo derivatives; phthalocyanine dyes and pigments; carbonium dyes and pigments such as diphenylmethane dyes, triphenylmethane dyes and pigments, xanthene dyes and acridine dyes; azine dyes, quinoneimine dyes such as oxazine dyes and thiazine dyes; methine dyes such as polymethine or cyanine dyes; quinoline dyes; nitro dyes; benzoquinone and naphthoquinone dyes; naphthalimide dyes and pigments; perinone dyes; sulfur dyes; fluorescent dyes; azoic dyes and reactive dyes, which can be used singly or in combination of two or more. Among these exemplified dyes and pigments, particularly preferred are azine dyes, thiazine dyes, and oxazine dyes. More specific examples of these dyes and pigments are as follows. Examples of azo dyes and pigments include the following. As monoazo and polyazo dyes, e.g.
Basic Yellow 32, 34 and 36; Basic Orange 2, 32, 33 and 34; Basic Red
17, 18, 22, 23, 24, 32, 34, 38, 39 and 40;
Basic Violet 26 and 28; Basic Blue 58, 59, 64, 65, 66, 67 and 68; Basic Brown 1, 4, 11 and 12; Basic Black 8; Azoic Diazo Component 4,
21, 27 and 38; Disperse Yellow 3, 4,
5, 7, 8, 23, 50, 60, 64, 66, 71, 72, 76,
78 and 79; Disperse Orange 1, 3, 5,
13, 20, 21, 30, 32, 41, 43, 45, 46, 49, 50 and 51; Dispersed 1, 5, 7, 12,
13, 17, 43, 52, 54, 56, 58, 60, 72, 73, 74,
75, 76, 80, 82, 84, 88, 90, 97, 99, 101,
103, 113, 117, 122, 125, 126, 128, and
129; Disperse Violet 10, 24, 33, 38,
41, 43 and 96; Disperse Blue 85, 92, 94
and 106; Daspers Brown 3 and 5;
Disperse Black 1, 2, 10, 26, 27, 28,
29, 30 and 31; Solvent Yellow 2, 6,
14, 15, 16, 19, 21 and 56; Solvent Orange 1, 2, 5, 6, 14 and 45; Solvent Red 1, 3, 23, 24, 25, 27 and 30; Solvent Brown 3, 5 and 20 ; Solvent Black 3; Pigment Yellow 1, 2, 3, 4, 5,
6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23,
65, 73 and 83; Pigment Orange 1, 2,
5, 13, 14, 15, 16, 17, 24 and 31; pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21,
22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48,
49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63,
64, 68, 112, 114 and 163; Pigment Blue
25; Pigment Green 10; Pigment Brown 1 and 2; Pigment Black 1; Direct Yellow 1, 8, 11, 12, 24, 26, 27, 28,
33, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100
and 110; Direct Orange 1, 6, 8, 10,
26, 29, 39, 41, 49, 51, 57, 102 and 107; Direct Red 1, 2, 4, 13, 17, 20, 23,
24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75,
79, 80, 81, 83, 84, 89, 95, 99, 113, 197,
201, 218, 220, 224, 225, 226, 227, 228, 229,
230 and 231; Direct Violet 1, 7,
9, 12, 22, 35, 51, 63, 90, 94 and 98; Direct Blue 1, 2, 6, 8, 15, 22, 25, 71,
76, 77, 78, 80, 120, 123, 158, 160, 163,
165, 168, 192, 193, 194, 195, 196, 203, 207,
225, 236, 237, 246, 248 and 249; Direct Green 1, 6, 8, 28, 30, 31, 33, 37, 59,
63, 64 and 74; Direct Brown 1A, 2,
6, 25, 27, 44, 58, 59, 101, 106, 173, 194,
195, 209, 210 and 211; direct black
17, 19, 22, 32, 38, 51, 56, 71, 74, 75, 77,
94, 105, 106, 107, 108, 112, 113, 117, 118,
132, 133 and 146; acid yellow 11, 17,
19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 61,
70, 72, 75, 76, 78, 79, 110, 127, 131, 135,
141, 142, 164 and 165; acid orange 1,
7, 8, 10, 19, 20, 24, 28, 33, 41, 43, 45,
51, 56, 63, 64, 65, 67 and 95; Assured 1, 6, 8, 9, 13, 14, 18, 26, 27, 32,
35, 37, 42, 57, 75, 77, 85, 88, 89, 97, 106,
111, 114, 115, 117, 118, 119, 129, 130, 131,
133, 134, 138, 143, 145, 154, 155, 158, 168,
249, 252, 254, 257, 262, 265, 266, 274, 276,
282, 283 and 303; Assisted Bioreduced 7,
11, 97 and 106; acid blue 29, 60, 92,
113, 117 and 120; acid green 19, 20 and 48; acid brown 2, 4, 13, 14, 20,
53, 92, 100, 101, 236, 247, 266, 268, 276,
277, 282, 289, 301 and 302; acid black 1, 7, 24, 26, 29, 31, 44, 76, 77, 94,
109 and 110; Mordant Yellow 1, 3, 5,
23, 26, 30, 38 and 59; Mordant Orange 1, 4, 5, 6, 8, 29 and 37; Mordant Red 7, 9, 17, 19, 21, 26, 30, 63 and 89;
Mordant Violet 5 and 44; Mordant Blue 7, 13, 44, 75 and 76; Mordant Green 11, 15, 17 and 47; Mordant Brown 1, 14, 15, 19, 21, 33, 38, 40 , 52 and 87;
Mordant Black 1, 3, 7, 9, 11, 17,
26, 32, 38, 43, 44, 51, 54, 65, 75, 77, 84,
85, 86 and 87; Food Yellow 3 and 4; Food Red 7 and 9; Metal complex azo dyes such as Solvent Yellow 61 and 80; Solvent Orange 37, 40
and 44; Solvent Red 8, 21, 83, 84,
100, 109 and 121; Solvent Brown 37; Solvent Black 23; Acid Black 51, 52,
58, 60, 62, 63, 64, 67, 72, 107, 108, 112,
115, 118, 119, 121, 122, 123, 131, 132, 139,
140, 155, 156, 157, 158, 159 and 191; acid yellow 59, 98, 99, 111, 112, 114, 116,
118, 119, 128, 161, 162 and 163; acid orange 74, 80, 82, 85, 86, 87, 88, 122, 123 and 124; acid red 180, 183, 184, 186,
194, 198, 199, 209, 211, 215, 216, 217, 219,
256, 317, 318, 320, 321 and 322; Acid Blue 75 and 78; Acid Blue 151,
154, 158, 161, 166, 167, 168, 170, 171, 175,
184, 187, 192, 199, 229, 234 and 236; acid green 7, 12, 35, 43, 56, 57, 60, 61,
65, 73, 75, 76, 78 and 79; acid brown
19, 28, 30, 31, 39, 44, 45, 46, 48, 224,
225, 226, 231, 256, 257, 294, 295, 296, 297,
299 and 300; Direct Yellow 39; Direct Violet 47 and 48; Direct Blue
90, 98, 200, 201, 202 and 226; Direct Brown 95, 100, 112 and 170; Examples of stilbene azo dyes include Direct Black 62; Examples of thiazole azo dyes include Direct Red 9 and 11. It will be done. Next, examples of anthraquinone dyes and pigments include the following. Examples of anthraquinone derivatives include Basic Violet 25; Basic Blue 21, 22,
44, 45, 47, 54 and 60; Azoituku Diazo Component 36; Butt Yellow 2, 3, 10, 20,
22 and 33; Butt Orange 13 and 15; Butt Red 10, 13, 16, 31, 35 and 52; Butt Violet 13 and 21; Butt Blue 4, 6, 8,
12, 14, 64, 66, 67 and 72; butt green 8, 13, 43, 44 and 45; butt brown 1,
3, 22, 25, 39, 41, 44, 46, 57, 68, 72 and
73; Butt Black 8, 14, 20, 25, 27, 36,
56, 59 and 60; Dispers Orange 11; Dispers Red 4, 9, 11, 15, 53, 55, 65,
91, 92, 100, 104, 116 and 127; Disperse Violet 1, 4, 8, 23, 26, 28, 30 and
37; Dispers Blue 1, 3, 5, 6, 7,
20, 26, 27, 54, 55, 56, 60, 61, 62, 64, 72,
73, 75, 79, 81, 87, 90, 91, 97, 98, 99, 103,
104 and 105; Disperse Yellow 51; Solvent Violet 13 and 14; Solvent Blue
11, 12, 35 and 36; Solvent Green 3; Pigment Red 83 and 89; Pigment Blue
22; Assisted Violets 31, 34, 35, 41, 43,
47, 48, 51, 54, 66 and 68; acid blue
23, 25, 27, 40, 41, 43, 45, 54, 62, 72, 78,
80, 82, 112, 126, 127, 129, 130, 131, 138,
140, 142, 143, 182, 183, 203, 204 and 205;
Acid green 25, 27, 28, 36, 40, 41 and
44; Acid Brown 27; Acid Black 48 and 50; Mordant Red 3 and 11; Mordant Blue 8 and 48; Mordant Black 13; Pigment Violet 5; As anthrone derivatives, for example, Butt Yellow 1 and 4; Butt Orange 1, 2, 3, 4
and 9; butt violet 1, 9 and 10;
Bat Blue 18, 19 and 20; Bat Green 1, 2, 3 and 9; Bat Black 9, 13, 29
and 57; Buttred 13; Assured 80,
82 and 83, etc. In addition, examples of indigoid dyes and pigments include the following. Indigo derivatives include, for example, Vat Blue 1, 3, 5, 35 and 41; Redeployed Vat Blue 1; Pigment Violet 19 and
122; acid blue 74 and 102; solubilized bat blue 5 and 41; solubilized bat black 1; food blue 1; as a thioindigo derivative, for example bat orange 5; bat red 1, 2 and 61; bat violet 2 and 3; Pigment Red 87 and 88; Butt Brown 3, and the like. Furthermore, as a phthalocyanine dye/pigment, for example, Solvent Blue 55; Pigment Blue
Pigment Green 36, 37 and 38; Direct Blue 86 and 199; Mordant Blue 58. Next, examples of carbonium dyes and pigments include the following. Diphenylmethane dyes include, for example, Basic Yellow 2; triphenylmethane dyes include, for example, Basic Red 9; Basic Violet 1, 3;
and 14; Basic Blue 1, 5, 7, 19,
26, 28, 29, 40 and 41; Basic Green 1
and 4; Solvent Violet 8; Solvent Blue 2 and 73; Pigment Violet 3; Pigment Blue 1, 2 and 3; Pigment Green 1, 2 and 7; Direct Blue
41; Acid Violet 15 and 49; Acid Blue 1, 7, 9, 15, 22, 83, 90, 93, 100,
103 and 104; acid green 3, 9 and
16; Mordant Violet 1; Mordant Blue 1, 29 and 47; Food Violet 2; Food Blue 2; Food Green 2; As xanthene dyes, for example, Basic Red 1; Solvent Red 49; Pigment Red
81 and 90; pigment violet 1, 2 and 23; acid red 51, 52, 87, 92 and 94;
Modern Red 15 and 27; Hood Red 14;
Examples of acridine dyes include Basic Orange 14 and 15. Further, examples of quinone imine dyes include the following. As azine dyes, for example, Basic Black 2; Basic Black 2; Solvent Black 5 and 7; Acid Blue 59; Acid Black 2; As oxazine dyes, for example, Basic Blue 3; Direct Blue 106 and 108; Basic Yellow 1; Basic Blue 9, 24 and 25. Examples of methine dyes include the following: Examples of polymethine (or cyanine) dyes include Basic Yellow 11, 13, 14, 19, 21,
25, 28, 33 and 35; Basic orange 21 and 22; Basic orange 12, 13, 14, 15, 27,
29, 35, 36 and 37; basic violet 7, 15, 21 and 27. Examples of quinoline dyes include Basic Green 6; Disperse Yellow 54 and 56; Solvent Yellow 33; Acid Yellow 3. Examples of nitro dyes include Disperse Yellow 1, 33, 39, 42, 49 and 54; Acid Yellow 1. Examples of benzoquinone and naphthoquinone dyes include Disperse Blue 58 and 108;
Acid brown 103, 104, 106, 160, 161, 165
and 188. Examples of naphthalimide dyes and pigments include:
Pigment Red 123; Butt Violet 23 and 29; Acid Yellow 7. Perinone dyes include, for example, Butt Orange 7 and 15. Sulfur dyes include, for example, Solubilized Sulfur Yellow 2; Sulfur Yellow 4; Sulfur Orange 3; Sulfur Red 2, 3, 5 and 7; Solubilized Sulfur Blue 15; Sulfur Blue 2. ,3,4,
6, 7, 9 and 13; Sulfur Green 2,
3, 6, 14 and 27; Solubilized Sulfur Brown 1 and 51; Sulfur Brown 7, 12, 15 and 31; Sulfur Black 1,
2, 5, 6, 10, 11 and 15; butt yellow
35, 42 and 43; Batt Blue 43 and 56. Examples of fluorescent paints include fluorescent paints.
Brightening Agent 14, 22, 24, 30,
32, 37, 45, 52, 54, 55, 56, 84, 85, 86, 87,
90, 91, 104, 112, 121, 134, 135, 153, 162,
163, 164, 166, 167, 168, 169, 170, 171, 172,
173, 174, 175, 176 and 177. Examples of azoic dyes include azoic diazo components 17, 20, 22, 24, 26, 31,
35, 41, 47, 48, 109 and 121; Azoitsuku coupling components 2, 3, 4, 5, 7,
8, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20,
23, 26, 28, 29, 35, 36, 37, 41 and 108; Azoitsuku Brown 2, 7, 11 and 15; Azoitsuku Black 1 and 5; Azoitsuku Yellow 1 and 2; Azoitsuku Orange 2, 3 and 7; Azoic violet 1, 2, 6, 9, 16 and 24; Azoic violet 1, 2, 6, 7, 9 and
10; Azoitsuku Green 1 is mentioned. Examples of reactive dyes include Reactive Yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14,
15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37 and 42; Reactive Orange 1, 2, 4, 5,
7, 13, 14, 15, 16, 18, 20, 23 and 24; Reactive leads 1, 2, 3, 4, 5, 6, 7,
8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22,
23, 4, 28, 29, 31, 32, 33, 34, 35, 36, 37,
38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58,
59, 63 and 64; Reactive Violet 1,
2, 4, 5, 8, 9 and 10; Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14,
15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29,
31, 32, 33, 34, 37, 38, 39, 40, 41, 43, 44 and 46; Reactive Green 5, 6, 7 and 8; Reactive Brown 1, 2, 5, 7, 8,
9, 10, 11, 14 and 16; reactive blacks 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14 and 18. Furthermore, pigments include chrome yellow, zinc yellow,
Examples include inorganic pigments such as ZTO type zinc chromate, red lead, iron oxide powder, zinc white, aluminum powder, and zinc dust. The present invention also relates to a method of using a combination of (a) at least one of the dyes and pigments described above and (b) at least one inorganic compound as a scale adhesion inhibitor, and applying these to the inner wall surface of a polymerization vessel, etc. By reducing the surface roughness to 1 μm or less before coating, scale adhesion can be effectively and reliably prevented. Although inorganic compounds themselves do not have a scale adhesion prevention effect, when they are combined with dyes and pigments as in the present invention, the scale adhesion prevention effect of the dyes and pigments is surprisingly further improved.
However, it has been found that this effect can be effectively exhibited by controlling the surface roughness of the coated surface to 1 μm or less. If the surface roughness exceeds 1 μm, the scale adhesion prevention effect is insufficient and scale adhesion cannot be effectively prevented. As mentioned above, when applying a mixture of component (a) dyes/pigments and component (b) inorganic compounds, component (a) and (b)
The ratio of component (B) to 100 parts by weight of component (A) is
It is preferably 0.1 to 2000 parts by weight, and more preferably 1 to 1000 parts by weight. The inorganic compounds of this (b) component include orthosilicic acid, metasilicic acid, mesodisilicic acid, mesotrisilicic acid,
Mesotetrasilicic acid, sodium metasilicate, sodium orthosilicate, sodium disilicate, sodium tetrasilicate, potassium metasilicate, potassium hydrogen disilicate, lithium orthosilicate, hexalithium orthodisilicate, water glass, 12-Si Tungstic acid, iso-12-silicotungstic acid, 10-silicotungstic acid, potassium 12-silicotungstate, iso-12-potassium silicotungstate, 10
- Silicates or silicates such as potassium silicotungstate, sodium 12-siliotungstate, iso-12-sodium silicate, silicic molybdic acid, potassium silicomolybdate, sodium silicomolybdate; magnesium, calcium, barium, etc. alkaline earth metals, zinc group metals such as zinc, aluminum metals such as aluminum, tin group metals such as titanium and tin, iron group metals such as nickel, chromium group metals such as chromium and molybdenum, manganese such as manganese. Oxygen acid salts and acetates of metals selected from group metals, copper group metals such as copper and silver, platinum group metals such as platinum, etc.
Metal salts such as nitrates, hydroxides or halides; gold colloids, silver colloids, sulfur colloids, ferric hydroxide colloids, stannic acid colloids, silicic acid colloids, manganese dioxide colloids, molybdenum oxide colloids, Examples include inorganic colloids prepared by mechanical grinding, ultrasonic irradiation, electrical dispersion, and chemical methods, such as colloids of barium sulfate, colloids of vanadium pentoxide, colloids of aluminum hydroxide, and colloids of lithium silicate. Ru. Among these, silicates, silicate colloids, ferric hydroxide colloids, etc. are particularly preferred. In order to apply a composition containing a combination of dyes and/or pigments, and in some cases the above-mentioned inorganic compounds, to the inner wall surface of a polymerization vessel, etc., it can be applied as is or by dissolving or dispersing it in an appropriate solvent to prepare a coating solution. do it. The concentration of the scale inhibitor in the coating liquid is usually preferably 0.01% by weight or more. Solvents for preparing the coating solution include water, various organic solvents, such as gasoline, petroleum, benzine, mineral spirits, petroleum naphtha, VM&
Aliphatic hydrocarbons such as P. naphtha, decalin, tetralin, P-cymene; Aromatic hydrocarbons such as benzene, toluene, xylene; Trichlorethylene, perchlorethylene, chloroform, carbon tetrachloride, trichlorethylene, Halogenated hydrocarbons such as benzene bromide, benzene monochloride, benzene dichloride; amyl alcohol, ethyl alcohol, isopropyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, methyl amyl alcohol, benzyl Alcohols such as alcohol and butyl alcohol; acetone, acetonylacetone, diisobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone, methyl cyclohexanone, methyl dipropyl ketone, methyl ethyl ketone, methyl normal hexyl ketone, methyl isobutyl Ketone, methylpropylketone,
Ketones such as medityl oxide; Esters such as acetate esters, butyrate esters, propionate esters, and formate esters; Butyl lactate, isopropyl lactate, ethyl lactate,
Alcohol esters such as ethyl oxypropionate and diethyl maleate; Ketone esters such as ethyl acetoacetate and ethyl pyruvate; Ethers such as isopropyl ether, ethyl ether, diethyl carbitol, diethyl cellosolve, butyl ether; acetonyl methanol, Ketone alcohols such as diacetone alcohol, dihydroxylacetone, pyruvyl alcohol; isopropyl cellosolve, carbitol, glycidol, cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butyl cellosolve, methyl derbitol, methyl cellosolve, triethylene glycol monoethyl Ether alcohols such as ether; Ketone ethers such as acetal ethyl ether, acetonylmethanol ethyl ether, methyl ethoxyethyl ether; butyl carbitol acetate, butyl cellosolve acetate, carbitol acetate, cellosolve acetate, acetic acid 3
- Ester ethers such as methoxybutyl, methyl carbitol acetate, and methyl cellosolve acetate; etc. can be used. Methyl alcohol, ethyl alcohol, allyl alcohol, n which are highly compatible with water as organic solvents
- Alcohols such as propyl alcohol and isopropyl alcohol; Ketones such as acetone, acetonyl acetone and diacetone alcohol; ethylene glycol monomethyl acetate,
Esters such as acetic acid diethylene glycol methyl ether and acetic acid monoethyl ether; Ethers such as dioxane, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; Furans such as tetrahydrofuran and furfuryl alcohol; Acetonitrile, N,N-dimethylformamide, When using an aprotic solvent such as N,N-dimethylacetamide, etc., water should be added to the coating solution to the extent that it does not impede the solubility and dispersibility of the scale adhesion inhibitor. It is possible to improve safety during storage. When the anti-scaling agent used is a water-soluble sulfonic acid type or carboxylic acid type dye having a sulfonic acid group or a carboxyl group in the form of an alkali metal salt or ammonium salt, Japanese Patent Publication No. 1986- As described in No. 5442, water can be used as a solvent for dissolution, and there are safety and health advantages in that the solvent is non-toxic and harmless. When using water as a solvent, as described in Japanese Patent Publication No. 56-5444, an alcohol, preferably a _C3-6 monohydric alcohol such as n _- propyl alcohol or n-butyl alcohol, is added to the coating solution. Polymerization of the coating solution by adding alcohol, iso-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, iso-amyl alcohol, sec-amyl alcohol, sec-hexyl alcohol, etc. The wettability to the inner wall surface of the container can be improved. Also,
As described in Japanese Patent Publication No. 56-5442, an organic solvent that is compatible with water, such as an alcohol solvent, an ester solvent, a ketone solvent, etc., is applied to facilitate drying of the coating solution after application. It can also be added to liquids. When applying a coating solution containing dyes/pigments and, in some cases, further inorganic compounds, etc. to the inner wall surface of the polymerization vessel according to the method of the present invention, it is necessary to Various fixing agents can be used. The fixing agent can be used by mixing it with a coating solution containing a scale adhesion preventive agent, or by applying the fixing agent or its solution on the wall surface etc. before applying the scale adhesion preventive agent. There is a method of overcoating scale adhesion preventive agent, etc., and the type of scale adhesion preventive agent,
Select an appropriate method of use depending on the type of fixing agent.
As such a fixing agent, the following polymer compounds can be used. Olefin polymers, such as polyethylene, polyethylene sulfonic acid, polypropylene,
Poly(1-butene), polyisobutene, polycyclopentene, polycyclopentylethylene, polycyclohexylethylene, poly(3-cyclohexyl-1-propene), poly(4-cyclohexyl-1-butene), poly(5-cyclohexyl-
1-pentene), poly(cyclotrifluoroethylene), poly(tetrafluoroethylene); diene polymers, such as polyalene, polybutadiene, polyisoprene, polychloroprene, poly(1-methoxybutadiene), poly(2-methoxybutadiene);
-tert-butyl-1,3-butadiene), poly(cyclopentadiene), poly(1,3-cyclohexadiene), poly(dimethylfulvene), poly(4-vinyl-1-cyclohexane), poly(1,
5-hexadiene), poly(1,5-cyclooctadiene), poly(bicyclo-[2,2,1]-hepta-2,5-diene), poly(5,7-dimethyl-1,6-octadiene) ), poly(diallyl phthalate), poly(diallyldimethylsilane), poly(diallylphenylphosphine oxide); acetylene polymers, such as polyacetylene, poly(cyanoacetylene), poly((hydroxymethyl)acetylene), poly( butoxyacetylene), poly(phenylacetylene), poly(diphenyldiacetylene), poly(pyridylacetylene); aliphatic vinyl, vinylidene polymers, such as polyvinyl alcohol, polyallyl alcohol, poly(vinyl formal), Poly(vinyl acetal), poly(vinyl butyral), poly(vinyl isobutyral), poly(vinyl cyclohexanone ketal), poly(vinyl acetate),
Poly(vinyl chloroacetate), poly(vinyl isobutyrate), poly(vinyl pivalate), poly(vinyl n-caproate), poly(vinyl caprylate), poly(vinyl laurate), poly(vinyl palmitate), poly (vinyl benzoate), poly(vinyl sulfate), poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl bromide), poly(vinyl methyl ether), poly(vinyl ethyl ether), poly(vinyl n- propyl ether), poly(vinyl isopropyl ether), poly(vinyl n-butyl ether), poly(vinyl isobutyl ether),
Poly(vinyl tert-butyl ether), poly(vinyl neopentyl ether), poly(vinyl carbomethoxymethyl ether), poly(vinyl-2
-methoxyethyl ether), poly(vinyl-2)
-chloroethyl ether), poly(vinyl 2,2,
2-trifluoroethyl ether), poly(vinylbenzyl ether), poly(vinyl methyl ketone), poly(methyl isopropenyl ketone), poly(1-nitropropylene), poly(vinyl sulfofluoride), poly(vinyl sulfone) poly(vinyl diphenylphosphine oxide), poly(vinyl diphenylphosphine sulfide), poly(dimethyl-2-cyano-2-propene-1-phosphonate), poly(diethyl-2-cyano-2)
-propene-1-phosphonate), poly(malate anhydride); aromatic vinyl polymers, such as polystyrene, poly(α-methylstyrene), poly(4-chlorostyrene), poly(4-bromostyrene) , poly(dichlorostyrene), poly(4-methoxystyrene), poly(2,5-dimethoxystyrene),
poly(vinyl-bis(1-ethoxyethyl)hydroquinone), poly(4-vinyl-phthalic acid), poly(4-vinyl-phenylboric acid), poly(diphenyl-4-styrylphosphine oxide), poly(diphenyl- 4-styrylphosphine sulfide), poly(9-vinylanthracene), poly(4-vinyl-biphenyl), poly(acenaphthylene), polyindene;
-vinylcarbazole), poly(9- ^Δ5 -pentenylcarbazole), poly(9- ^Δ5 -hexenylcarbazole), poly(N-vinylpyrrolidone),
Poly(2-vinylpyridine), poly(4-vinylpyridine), poly(2-methyl-2-vinylpyridine), poly(2,4-dimethyl-6-vinyl-
S-triazine), poly(N-vinyl-1,2,
4-triazine), poly(N-vinylbenztriazole), poly(N-morpholinone-(3)), polycoumarone; acrylic and methacrylic polymers, such as polyacrylic acid, polymethacrylic acid, poly(methyl acrylate), Poly(ethyl acrylate), poly(butyl acrylate), poly(5-cyano-3-thia-phenyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate),
Poly(n-butyl methacrylate), poly(isobutyl methacrylate), poly(n-hexyl methacrylate), poly(2-ethylbutyl methacrylate), poly(n-octyl methacrylate), poly(n-lauryl methacrylate), poly(4 -(tert-butyl)phenyl methacrylate),
Poly(bornyl methacrylate), poly(β-(N
-carbasyl)ethyl methacrylate), poly(tert-butyl crotonate), polyacrylonitrile, polymethacrylonitrile, polyacrylamide, poly(N,N-dimethylacrylamide), poly(N-(1,1-dimethyl-3-oxobutyl) ) acrylamide), poly(acrylopiperidine), poly(acrylomorpholide), poly(9
-acrylic anhydride), polymethacrylamide, polyacrolein, poly(α-methylacrolein), poly(diacrylylmethane), poly(acrylic anhydride), poly(methacrylic anhydride); polyethers , for example, polyformaldehyde, polyacetaldehyde, poly(monochloroacetaldehyde), polychloral, polypropionaldehyde, polyacrolein, poly(2-
formyl-Δ ⁵ -dihydropyran), poly(trans-1,2-cyclohexanedicarboxaldehyde), poly(glutardialdehyde), poly(β
-methylglutardialdehyde), poly(β-phenylglutardialdehyde), poly(dimethylketene), polyacetone, poly(monobromoacetone), poly(7-oxa-bicyclo[2,2,
1] heptane), poly(3-phenoxylene), poly(2,6-xylenol), poly(ethylene oxide), poly(propylene oxide), poly(cyclopentene oxide), poly(cyclohexene oxide), poly(phenyl glycidyl ether) ), poly(1,2-di(epoxyethyl)benzene), poly(3,3-bis(chloromethyl)oxetane), poly(tetrahydrofuran); polysulfides, polysulfones, such as poly(thiocarboxyl fluoride), poly(ethylene dichloride-sodium tetrasulfide),
Poly(dichlorodiethyl ether-sodium disulfide), poly(dichlorodiethyl ether-sodium tetrasulfide), poly(phenylene sulfide), poly(ethylene sulfone), poly(propylene sulfone), poly(1- butenesulfone), poly(5-norbornenesulfone), poly(styrenesulfone), poly(1-pentinsulfone), poly(1-hexynesulfone), poly(1-heptinesulfone), poly(butadienesulfone) , poly(isoprene sulfone), poly(dimethylbutadiene sulfone), poly(1,5-hexadiene sulfone), poly(cis,cis-cyclo-octadiene sulfone), poly(norbornadiene sulfone); various addition polymers, e.g. , poly(methylene diisocyanate), poly(ethylene diisocyanate), poly(trimethylene diisocyanate),
poly(tetramethylene diisocyanate), poly(5-iminohydantoin), poly(perfluoroglutarodinitrile), poly(1-perfluorobutyryl)aziridine); formaldehyde resins, such as phenol-formaldehyde resin, melamine-formaldehyde Resin, urea-formaldehyde resin, aniline-formaldehyde resin, p-toluenesulfonamide-formaldehyde resin; polyesters, such as poly(11-oxyundecanoate), poly(hexamethylene succinate), poly(hexamethylene sebacate) ), poly(hexadecamethylene sebacate), poly(hexamethylene α,α′-dibutyl sebacate), poly(octamethylene cis-hexahydroterephthalate), poly(octamethylene trans-
hexahydroterephthalate), poly(hexamethylene maleate), poly(hexamethylene fumarate), poly(hexamethylene acetylene dicarboxylate), poly(ethylene terephthalate), poly(p-phenylene isophthalate), poly(4 , 4'-biphenylene isophthalate), poly(hexamethylene carbonate), poly(p-
phenylene carbonate), poly(m-phenylene carbonate), poly(4,4'-isopropylidene diphenylene carbonate), poly(4,
4'-(2-pentylene) diphenylene carbonate), poly(1,2-bis(hydroxymethyl)
carborane-adipic acid), poly(allyl sulfonate), poly(hydroquinone-aryloxy-phosphoryl dichloride), poly(hydroquinone-(chloromethyl)phosphoryl dichloride),
Poly(hydroquinone-(N-dimethyl)phosphoramidic acid) dichloride; polyamides such as poly(isocyanate), poly(vinyl isocyanate), poly(butyl isocyanate), poly(3-aminopropionic acid), poly( 6-aminopropionic acid), poly(11-aminoundecanoic acid), poly(hexamethyleneadipamide), poly(decamethyleneadipamide), poly(3,3'-(methylimino)bistrimethyleneadipamide) , poly(benzidine-isophthalic acid), poly(pyromellit dianhydride-aromatic diamine), poly(1,6-hexamethylene-bis(carboxyethyl) sulfide), poly(1,6-hexamethylenediamine-
benzene-1,3-bis-sulfonic acid chloride), poly(trans-2,5-dimethyl-piperazine-4,4'-sulfonyl-dibenzoyl chloride), poly(bis(3-aminopropyl)phenyl phosphine-adipine) acid), poly(bis(3-aminopropyl)phenyl phosphine)
terephthalic acid), poly(bis(3-aminopropyl)methyl phosphine oxide-adipic acid),
poly(bis(3-aminopropyl)n-octylphosphine-adipic acid), poly(bis(3-aminopropyl)phenylphosphine oxide-adipic acid), poly(hexamethylenediamine-bis(2-carboxyethylene) ) phenylphosphine oxide), poly(hexamethylene diamine)
bis(p-carboxyphenyl)phenylphosphine oxide), poly(piperazine-bis(2-
(carboxyethyl)-phenylphosphine oxide); polyurea, polyurethanes, such as polyurea, poly(1,10-decamethylenediamine)
1,6-hexamethylene-bis-ethylurethane), poly(diphenylmethane-4,4'-diisocyanate-4,4'-diphenylmethane), poly(toluene-2,4-diisocyanate-N,
N'-bis(trimethylsilyl)-p,p'-diaminodiphenyl ether, polyurethane, polyurethane poly(propylene oxide) basis; various linear condensation polymers, e.g. poly(diethylcarbodiimide), poly(diallyl); carbodiimide), poly(di-n-butylcarbodiimide), poly(methylisopropylcarbodiimide), poly(di-n-hexylcarbodiimide),
Poly(diphenylcarbodiimide), poly(4,
4′-diphenylenemethane-carbodiimide), poly(hexamethylenecarbodiimide), poly(1,
3-xylylenecarbodiimide), poly(3-methyl-1,4-phenylenecarbodiimide), poly(2,2'-dimethyl-biphenylenecarbodiimide), poly(2,2'-dimethoxy-biphenylenecarbodiimide) ), poly(1,5-naphthylenecarbodiimide), poly(adipyl dihydrazide-succinoyl chloride), poly(adipyl dihydrazide-isophthaloyl chloride), poly(isophthalic dihydrazide-terephthaloyl chloride), Poly(2,5-dimethylbenzylene), poly(p-xylylene), poly(2,5-dimethylxylylene), poly(2,5-dimethoxy-p-xylylene), poly(p-xylylidene),
Poly(α-cyano-m-xylylidine), poly(α-cyano-p-xylylidine), poly(nitrophenylene), poly(tetramethyl-p-phenylene dimethylene), poly(2,5-dihydroxy-p- phenylene dimethylene), poly(4,4'-
oxydiphenylene dimethylene), poly(2,5
-dimethoxy-p-phenylene dimethylene); Heterocyclic condensation polymers, such as poly(benzimidazole), poly(alkylene-5,5'-
dibenzimidazole), poly(arylene-5,
5'-dibenzimidazole), poly(pyromellituimide), poly(benzoxazole), poly(oxadiazole), poly(oxadiazolidine), poly(dithiazole), poly(benzothiazole), poly((1, (4-xylylenyl)-2-methylpiperazine), poly(quinoxaline), poly(S-triazinyleneimide); natural polymers, modified natural polymers, such as natural rubber, cyclized rubber, hydrochloric acid rubber, chlorinated rubber Rubber, gutta percha, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, allyl cellulose, benzyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose triformate, cellulose acetate, cellulose triacetate, cellulose tripropionate, Cellulose tributyrate, cellulose tricaproate, cellulose tricarbanilate, cellulose nitrate, cellulose trinitrate, starch, amylose, amylose acetate, amylose carbanilate, amylopectin, alginic acid, chitin, glycogen, gum arabic, gum tragacanth, heparin , pectin, rosin, copal, sierracus, casein,
Collagen (Calf-skin), Collagen (ichthyocol), Gelatin, Peanut protein, Soy protein, Nuclear protein (calf
thymus), nuclear protein (sperm of
seaurchin), poly(sarcosine), sericin, silk, wool, zein, polyadenylic acid, deoxyribonucleic acid, ribonucleic acid; polysiloxanes, such as polysiloxane,
Polydimethylsiloxane; Organometallic polymers, such as poly(bis(imidazolate)-metal()), poly(aluminum triisopropylate-ethylenediamine);
and inorganic polymers, such as polymetaphosphate,
etc. By the method of the present invention, dyes/pigments and, in some cases, further inorganic compounds are applied to the inner wall surface of the polymerization vessel and the areas of the polymerization vessel accessory equipment where scale is likely to adhere, that is, the areas where monomers come into contact during the polymerization process (contact). (including areas where it is likely to occur). The monomers come into contact with the equipment attached to the polymerization reactor:
Examples include stirring blades, stirring shafts, condensers, headers, buffers, search coils, bolts, nuts, etc. There are no particular restrictions on the method of applying the scale adhesion preventive agent to the inner wall surface of the polymerization vessel, such as brush coating, spray coating, filling the polymerization vessel with the coating solution and then drawing it out, and other methods. -No. 61001, No. 55-36288, Special Publication 1987-
The automatic coating methods described in No. 501116, No. 56-501117, JP-A-59-11303, etc. can be used. The method of the present invention can be applied to the polymerization of various vinyl monomers in an aqueous medium, and typical examples of such polymerization include vinyl halides such as vinyl chloride, or vinyl monomers mainly composed of vinyl chloride. Production of monomer mixtures such as vinyl chloride-vinyl acetate by suspension polymerization or emulsion polymerization; Production of beads and latex of polymers such as polystyrene, polymethyl methacrylate, and polyacrylonitrile; SBR, NBR, CR, IR,
Production of synthetic rubbers such as IIR (these synthetic rubbers are usually produced by emulsion polymerization); production of ABS resins, etc. The type of polymerization may be suspension polymerization or emulsion polymerization. Vinyl monomers that can be subjected to polymerization include vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, methacrylic acid or their esters or salts, maleic acid or fumaric acid, and Examples thereof include esters or anhydrides thereof, diene monomers such as butadiene, chloroprene, and isoprene, as well as styrene, acrylonitrile, vinylidene halides, and vinyl ethers. When one or more of these monomers are polymerized, the purpose of preventing scale can be effectively achieved regardless of the polymerization type or polymerization recipe. In these suspension polymerizations and emulsion polymerizations, polymerization catalysts such as t-butyl peroxyneodecanate, di-2-ethylhexyl peroxydicarbonate, 3,5,5-trimethylhexanoel peroxide, α- Cumyl peroxy neodecanoate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl peroxy pivalate, di-2-ethoxyethyl peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-
Organic peroxides such as dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate and acetylcyclohexyl peroxide, α,α′-azobisisobutyronitrile, α,
Azo catalysts such as α'-azobis-2,4-dimethylvaleronitrile, water-soluble peroxides such as potassium persulfate, ammonium persulfate, and the like are used. Further, as dispersants, for example, partially saponified polyvinyl acetate, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropyl methylcellulose, natural and synthetic polymer compounds such as gelatin, etc. Suspending agents; emulsifiers such as nonionic emulsifiers such as sorbitan monolaurate and sorbitan triolate, anionic emulsifiers such as sodium lauryl sulfonate and sodium alkylbenzene sulfonate, and other additives such as calcium carbonate,
Fillers such as titanium oxide, stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, dioctyltin mercaptide,
Lubricants such as rice wax, stearic acid, and cetyl alcohol, plasticizers such as DOD and DBP, chain transfer agents such as trichlorethylene and mercaptans, and PH regulators are added to the polymerization system. According to the method of the present invention, scale adhesion can be effectively prevented in any polymerization system, regardless of the types of catalysts, dispersants, and additives. [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the scope of the present invention is not limited thereto. Note that parts represent parts by weight unless otherwise specified. Example 1 As shown in Table 1, the internal volume for each experiment was
A 100, 1000, 2000, 40M ³ or 130M ³ stainless steel polymerization vessel was selected, and its inner wall surface was adjusted to the surface roughness (Rmax) shown in the table. The surface roughness was adjusted by buffing using an abrasive with an appropriate particle size. In particular, in the experiment corresponding to the example, while measuring the surface roughness of the inner wall surface using the optical measurement method specified in JIS B0652, the front surface of the inner wall surface was first buffed with an abrasive with a grain size of No. 150, and then
Similar buffing was performed using abrasives of No. 200, No. 250, and No. 350 in this order in stages, so that the surface roughness was 1 μm or less over the entire inner wall surface. For each experiment, a coating solution was prepared by dissolving or dispersing dyes or pigments in a solvent as shown in Table 1, and adding inorganic compounds and polymeric compounds shown in the same table as necessary. Table 1 also shows the blending ratios of the inorganic compounds and polymer compounds and the dye/pigment concentrations of the coating solutions for each experiment. The coating solution prepared in this way is
As mentioned above, it was applied to the inner wall of the polymerization vessel having a predetermined surface roughness and to the parts that come into contact with the monomer, such as the stirrer, dried at 80°C for 10 minutes, and then thoroughly washed with water. Next, 100 parts of vinyl chloride monomer, 200 parts of ion-exchanged water, 0.022 parts of partially saponified polyvinyl alcohol, 0.028 parts of hydroxymethylcellulose, and 0.03 parts of t-butyl peroxyneodecanate were added to the polymerization vessel coated in this way. The mixture was charged and polymerized at 52°C for 7 hours. After the polymerization was completed, the polymer was taken out, and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr for the time shown in Table 1. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 200 batches. In addition, the state of scale adhesion after each batch of 10th, 30th, 50th, 100th, 150th, and 200th batches was visually evaluated according to the following criteria, and after the final batch, the amount of scale adhesion (g/m ² ) was evaluated. was also measured. These results are also shown in Table 1. A: No scale adhesion B: A few percent of sand-like scale adhesion C: Partially thin scale adhesion (adhesion rate 10%)
Degree) D: Partially thick scale adhesion (approximately 10% adhesion rate) E: Partially thin scale adhesion (adhesion rate 50%)
degree) F: Partially thick scale adhesion (approximately 50% adhesion rate) G: Thin scale adhesion to the entire surface H: Thick scale adhesion to the entire surface In addition, experiment numbers marked with * in Table 1 are for comparison. Indicates that it is an example. In particular, Experiments Nos. 1 to 6 are examples in which no compound was applied to the inner wall surface of the polymerization vessel. In addition, the coating solution for Experiment Nos. 23 and 57 was prepared by dissolving 1 part of sodium sulfide in 100 parts of water, adding 0.5 part of dye, and adding 80 parts of dye.
Prepared by heating at ℃ for 30 minutes.

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 2 As shown in Table 2, the internal volume for each experiment
A 100, 1000, 2000, 40M ³ or 130M ³ stainless steel polymerization vessel was selected, and its inner wall surface was adjusted to the surface roughness (Rmax) shown in the table in the same manner as in Example 1. For each experiment, a coating solution was prepared by dissolving or dispersing dyes or pigments in a solvent as shown in Table 2, and adding inorganic compounds and polymeric compounds shown in the same table as necessary. The blending ratio of inorganic compounds and polymer compounds in each experiment, and the dye and
Pigment concentrations are also shown in Table 2. The coating liquid thus prepared was applied to the inner wall surface of the polymerization vessel, which had a predetermined surface roughness as described above, and to the parts that come into contact with the monomer, such as the stirrer, dried at 80° C. for 10 minutes, and then thoroughly washed with water. Next, 100 parts of vinyl chloride monomer, 200 parts of ion-exchanged water, 0.125 parts of hydroxypropyl methylcellulose, 0.125 parts of sorbitan monolaurate, and α,α′-azobis-
0.025 part of 2,4-dimethylvaleronitrile was added and polymerized at 52°C for 10 hours. After the polymerization was completed, the polymer was taken out, and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr for the time shown in Table 2. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 200 batches. In the same manner as in Example 1, the 10th, 30th, 50th, 100th,
The state of scale adhesion after the 150th and 200th batches was visually evaluated, and the amount of scale adhesion (g/m ² ) was also measured after the final batch. These results are also shown in Table 2. Note that the experiment numbers marked with * in Table 2 indicate comparative examples. In particular, Experiment Nos. 65 and 66 are examples in which no compound was applied to the inner wall surface of the polymerization vessel. In addition, the coating solution for Experiment Nos. 105 and 133 was prepared by dissolving 1 part of sodium sulfide in 100 parts of water and adding 0.5 part of dye.
It was prepared by heating at 80°C for 30 minutes.

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 3 As shown in Table 3, the internal volume for each experiment
A 100, 1000, 2000, 40M, or 130M stainless steel polymerization vessel was selected, and its inner wall surface was adjusted to the surface roughness (Rmax) shown in the table in the same manner as in Example 1. For each experiment, dyes or pigments were dissolved or dispersed in a solvent as shown in Table 3, and inorganic compounds and polymeric compounds shown in the table were added as necessary to prepare a coating solution. The blending ratio of inorganic compounds and polymer compounds in each experiment, and the dye and
Pigment concentrations are also shown in Table 3. The coating liquid thus prepared was applied to the inner wall surface of the polymerization vessel, which had a predetermined surface roughness as described above, and to the parts that come into contact with the monomer, such as the stirrer, dried at 80° C. for 10 minutes, and then thoroughly washed with water. Next, 80 parts of vinyl chloride monomer, 20 parts of vinyl acetate monomer, 200 parts of ion exchange water, 0.3 part of gelatin, 1 part of trichlene,
and 0.175 parts of lauroyl peroxide were added and polymerized at 70°C for 6 hours. After the polymerization was completed, the polymer was taken out and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr for the time shown in Table 3. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 200 batches. In the same manner as in Example 1, the 10th, 30th, 50th, 100th,
The state of scale adhesion after the 150th and 200th batches was visually evaluated, and the amount of scale adhesion (g/m ² ) was also measured after the final batch. These results are also shown in Table 3. Note that the experiment numbers marked with * in Table 3 indicate comparative examples. In particular, Experiment Nos. 136 and 137 are examples in which no compound was applied to the inner wall surface of the polymerization vessel. In addition, the coating solution in Experiment Nos. 177 and 178 was 100% water.
Dissolve 1 part of soda sulfide in 1 part, add 0.5 part of dye,
It was prepared by heating at 80°C for 30 minutes.

【table】

【table】

【table】

【table】

[Table] Example 4 As shown in Table 4, the internal volume for each experiment
A stainless steel polymerization vessel of 100, 1000, 2000, 40M ³ or 130M ³ was selected, and its inner wall surface was prepared in Example 1.
The surface roughness (Rmax) shown in the same table was prepared in the same manner as above. For each experiment, dyes or pigments were dissolved or dispersed in a solvent as shown in Table 4, and inorganic compounds and polymeric compounds shown in the same table were added as necessary to prepare a coating solution. The blending ratio of inorganic compounds and polymer compounds in each experiment, and the dye and
Pigment concentrations are also shown in Table 4. The coating liquid thus prepared was applied to the inner wall surface of the polymerization vessel, which had a predetermined surface roughness as described above, and to the parts that come into contact with the monomer, such as the stirrer, dried at 80° C. for 10 minutes, and then thoroughly washed with water. Next, 100 parts of vinyl chloride monomer, 200 parts of ion-exchanged water, 0.02 parts of partially saponified polyvinyl alcohol, 0.03 parts of hydroxymethyl cellulose, and 0.04 parts of di-2-ethylhexyl peroxydicarbonate were added to the polymerization vessel coated in this manner. was charged and polymerized at 57°C for 7 hours. After the polymerization is completed, the polymerized product is taken out and the interior of the polymerization vessel is flushed with water at a flow rate of 0.1 m ³ /m ² hr.
Washing with water was carried out for the time indicated in the table. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 200 batches. In the same manner as in Example 1, the 10th, 30th, 50th, 100th,
The state of scale adhesion after the 150th and 200th batches was visually evaluated, and the amount of scale adhesion (g/m ² ) was also measured after the final batch. Also, the 10th, 30th, 50th, 100th, 150th and
The number of fibers of the product obtained from the 200th batch of polymer was measured as follows. Polymer obtained by dehydrating and drying slurry after polymerization
100 parts, DOP50 parts, dibutyltin dilaurate 1
A mixture of 1 part of cetyl alcohol, 0.25 part of titanium oxide, and 0.05 part of carbon black was kneaded for 7 minutes with two rolls at 150°C to form a sheet with a thickness of 0.2 mm, and this was coated with 100 cm ² by a light transmission method.
The number of fisheyes contained in a winning sheet was investigated. The above measurement results are shown in Table 4. Note that the experiment numbers marked with * in Table 4 indicate comparative examples. Experiment Nos. 181 and 182 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

【table】

[Table] Example 5 As shown in Table 5, for each experiment, the internal volume 5
, 20, or 100 were selected, and their inner wall surfaces were adjusted to the surface roughness (Rmax) shown in the table in the same manner as in Example 1. For each experiment, dyes or pigments were dissolved or dispersed in a solvent as shown in Table 5, and inorganic compounds and polymeric compounds shown in the table were added as necessary to prepare a coating solution. Table 5 also shows the blending ratios of the inorganic compounds and polymer compounds and the dye/pigment concentrations of the coating solutions for each experiment. The coating liquid thus prepared was applied to the inner wall surface of the polymerization vessel, which had a predetermined surface roughness as described above, and to the parts such as the stirrer that come in contact with the monomer, and was heated at 90°C for 10 minutes.
After drying for a minute, it was thoroughly washed with water. Next, 75 parts of styrene, 25 parts of acrylonitrile, and ion-exchanged water were added to the polymerization vessel coated in this way.
120 parts, tricalcium phosphate 0.5 part, sodium dodecylbenzenesulfonate 0.01 part, and lauroyl peroxide 0.4 part were charged and polymerized at 90°C for 8 hours. After the polymerization was completed, the polymer was taken out and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr for the time shown in Table 5. The above operations from coating and preparation to washing with water after polymerization are repeated for each batch to achieve the best results.
The experiment was repeated in 10 batches. Using the same method as in Example 1, the state of scale adhesion after the first, second, third, fifth, and seventh batches was visually evaluated, and the amount of scale adhesion (g/m ² ) was also measured. These results are also shown in Table 5. Note that the experiment numbers marked with * in Table 5 indicate comparative examples. In particular, Experiment Nos. 190 and 191 are examples in which no compound was applied to the inner wall surface of the polymerization vessel. The coating solution for Experiment No. 215 was prepared by dissolving 1 part of Sozo sulfide in 100 parts of water, adding 0.5 part of dye, and heating it at 80°C.
It was prepared by heating for 30 minutes.

【table】

【table】

[Table] Example 6 As shown in Table 6, for each experiment, the internal volume 5
, 20, or 100 stainless steel polymerization vessels were selected, and their inner wall surfaces were adjusted to the surface roughness (Rmax) shown in the table in the same manner as in Example 1. For each experiment, dyes or pigments were dissolved or dispersed in a solvent as shown in Table 6, and inorganic compounds and polymeric compounds shown in the same table were added as necessary to prepare a coating solution. Table 6 also shows the blending ratio of inorganic compounds and polymer compounds and the dye/pigment concentration of the coating solution for each experiment. The coating liquid thus prepared was applied to the inner wall surface of the polymerization vessel, which had a predetermined surface roughness as described above, and to the parts such as the stirrer that come in contact with the monomer, and was heated at 90°C for 10 minutes.
After drying for a minute, it was thoroughly washed with water. Next, 100 parts of styrene monomer, 250 parts of ion-exchanged water, 0.2 parts of polyvinyl alcohol, and t-dodecyl mercaptan were added to the polymerization vessel coated in this manner.
0.75 part of lauroyl peroxide and 0.5 part of lauroyl peroxide were charged, and the internal temperature was kept at 70°C for 5 hours with stirring, then the temperature was raised from 70°C to 80°C over 2 hours, and then at 80°C for 1 hour.
Polymerized for hours. After the polymerization is completed, take out the polymerized product,
The inside of the polymerization vessel was washed with water at a flow rate of 0.1 m ³ /m ² ·hr for the time shown in Table 6. The above operations from coating and preparation to washing with water after polymerization were repeated for each batch, up to a maximum of 10 batches. The operation up to washing with water after polymerization was performed for each batch, and the process was repeated for an optimal 10 batches. Using the same method as in Example 1, the state of scale adhesion after the first, second, third, fifth, and seventh batches was visually evaluated, and the amount of scale adhesion (g/m ² ) was also measured. These results are also shown in Table 6. Note that the experiment numbers marked with * in Table 6 indicate comparative examples. In particular, Experiment Nos. 219 and 220 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

【table】

【table】

[Table] Example 7 As shown in Table 7, for each experiment, the internal volume 5
, 20, or 100 steel polymerization vessels were selected, and their inner wall surfaces were adjusted to the surface roughness (Rmax) shown in the table in the same manner as in Example 1. For each experiment, dyes or pigments were dissolved or dispersed in a solvent as shown in Table 7, and inorganic compounds and polymeric compounds shown in the table were added as necessary to prepare a coating solution. Table 7 also shows the blending ratio of inorganic compounds and polymer compounds and the dye/pigment concentration of the coating solution for each experiment. The coating liquid thus prepared was applied to the inner wall surface of the polymerization vessel, which had a predetermined surface roughness as described above, and to the parts that come into contact with the monomer, such as the stirrer, dried at 90° C. for 10 minutes, and then thoroughly washed with water. Next, add 148 ml of water into the polymerization vessel coated in this way.
parts, sodium oleate 1.85 parts, polybutadiene latex 48 parts (solid content 45%), styrene monomer 33 parts
19 parts of acrylonitrile monomer, 0.15 parts of t-dodecyl mercaptan, and 0.5 parts of cumene hydroperoxide, and 0.74 parts of glucose at an internal temperature of 65°C.
0.0074 part of ferrous sulfate and 0.37 part of sodium pyrophosphate were charged, and polymerization was carried out at 65°C for 5 hours with stirring. After polymerization is complete, take out the polymer and clean the inside of the polymerization vessel.
Washing was carried out with water at a flow rate of 0.1 m ³ /m ² ·hr for the time listed in Table 7. The above operations from coating and preparation to washing with water after polymerization are performed for each batch, and up to 10
It was repeated in batches. Using the same method as in Example 1, the state of scale adhesion after the first, second, third, fifth, and seventh batches was visually evaluated, and the amount of scale adhesion (g/m ² ) was also measured. These results are also shown in Table 7. Note that the experiment numbers marked with * in Table 7 are comparative examples. In particular, Experiment Nos. 248 and 249 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

【table】

【table】

[Table] Comparative Example 1 The inner wall surface of a polymerization vessel with an internal volume of 1000 was first buffed with an abrasive with a grain size of 150, and then
Buffed with 200 grit abrasive. This polishing was carried out without particularly setting a target value for surface roughness, and after polishing, the surface roughness was measured in the same manner as in Example 1.
The surface roughness was measured to be 4.2-7.5 μm. In Experiment Nos. 277 to 279 (comparative examples), Experiment No. 60 of Example 1, Experiment No. 126 of Example 2, and and the operation of Experiment No. 148 of Example 3,
repeated. The results are shown in Table 8.

[Table] [Effects of the Invention] As is clear from the above Examples and Comparative Examples, according to the present invention, the surface roughness of the inner wall of the polymerization vessel and other areas where monomers come into contact during the polymerization process was reduced to 5 μm.
As described below, by applying dyes and/or pigments thereon, the scale-preventing action of the dyes and pigments can be reliably and strongly brought out, and scale adhesion can be effectively prevented.
In addition, when inorganic compounds are used in combination with dyes and pigments, the scale prevention effect is improved, but in this case as well, this effect can be made effective and reliable by keeping the surface roughness of the inner wall of the polymerization vessel to 5 μm or less. . Therefore, the labor and time for removing scale can be saved, the polymerization vessel can be used continuously, and the operating rate can be improved. Furthermore, the cooling capacity of the polymerization vessel can be maintained constant and there is no risk of scale being mixed into the product, improving the quality of the product polymer.

Claims (1)

[Scope of Claims] 1. In a method of suspension polymerization or emulsion polymerization of one or more vinyl monomers in an aqueous medium, the inner wall surface of the polymerization vessel and the monomers in the equipment attached to the polymerization vessel are in contact with each other. The surface roughness of the part to be removed is 1μm or less,
A method for producing vinyl polymers, which comprises applying dyes and/or pigments to their surfaces in advance. 2. In a method of suspension polymerization or emulsion polymerization of one or more vinyl monomers in an aqueous medium, the surface roughness of the inner wall surface of the polymerization vessel and the parts of the equipment attached to the polymerization vessel that come into contact with the monomers must be checked. 1μm or less,
A method for producing vinyl polymers, which comprises applying (a) at least one dye or pigment and (b) at least one inorganic compound to the surface of the vinyl polymer in advance.