JPS6151001A - Production of vinyl polymer - Google Patents

Abstract

PURPOSE:To prevent effectively deposition of vinyl polymer scale, by applying a dye and/or a pigment to the inside wall or monomer contact areas of a polymerizer having a specified surface roughness. CONSTITUTION:A mixture comprising 100pts.wt. dye (e.g., Basic Yellow 32) and/ or pigment (e.g., Pigment Yellow 1) and 0.1-2,000pts.wt. inorganic compound (e.g., colloidal silica) is applied to the inside wall of a polymerizer and monomer contact areas of the related devicer (said inside wall and said areas having surface roughness <=5mum). One or more vinyl monomers are placed in the polymerizer and suspension-polymerized or emulsion-polymerized in an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] 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.

C Prior Art and Related Issues J For example, in the method of rIAW1 polymerization or emulsion polymerization of vinyl monomers such as vinyl chloride monomers in an aqueous medium in the presence of a polymerization catalyst, the There is a problem in that polymer scale adheres to the walls and portions of equipment attached to the polymerization vessel such as the stirrer that come into contact with the monomer. If this scale adheres to the inner walls of the polymerization vessel, etc., 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. Decrease the quality of the product. Furthermore, removing this attached scale not only requires excessive labor and time, but also unreacted monomers are absorbed into this scale, which has recently become a very serious problem. monomer (1, if there is a risk of human injury due to vinyl chloride)
) is at a disadvantage.

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 has been. Among various known methods, a method using dyes and/or pigments as an anti-scaling agent is known as a particularly excellent method (Japanese Patent Publication No. 30835/1983). 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. Dedicated to providing manufacturing methods.

The inventors have attempted to improve the method disclosed in Japanese Patent Publication No. 45-30835, and as a result, when applying dyes and/or pigments to the inner wall surface of a polymerization vessel as a scale adhesion prevention agent, the surface roughness of the dyes and/or pigments can be reduced. It has been found that scale adhesion can be effectively and reliably prevented by controlling.

[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 5 μm or less, preferably 2 μm or less, and the surface is coated with dye and/or pigment in advance. A method of making a based polymer is provided.

"Surface roughness" in the present invention refers to 0SB 060
1 means Rmax (maximum height). This surface roughness Rmax is determined by the stylus method (JIS B
0651), optical degree measurement method (JIS B 06
52).

It is not necessarily clear why scale adhesion can be effectively prevented by setting the surface roughness of the surface to which dyes and/or pigments are applied to 5 mm or less as in the present invention. However, if the surface roughness is larger than 5 μm, even if the dye/pigment is applied to the inner wall surface of the polymerization vessel, it will not be effective as a scale adhesion preventive agent, and it will not be possible to effectively prevent scale adhesion. Can not.

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 polymerization vessel bending equipment that come in contact with monomers. Polymerization vessels and auxiliary equipment are usually made of materials such as stainless steel, carbon steel, Monel, and titanium, and some have glass-lined interior walls, or if they are made of any of these materials, the surface roughness must be By applying dyes/pigments so that the thickness is less than m, scale adhesion can be effectively prevented.

If the surface roughness of the inner wall surface of the polymerization vessel is more than 5 mm as it is, it is polished by an appropriate polishing method to reduce the surface roughness to 5 mm or less before applying the dye/pigment. There are no particular restrictions on the polishing methods that can be used, and examples include methods such as puff polishing, electric M polishing, and emery paper polishing.

Dyes and pigments used as scale adhesion inhibitors in the method of the present invention include, for example, monoazo and polyazo dyes/pigments, azo dyes/pigments such as metal 2vi salt azo dyes/pigments, stilbene azo dyes, thiazole azo dyes; anthraquinones; Anthraquinone dyes and pigments such as derivatives and anthrone derivatives; Indigoid dyes and pigments such as indigo derivatives and thioindigo derivatives; Phthalocyanine dyes and pigments; Carbonium dyes such as diphenylmethane dyes and pigments, Santen dyes, and macridine dyes; Pigments; Quinoneimine dyes such as azine, oxazine and thiazine dyes; Methine dyes such as polymethine or cyanine dyes; Ki/phosphorous dyes: Nitro dyes: Henzoquinone and naphthoquinone dyes; Nuclimide dyes and pigments; Perinone dyes; Sulfur dyes: Fluorescence Dyes; azoic dyes; and reactive dyes can be mentioned, and these 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. Specific examples of these dyes and pigments are as follows.

1 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 17.18.22.23.24.32.34.38.3
8 oyobi 4o; basic violet 26 and 28
;Basic Blue 58.59.64.65.6B, 6
7 and 68; Basic Brown 1.4.11 and 12: Basic Black 8 Near Shikku Diazo Component 4.21.27 and 38; Disverse Yellow 3° 4.5.7.8.23.5o, 6o, 64 .6
6.71.72.76.78 and 79; Disbirds Orange 1.3°5.13.20.21.3o, 32.
41.43.45.4G, 49.50 and 51; Disbirds Red 1.5.7, L2, L3, L7.43
．． 52.54.56.5B, 6o, 72.73.74.
75.78.80.82.84.88.9o, 87.9
8.101, 103, 113, 117, 12
2, 125, 126, 128, and 129; Disbirds Violet IG, 24.33.38.41
．． 43 and 96: Disperse Blue 85.92.8
4 and 1o6; Disperse Brown 3 and 5; Disperse Black 1, ? , 10.26.27.28.
29.30 and 31: Solvent Yellow 2.6.
14.15.16.18.21 and 56; Solvent Orange 1.2.5.6.14 and 45; Solvent Red l, 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 l, 2.5.13.14.15.16.17.24
and 31, Pigment Red 1.2.3.4.5.
6.7.8. 9.10.11. +2.13.14.
15.16.17, [8.19.21. :22.23
．． 30.31.32.37.38.38.40.41.
48.49.50.51.52.53.54.55.5
7.58.60.63.64.68.112, 114
and 163: Pigment Blue 25; Pigment Green 10; Pigment Brown I, and 2: Pigment Black L; Direct Yellow 1.8.11.
12.24.26.27.28.33.44.50.5
8.85.86.87.88.89.98.100 and 110; evening direct orange l, 6.8.10.2
6.29.39.41.49.51.57.102 and 107; Direct Red 1.2.4.13.17.
20.23.24.2.8.31.33.37.38.
44.46.82, 63.75.79.80.81.
83.84.88.85.99.113, 197
．． 201. 218. 220. 224. 225
．． 226, 227, 228, 229, 230 and 231; Direct Violet 1.7.9.12
．． 22.35.5 [, 63, 80, 84 and 98: Direct Green 2゜6.8.15.22.25.7
1.7G, 77.7 days, 80.120, 123,
1'li8, 160.163, 165, 1
88.192, +83. 194, 195.1
96: 203, 207.225, 236, 2
37, 246.248 and 249; Direct Green 1.6.8.28.30.31.33.37.58
．． 63.64 and 74; Direct Brown IA, 2
．． 6.25.27.44.58.58,101, 1
013.173, 194, 195, 209,
2105 and 211: Direct Black 17.19.
22.32.38.51.56.71.74.75.7
7.94.105, 106. 107, 10B
, 112 , 113 , 117 , 118 , 132
, 133 and 146: Acid Yellow 11.17.
19.23.25.29.36.38.40.42.4
4.49.81.70.72.75.7G, 78.78
．． 110.127, 131, 135, 141.1
42, 164 and 165; acid orange 1.7
．． 8.10.19.20.24.28.33.41.4
3.45.51.56.63.64.65.67 and 95; Acid Red I, 6.8.9, I3.14.
18.213.27.32.35.37.42.57.
75.77.85.8B, 89.97.108, 11
1.114 , 115 , 117 , 118 , 119
, 129 , 130.131.133 , 134 ,
138, 143, 145, 154°155,
158 , 1lli8 , 249 , 252 , 254
．． 257.262, 2Ei5, 266, 274
, 278, 282, 283 and 303; Acid Violet 7.11.97 and lO6: Acid Blue 28.60.82, 113, 117 and 120
; Acid Green 19.20 and 48 Near Aged Brown 2.4.13.14.20.53.82.100
, lot , 238 , 247 , 288 , 2Ei
8, 2713, 27? , 282 , 289 , 30
1 and 302; Acid Black 1.7.24.2B
, 29.31.44.7B, 77.84.108 and 110; Mordant Yellow 1, 3.5.23.2G,
30.38 and 59: Mordant Yellow 1.4.5
．． 6.8.28 and 37; Modern Tread 7.9.
17.19.21.26.30.63 and 88; Mordant Violet 5 and 44: Mordant Blue-7
, 13, 44, 75 and 76; Mordant Guerin 1
1.15.17 and 47: Mordant Yellow 1.1
4.15.19.21.33.38.40.52 and 87; Mordand 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. 21.83.84.10
0, 109 and Hi 121; Solvent Brown 37;
Solvent Black 23; Acid Black 51.5
2.58.60.62.63.64.67.72.10
7, 108, 112, 115, 118, 1
19 , 121 , 122 , 123 , 131 , 1
32, 139, 140, 155, 158, 1
57, 158, 159 and 191 Near Zid Yellow 58.88.99.111, 112, 1
14, II6. 118, 119, 12
8, 161, 182 and 163; Acid Orange 74.80.82.85.88.87.88.122
, 123 and 124 near-zit led 180 , 1
83, 184, 188, 194°198,
199, 209, 211, 215,
216. 217, 219, 2513, 317
, 318, 320, 321 and 322 near-zit eight iolets 75 and 78 near-zit blue 151
, 154 , 158 , 1f31 , 1613 ,
187, 168, 170, 171, 17
5, 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 19.28.30.31.38.44.45.4G,
4th, 224, 225, 228, 231, 25
G, 257, 294, 295, 296, 29
7, 299 and 300; Direct Yellow 39;
Direct Violet 47 and 48; Direct Blue 90.98, 200, 201, 202 and 2
26; Direct Brown 95, too, 112, and 170 Nistilben azo dyes include, for example, Direct Black 62; Thiazole azo dyes include, for example, Direct Red 9 and 11.

Next, examples of anthraquinone dyes and pigments include the following.

As the anthraquinone derivative, for example, Paysic Violet 25; Paysic Blue 21.22.44.4
5.47.54 and 6o Near Shikku Diazo Component 36; Bat Yellow 2.3.1O120,22
and 33; Bat Orange 13 and 15: Bat Red 10.13.16.31.35 and 52: Bat Violet 138 and 21; Bat Blue 4.6.
8.12.14. Ei4.66.67 and 72; Bat Green 8.131.43.44 and 45: Bat Brown 1.3.22.25.39.41.44.4
G, 57.68.72 and 73; butt black 8.
14.2o, 25.27.36.56.59 oyobi 6o
: Disbirds Orange ll: Disbirds Red 4.
9.11.15.53.55.65.91.92.10
0, 104, 116 Oyobi 127: Dispers Bio L/7 Tol, 4, 8.23.26.28.3° and 37: Dispers Blue 1.3.5.6.7.2
0.26.27.54.55.56.6o, 61.62
．． 64.72.73.75.78.81.87.90.
91.97.98.99, 103, 104 and 1
05: Snow Blue Yellow 51: Solvent Violet 13 and 14; Solvent Blue Ratio 12.3
5 and 38; Solvent Green 3; Pigment Red 83 and 89; Pigment Blue 22; Acid Violet 3 [, 34.35.41.43.47.
48.51.54.66 and 68;7 side blue 2
3.25.27.40.4I, 43.45.54.62
．． 72.78.80.82.112, 126, 12
7, 129, 130, 131, 138,
140 , 142 , 143 , 182 , 183
, 203, 204 and 205; Acid Green 2
5.27.28, 3G, 4(+, IN and 44; Acid Brown 27: Acid Black 48 and 50
:Modant Tread 3 and 11:Modant Blue-8
and 48: Mordant Black 13; Pigment Violet 5 as an anthrone derivative, for example /kuttoye; 1°−”834′/<−/ ) r′7&1
．． 2゛3.4 and 9: Bat Violate/To 1.9
and 10: Bat Blue 18.19 and 20: Bar
/) Green l, 2.3 and 9; Butt black 9
．． 13. '29 and 57; Bat Red 13; Acid Red 80.82 and 83, and the like.

In addition, examples of indigoid dyes and pigments include the following.

Indigo derivatives such as Bat Blue 1.3.
5.35 and 41: Reduced Bat Blue
: Pigment Violet 18 and 122; Acid Blue 48 and 102; Solubilized Vat Blue-5 and 41; Solubilized Vat Black 1: Food Blue 1: As a thioindigo derivative, e.g. Bar/Torange 5: Vat red l, 2
and 61; Bat Violet 2 and 3; Pigment Red 87 and 88; Bat Brown 3, and the like.

Furthermore, examples of phthalocyanine dyes and pigments include Solvent Blue 55; Pigment Blue 15, IB and 17; Pigment Green 36, 37 and 38.
Direct Blue 88 and 198; Mordand Blue 5B.

Next, examples of carbonium dyes and pigments include primary ones.

As diphenylmethane dyes, for example, Paythic Yellow 2 As nitriphenylmethane dyes, for example, Paythic Red 9; Paythic Violet 1, 3 and 14; Paythic Blue 1.5.7.19.26.28.29.
40 and 41; Paysic Green 1 and 4; Solvent Violet 8; Solvent Blue 2 and 73
; Pigment violet 3: Pigment blue l,
2 and 3: Pigment Green 1.2 and 7: Direct Blue 41; Acid Violet 15 and 4
9; acid blue l, 7.9.15.22.83.8
0.83.100, t.

3 and 104; Acid Green 3.9 and 18;
Morpunto Violet L; Mordand Blue 1.29
and 47; Food Violet 2: Food Blue 2; Food Green 2; As a xanthine dye, for example Baylac Red I;
Solvent Red 48; Pigment Red 81 and 9
Pigment Violet 1, 2 and 23; Acid Red 51.52.87.82 and 94: Modern Red 15 and 27; Food Red 14; Examples of acridine dyes include Paythic Orange 14 and 15.

Further, examples of quinone imine dyes include the following.

As an Azire dye, for example, Paythic Red 2; Basic Black 2; Solvent Black 5 and 7; Acid Blue 58; Acid Black 2 As a nioxazine dye, for example, Paythic Blue 3:
Direct Blue 108 and 108; Thiazine dyes include, for example -Pasic Yellow I; Pesic Blue 9.24 and 25.

Examples of methine dyes include the following. Examples of polymethine (or cyanine) dyes include PASIC YELLOW 11% 13.14.19.21, 25.28.
33 and 35; Basic Orange 21 and 22;
Basin Red L2, +3, +4, +5.27.29
．． 35.36 and 37: Peisic Violet 7.
15.21 and 27.

Examples of quinoline dyes include Paysic Green 6
: Disbirds Yellow 54 and 56; Solvent Yellow 33; Acid Yellow 3.

As a nitro dye, for example, Disbirds Yellow 1
．． 33, 39, 42, 49 and 54; Acid Yellow 1.

Henzoquinone and naphthoquinone dyes include, for example, Disperse Blue 58 and 108;
．． 165 and 18 days.

Examples of naphthalimide dyes and pigments include Pigment Red 123; Pat Violet 23 and 28;
Acid Yellow 7 is mentioned.

Examples of perinone dyes include Per/ ) 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? , 3.6.14 and 27; Solubilized Sulfur Brown 1 and 51; Sulfur Brown 7.12. 15 and 31; Sulfur Black I, 2.5.6.10.11 and 15: Yatsuto Yellow 35.42 and 43; Yatsuto Blue-43 and 56.

Examples of fluorescent paints include Fluorescent Brightening Agene 4.22.24.3o, 32.3
7.45.52.54.55.56.84.85.86
．． 87.90.91.104.112 , 121 , 1
34, 135, 153.162.1133, 11
34, leG, 187, 168, 1e9
．． 170, 171, 172, 173, 174.
175, 176 and 177.

Examples of azoic dyes include azoic diazo component 17.20.22.24.26.31.3
5.41.47.48.108 and 121 Near Seat Coupling Components 2.3, 4.5.7.8
．． 10.11. +2.14.15.1G, 17.18
．． 19.20.23.26.28.29.35.36.
37.41 and 108; Azoic Brown 2.7,
H and +5; Azoic Black 1 and 5; Azoic Yellow 1 and 2; Azoic Orange 2, 3 and 7: Azo Ink Red 1.2.6.9, 16 and 24: Azo Ink Violet 1.2.6 .7.9 and 10 Near Strike Green 1.

Examples of reactive dyes include Reactive Yellow 1.
2.3.4.6.7, If, 12, +3, +4.15
．． 16.17.18.22.23.24.25.2G,
27.37 and 42; Reactive Orange 1.2
．． 4.5.7.13.14.15.16.18.20.
23 and 24: Reactive Red 1.2.3,
4.5.6.7.8.11.12.13.15.16.
17.19.2o, 21.22.23.24.28.2
9.31.32.33.34.35.36.37°38
．． 39.40.41.42.43.45.4B, 48.
5o, 58.59.63 and 64; Reactive Violet 1.2.4.5.8.9 and 1o; Reactive Blue 1.2.3.4.5.7, 8.9.13
．． 14, 15.17.18.19.2o, 21.25.
26.27.28.29.31.32.33.34.3
7.38.39.4o, 41.43.44 and 46;
Reactive Green 5, 6.7 and 8; Reactive Brown 1, 2.5, 7.8.9.10.11.1
4 and 16; Reactive Butch 1.3.4.
5.6.8.9.10.12.13.14 and 18.

Examples of pigments include baseless pigments such as chromium yellow, Ti lead yellow, 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 an anti-scaling agent. By reducing the surface roughness to 5 gm or less before applying the product to other surfaces, it is possible to effectively prevent scale formation. 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 setting the surface roughness of the surface to be coated to 5 JLm or less.If the surface roughness exceeds 5 gm, the scale adhesion prevention effect is insufficient, and the scale adhesion prevention effect is insufficient. cannot be prevented.

As mentioned above, when applying a mixture of component (a) dyes/pigments and component (b) inorganic compounds, component (a) and (
The ratio of component (b) to component (b) is preferably 0.1 to 2,000 parts by weight, more preferably 1 to 1,000 parts by weight, per 100 parts by weight of component (a).

1 The inorganic compounds of this (b) component are:
Ortho-1 silicic acid, meta-silicic acid, meso-trisilicate, meso-trisilicate, mentetra-silicic acid, sodium metasilicate, or-I sodium silicate, sodium disilicate, sodium tetrasilicate, potassium metasilicate, hydrogen disilicate Potassium, lithium orthosilicate, hexalithium orthodisilicate, water glass, 12-tungsilicate, iso-
12-silicotungstic acid, IO-silicotungsten, potassium 12-silicotungstate, iso-12-potassium silicotungstate, IO-potassium silicotungstate, sodium 12-silicotungstate, iso-12-sodium silicotungstate , silicates or silicates such as silicic molybdic acid, potassium silicomolybdate, and sodium silimolybdate; alkaline earth metals such as magnesium, calcium, and barium, zinc group metals such as zinc, aluminum such as aluminum, and titanium. , tin group metals such as soot, iron group metals such as iron and nickel, chromium group metals such as chromium and molybdenum,
Total conversion of metals selected from manganese group metals such as manganese, copper group metals such as copper and silver, and platinum group metals such as platinum, etc. Foundation colloid, silver colloid, sulfur colloid, ferric hydroxide colloid, tin oxide, silicic acid colloid, manganese dioxide colloid, m-hydroxide colloid, barium sulfate colloid. Colloids, henadine pentoxide colloids, aluminum hydroxide colloids, lithium silicate colloids, etc. Mechanical crushing, ultrasonic irradiation,
Inorganic colloids produced by: A by electrical dispersion and chemical methods are exemplified. Among these, silica salts, silicate colloids, ferric hydroxide colloids, etc. are particularly preferred.

Dyes and/or pigments, optionally further rif
In order to apply a composition containing the above-mentioned inorganic compounds to the inner wall surface of a polymerization vessel, it is sufficient to prepare a coating liquid as it is or by dissolving or dispersing it in an appropriate solvent and apply it.Scale preservative in the coating liquid The concentration of is usually preferably 0.01% by weight or more.

Examples of solvents for preparing the coating solution include water and various organic solvents, such as gasoline, petroleum, benzine, mineral spirit, petroleum natsuta, V, and M.

Aliphatic hydrocarbons such as &P, naphtha, decalin, tetralin, P-cymene; Aromatic hydrocarbons such as benzene, toluene, xylene; Trichlorethylene, perchlorethylene, chloroform, carbon tetrachloride, ethylene trichloride, -benzene bromide,
-Halogenated hydrocarbons such as benzene chloride and benzene dichloride; amyl alcohol, ethyl alcohol, inpropyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, methyl amyl alcohol, benzyl alcohol,
Alcohols such as butyl alcohol; acetone, acetonylacetone, diisobutyl ketone,
Ketones such as 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, methyl propyl ketone, medicyl oxide; acetic acid esters, Esters such as butyrate esters, propionate esters, formate esters: milk butyrate,
Alcohol esters such as isopropyl milk, ethyl oxypropionate, diethyl maleate; Ketone esters such as ethyl acetacetate and ethyl pyruvate; Ethers; Ketone alcohols such as acetonylmethanol, diacetone alcohol, dihydroxylylacetone, pyruvyl alcohol; isobrobylceronelube, carbitol, glycidol, cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butyl cellosolve, methyl derbitol , methyl cellosolve, triethylene glyconyl monoethyl ether, and other ether alcohols; acetal ethyl ether, acetonyl methanol ethyl ether, methyl ethoxyethyl ether, and other ketone ethers; butyl carbitol acetate, butyl cellosolve acetate, butyl carbitol acetate, Ester ethers such as cellosolve acetate, 3-methoxybutyl acetate, methyl carbitol acetate, and methyl cellosolve acetate can be used.

Alcohols such as methyl alcohol, ethyl alcohol, allyl alcohol, n-propyl alcohol, and isopropyl alcohol that are highly compatible with water as organic solvents; Ketones such as acetone, acetonyl aquitone, and diacetone alcohol; Acetate ethylene glycol monomethyl ether , diethylene glycol methyl ether acetate, monoethyl acetate, and other esters; dioxane, ethylene glycol monomethyl ether,
Ethers such as ethylene glycol monoethyl ether; furans such as tetrahydrofuran and furfuryl alcohol; aprotic melts such as acetonitrile and N,N-dimethylacetamide; etc. When using, dissolve in a scale adhesion preventive agent. By adding water to the coating solution within a range that does not impede the properties and dispersibility, it is possible to improve the economic efficiency of the coating solution and the safety during transportation and storage. 'Sulfone fi,',6 in which the anti-scaling agent used is in the form of an alkali metal salt or an ammonium salt.
Or, in the case of a water-soluble sulfonic acid type or carboxyl group dye having a carboxyl group,
As described in No. 5442, water can be used as a solvent for dissolving, which has the safety and health advantage of being solvent-free and harmless. When water is used as a solvent, as described in Japanese Patent Publication No. 58-5444, an alcohol, preferably 03 to 6 m alcohols, such as n-propyl alcohol, n-butyl alcohol, is added to the coating solution.゛, iso-butyl alcohol, Sec-butyl alcohol゛, t-butyl alcohol, n-7 methyl alcohol, t-7 methyl alcohol, iso-amyl alcohol, sec-7 methyl alcohol, sec-hexyl alcohol, etc. are added, It can improve the wettability of the coating liquid to the inner wall surface of the polymerization vessel. In addition, special public service Sho 513-5
As described in No. 442, organic solvents that are compatible with water, such as alcohol solvents, ester solvents, ketone solvents, etc., are added to the coating solution in order to facilitate drying after coating. You can also add

When applying a coating solution containing dyes/pigments and, in some cases, inorganic compounds, etc., to the inner wall surface of the polymerization vessel according to the method of the present invention, various coatings may be applied as necessary to improve stability on the wall surface, etc. A fixative can be used.
The fixing agent can be used by adding it to a coating solution containing a scale adhesion preventive agent, or by applying the fixing agent or its solution to the wall surface etc. in advance before applying the scale adhesion preventive agent. There are methods such as overcoating a scale adhesion preventive agent on top, and an appropriate method of use is selected depending on the type of scale adhesion preventive agent and 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), polyisobutyne, polycyclopentene, polycyclopentylethylene, polycyclohexylethylene, poly(3-cyclohexyl-1-propene), poly(4 -cyclohexyl-1-butene), poly(5-cyclohexyl-1-hentene), poly(cyclotrifluoroethylene), poly(tetrafluoroethylene); diene polymers, such as polyalene, polybutadiene, polyisoprene, polychloroethylene Lopyrene, poly(l-methoxybutadiene), poly(2-tert-butyl-1,3-butadiene), poly(cy'1 clopentadiene),
Poly(1,3-cyclohexadiene), poly(dimethylfulvene), poly(4-vinyl-1-cyclohexane)
, poly(1,5-hexadiene), poly(l,5-cyclooctadiene), poly(bicyclo-2,2,1-hebuta-2,5-diene), poly(5,7-dimethyl-1.
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 (vinylcyclohexanone ketal), poly(vinyl acetate), poly(vinyl chloroacetate), poly(vinyl isobutyrate), poly(vinyl vivalate)
, poly(vinyl n-caproate), poly(vinyl caprylate), poly(vinyl laurate), poly(vinyl palmitate), poly(vinyl benzoate), poly(
vinyl chloride), 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 in butyl 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(vinyl benzyl ether), poly(
poly(vinyl methyl ketone), poly(methyl isopropenyl ketone), poly(1-nitropropylene), poly(vinyl sulfofluoride), poly(vinyl sulfone butylene), poly(vinyl diphenylphosphine oxide), poly(vinyl diphenyl) phosphine sulfide), poly(dimethyl-2-cyano-2-propene-1-phosbonate)
, poly(diethyl-2-cyano-2-propene-1-phosphonate), poly(maleic anhydride); aromatic vinyl polymers, such as polystyrene, poly(α-methylstyrene), poly(4-chloro styrene)
, poly(4-/lomostyrene), poly(dichlorostyrene), poly(4-methoxystyrene), poly(2,5
-dimethoxystyrene), poly(vinyl-bis(1-ethoxyethyl)hydroquinone), poly(4-vinyl-phthalic acid), poly(4-vinyl-phenyl), poly(diphenyl-4-styrylphosphineoxy) ), poly(diphenyl-4-styrylphosphine sulfide), poly(9-vinylanthracene), poly(4-vinyl-biphenyl), poly(acenaphthylene), polyindene; Heterocyclic polymers, such as poly( N-vinylcarpazole), poly(9-Δ5-pentenylcarpane), poly(9-Δ5-hexenylcarpasol/hesol), poly(N-vinylpyrrolidone), poly(2-vinyl pyridine), 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-molporinone-(3
)), polycoumarone; acrylic and methacrylic polymers, such as polyacrylic acid, polymethacrylic acid, poly(menal acrylate), poly(ethyl acrylate-I), poly(butyl acrylate), poly(5-cya/-) 3-thia-
Phenyl acrylate I), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-propyl methacrylate), poly(n-butyl methacrylate)
1.), poly(inbutyl methacrylate), poly(n
-hexyl methacrylate), poly(2-ethylbutyl methacrylate), poly(n-octyl methacrylate), poly(n-lauryl methacrylate), poly(4-
(tert-butyl) phenyl methacrylate), poly(fornyl methacrylate), poly(β-(N-carbasyl)ethyl methacrylate), poly(tert-butyl crotonate), polyacrylonitrile, polymethacrylonitrile, polyacrylamide, poly( N, N-
dimethylacrylamide), poly(N-(1,1-dimethyl-3-okynebutyl)acrylamide), poly(acrylopiperidine), poly(acrylomorpholide), poly(9-acrylylcarbazolein), poly (α-methylacrolein), poly(diacrylylmethane), poly(acrylic anhydride), poly(methacrylic anhydride); polyethers, such as polyformaldehyde, polyacetaldehyde, poly(monochloroacetaldehyde), polychloral, polypropylene aldehyde,
Polyacrolein, poly(2-formyl-Δ5-dihydropyran), poly(trans-1,2-cyclohexanedicarboxaldehyde), poly(glutardialdehyde), poly(β-methylglutardialdehyde), poly(β-phenylglutardehyde) dialdehyde), poly(dimethylketene), polyacetone, poly(monobromoacetone), poly(7-oxa-bicyclo(2,2,l]heftane), 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-franc sulfone), poly(5-norpor delta sulfone), poly (
styrene sulfone), poly(1-pentynesulfone),
Poly(1-hexynesulfone), poly(i-heptynesulfone), poly(butadienesulfone), poly(imprenesulfone), poly(dimethylbutadienesulfone)
, poly(1,5-hexadiene sulfone), poly(cis, cis-cyclo-octadiene sulfone), poly(norbornadiene sulfone); various addition polymers such as poly(methylene diisocyanate), poly( ethylene diisocyanate), poly(
trimethylene diisocyanate), poly(tetramethylene diisocyanate), poly(5-iminohydantoin), poly(perfluorogeltalodinitrile), poly(l-(perfluorobutyryl)aziridine); formaldehyde resins, e.g. 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 di/<-cate),
Poly(hexadecamethylene sepacate), poly(]hexamethylene α,α′-dibutylsenocucate], poly(octamethylene cis-hexahydroterephthalate), poly(octamethylene trans-hexahydroterephthalate), poly( hexamethylene maleate),
Poly(hexano□1 tyrene fumarate),
Poly(hexamethylene 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 sulfonate), poly(4,4'-isopropylidene diphenylene sulfonate),
'-(2-pentylene)diphenylene sulfonate),
Poly(1,2-bis(hydroxymethyl)carporan)
adipic acid), poly(allyl sulfonate), poly(hydroquinone-7lyloxy-phospholyl dichloride), poly(hydroquinone-(chloromethyl)phosphoryl dichloride), poly(hydroquinone-(N-dimethyl)porformamide)
acid) dichloride; polyamides, such as poly(incyanate), poly(vinyl isocyanate), poly(butyl isocyanate), poly(3-aminopropionic acid), poly(6-aminopropionic acid), poly(It-amino undecanoic acid), poly(hexamethylene adipamide), poly(decamethylene adipamide), poly(3,3'-C menalimide/
) trimethylene adipamide), poly(penzidine-isofucric acid), poly(pyrromeric dianhydride-aromatic diamine), poly(1,8-hexamethylene-bis(carboxyethyl) sulfide), poly (
l,6-hexamethylenediamine-benzene-1,3-
(bissulfone chloride), poly(trans-2,
5-dimethyl-piperazine-4,4'-sulfonyl-dibenzoyl chloride), poly(bis(3-7minopropyl)phenyl phosphine-adipic acid), poly(bis(3-aminopropyl)phenyl phosphine-terephthalic acid), poly(bis(3-aminopropyl)methylphosphine oxide-adipic acid), poly(bis(3-
7 minoprovir) n-cutylphosphine-adipic acid), poly(bis(3-aminopropyl)phenylphosphine oxyto-adipic acid), poly(hexamethylenediamine-bis(2-carboxyethylene)phenylphosphine oxide) , poly(hexamethylenediamine-bis(p-carboxydiphenyl)phenylphosphine oxide), poly(piperazine-bis(2-carboxyethyl)-7-22ylphosphine oxide) polylia,
Polyurethanes, such as Voluria, poly(1,10
-decamethylene diamine-1,6-hexamethylene-bis-ethyl urethane), poly(diphenylmethane-4,
4'-diisocyanate-N, 4'-diphenylmethane), polyluene-2,4-diisocyanate-N,
N'-bis(trimethylsilyl)-p,p'-diaminodiphenyl ether, polyurethane, polyurethane poly(propylene oxide) basis; various linear condensation polymers, such as poly(diethylcarbodiimide diimide), poly(diimide) -butylcarbodiimide)
, poly(di-n-hexylcarbodiimide), poly(
poly(diphenylcarbodiimide), poly(4,4'diphenylenemethane-carbodiimide), poly(hexamethylenecarbodiimide), poly(I,3-xylylenecarbodiimide), poly(3-menal-1,4-phenylenecarbodiimide) , poly(2,2'-dimethyl-biphenylene carbodiimide), poly(2,2'-dimethoxybiphenylene carbodiimide), poly(1,5-
naphthyrefcarbodiimide), poly(azibyl dihydrazide 1:-succinoyl chloride), poly(adipyl dihydrazide-isophthaloyl chloride), poly(inphthalic dihydrazide-terephthaloyl chloride)
, poly(2,5-dimethylbenzylene), poly(p-xylylene), poly(2,5-dimethylxylylene), poly(2,5-dimethoxy-p-xylylene), poly(p-xylylene)
-xylylidene).

Poly(α-cyano-m-xylylidine), Poly(α-
cyano-p-xylylidine), polytrophenylene)
, poly(tetramethyl-p-)22 dimethylene),
poly(2,5-dihydroxy-p-)22 dimethylene), poly(4,4'-oxydiphenylene dimethylene), poly(2,5-dimethoxy-p-)22 dimethylene); heterocycle Formula condensation polymers, such as poly(benzimidazole), poly(alkylene-5,5'-dibenzimidazole), poly(arylene-5,5'-dibenzimidazole), poly(pyromellitimide),
Poly(benzoxazole), poly(oxadiazole), poly(oxadiazolidine), poly(dithiazole), poly(benzothiazole), poly((1,4-xylylenyl)-2-methylpiperazine), poly(quinoxaline) ), poly(S-dryazinyleneimide); natural polymers, modified natural polymers, such as natural rubber, cyclized rubber, salt-ugly rubber, chlorinated rubber, gutta percha, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose , butyl cellulose, allyl cellulose, benzyl cellulose, hydroxyethyl cellulose,
Carboxymethyl cellulose, cyanoethyl cellulose, cellulose triacetite, cellulose acetite,
Cellulose triacetite, cellulose tripropionate, cellulose tributyrate, cellulose tricaproate, cellulose trical distate, cellulose nitrate, cellulose trinitrate, scouch, amylose, amylose acetate, amylose carbanilate, amylopectin , alginine, chitin, glycogen, gum arabic, gum tragacanth, heparin,
Pectin, rosin, copal, shellac, casein,
Collagen (calf-skin), Collage 7 (
:1chthyocol), gelatin, peanut protein, soybean protein, nuclear protein (ca
lf thymus), nuclear protein (sperm
of 5eaurchin), poly(sarcosine), sericin, silk, wool, zein, polyadenyls, deoxyliponucleic acid, liponucleic acid; polysiloxanes, e.g. polysiloxane, polydimethylsiloxane; alpha metal polymers, e.g. poly(bis) (imidazolate)-total (■)), poly(aluminum triisopropylate-ethylenediamine); and solid polymers such as polymetaphosphate.

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 parts of the attached equipment of the polymerization vessel where scale may adhere; (including sexual areas).

Equipment attached to the polymerization vessel that the monomer comes into contact with includes, for example, stirring blades, stirring shafts, condensers, heaters, 8-furs, search coils, bolts, nuts, and the like.

There are no particular restrictions on the method of applying the scale adhesion preventive agent to the inner wall surface of the polymerization vessel. No. 57-131001, 5
No. 5-38288, Special Publication No. 5Ei-501116,
The automatic coating method described in JP-A No. 5G-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 monomers. Production of (co)polymers 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 S SBR, NBR,CR,I
Production of synthetic rubbers such as R and IIR (these synthetic rubbers are usually produced by emulsion polymerization); production of ABS resin, etc. can be mentioned.

The type of polymerization may be ar4 polymerization or emulsion polymerization. The vinyl monomers subjected to the polymerization include vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters, methacrylic esters, etc. or esters or salts thereof, maleic acid or fumaric acid,
And those varnishes! chill or anhydride, butadiene, chloroprene, '4/7'L=7(
7) Yoyo, -78□yo, aaa-.

Examples include vinyl, acrylonitrile, vinylidene halide, and vinyl ether.

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, 1, for example, t-butyl peroxyneodecanate, di-2-ethylhexyl peroxydicarbonate, 3,
5.5-Trimethylhexanoel peroxide, α-
Cumyl peroxy neodecanoate, cumene hydroperoxide, cyclohexanone peroxide, t-
Butyl peroxypivalate, di-2-ethoxyethyloxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-diglorbenzoyl peroxide, diisobrobyloxydicarbonate, and acetylcyclohexyl peroxide. Harsh organic substances such as α,α′-azobisisobutyronitrile, azo catalysts such as α,α′-azobis-2,4-dimethyloctaleronitrile, water-soluble peroxides such as potassium persulfate, ammonium persulfate, etc. used.

In addition, as dispersants, for example, partially etched polyvinyl acetate, polyacrylic alcohol, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropyl methyl cellulose, and 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 alkylbenzene sulfonate are used, and other additives such as calcium carbonate and titanium oxide are used. Three fillers;! Stabilizers such as lead sulfate, calcium stearate, dibutyltin dilaurate, dioctyltin mercaptide, rice wax, stearic acid, cetyl alcohol, plasticizers such as DBP, chain transfer agents such as trichloroethylene and mercaptans. , pI (regulator, etc.) 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 type of catalyst, dispersant, or additive. can be prevented.

[Example] The present invention will be specifically explained below with reference to Examples, but the scope of the present invention is not limited thereto. In addition,
Parts represent parts by weight unless otherwise specified.

Example 1 As shown in Table 1, for each experiment, the internal volume was 100M,
A 1000mm, 2000mm, 40M3, or 130M3 stainless steel polymerization vessel was selected, and its inner wall surface was manufactured to the surface roughness (Rmax) shown in the table. For each experiment, dyes or pigments were dissolved or dispersed in a solvent as shown in Table 1, and inorganic compounds and polymeric compounds shown in the table were added as necessary to prepare a coating solution. 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 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 monomers, such as the stirrer, and heated to 80°C at 1O2.
After drying for a minute, it was thoroughly washed with water.

Next, vinyl chloride
100 parts of polymer, 200 parts of ion-exchanged water, 0.022 parts of partially phosphorized polyvinyl alcohol, 0.028 parts of hydroxymethyl cellulose, and 0.03 parts of t-butyl peroxyneodecanate were charged, and polymerized at 52°C for 7 hours. did. After the polymerization is completed, take out the polymerized product and adjust the inside of the polymerization vessel to Ll m″/
Washing was performed with water at a flow rate of m'·hr for the time listed in Table 1. The above operations from coating and preparation to washing with water after polymerization were performed for each batch, and the process was repeated for a maximum of +;'++ 200 patches.

Also, No. 10.30.50.100, 150 and 2
The state of scale adhesion after each patch of 008-I was visually evaluated according to the following criteria, and the final patch end r1°
Regarding the cross, scale adhesion M (g/m') 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 (approximately 10% adhesion rate)) D: Partially thick scale adhesion (adhesion rate approximately 10%) E: Partially tingling scale adheres (approximately 50% reduction rate) F: Partially thick scale adheres (approximately 50% reduction rate) G: Thick scale adheres to the entire surface H: Thick scale adheres to the entire surface Attachment Note that the experiment numbers marked on the back of Table 1 indicate comparative examples. In particular, experiment numbers 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 heating the solution at 80°C.
It was prepared by heating for 30 minutes.

was taken out, and the inside of the polymerization vessel was washed with water at a flow rate of 0.1 rn'/m'·hr for the time shown in Table 2. The above operations from coating and preparation to washing with water after polymerization were performed for each batch, and repeated for a maximum of 200 batches.

In the same manner as in Example 1, No. 10.30.50°100
, 150th and 200th batch The state of scale adhesion after each batch was visually evaluated, and the amount of scale adhesion (g/m') was also measured after the final batch was completed. These results are also shown in Table 2.

Note that the experiment No. marked with 1 in Table 2 indicates that it is a comparative example. In particular, experiment No. Ef5.6B is an example in which no compound was applied to the inner wall surface of the polymerization vessel.

In addition, the coating solution of experiment No. 105, 133 was 1 part water.
It was prepared by dissolving 1 part of sodium sulfide in 0.00 parts, adding 0.5 part of dye, and heating at 80°C for 30 minutes.

Example 3 As shown in Table 3, for each experiment, the internal volume was 100 sentences,
tooofL, 2000 views, 40M or 130M
stainless steel? A 1J polymerization vessel was selected, and its inner wall surface was adjusted to the surface roughness (Rmax) shown in the same table. For each experiment, dyes or pigments were dissolved or dispersed in the solvent as shown in Table 3, and inorganic compounds as shown in the table were added as needed.
A coating solution was prepared by adding a polymer compound. The blending ratio of inorganic compounds and polymer compounds in each experiment, and the dye and
The coating solution prepared in this way, whose pigment concentration is also shown in Table 3,
It was applied to the inner wall surface of the polymerization vessel having a predetermined surface roughness as described above and to the portions 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, and 20 parts of ion-exchanged water were added to the polymerization vessel coated in this manner.
0 parts, gelatin 0.3 parts, trichlene 1 part, and lauroyl peroxide 0.175 parts, and heated at 70°C.
After 6 hours of polymerization, the polymer was taken out and the inside of the polymerization vessel was washed with running water at 0.1 rIf/rn'·hr for the time shown in Table 3. The above operations from coating and preparation to washing with water after polymerization are performed in 4σ batches.
The experiment was repeated for a maximum of 200 batches.

10.30.50.100 in a similar manner to Example 1.
, 150 and 200 The scale adhesion state after each batch was visually evaluated, and the scale adhesion (Fidg/m'') was also measured after the final batch.These results are also shown in Table 3. .

Note that the experiment numbers marked with a mark in Table 3 indicate comparative examples. In particular, experiment numbers 136 and 137 are examples in which no compound was applied to the inner wall surface of the polymerization vessel. In addition, the coating liquid of experiment No. 177.178 was 1 part water.
It was prepared by dissolving 1 part of sodium sulfide in 0.00 parts, adding 0.5 part of dye, and heating at 80°C for 30 minutes.

Example 4 As shown in Table 4, each experiment had an internal volume of 100 sentences,
1ooofL, 20001.40M3 or 130M
3 stainless steel? M polymerization vessel was selected, and its inner wall surface was adjusted to the surface roughness Rmax) shown in the same table. 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 polymeric compounds and the dye/pigment concentration of the coating solution for each experiment are also shown in Table 4. Apply it to the area in contact with monomers such as, and heat it at 80℃ for 1
After drying for 0 minutes, it was 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 di-2-ethylhexyl peroxide were added to the polymerization vessel coated in this way. After 0.04 parts of oxydicarbonate was charged and polymerization was completed at 57°C for 7 hours, the polymer was taken out and the inside of the polymerization vessel was adjusted to 0.1 parts.
Washing was carried out with water at a flow rate of 1200 mm/hour for the time shown in Table 4. The above operations from coating and preparation to washing after polymerization were repeated for each batch, and the process was repeated for up to 1,200 patches.

10.30.50.100 in a similar manner to Example 1.
, 150th and 200th batch after each batch
.

The state of scale adhesion was visually evaluated, and after the final batch, the scale adhesion Fl (g/m') was also measured.

Also, 10.30.50, 100, 150 of each ¥ test
And the number of fish 7 of the product obtained from the polymer produced in the 200th batch was added to 71111 as follows.

Polymer 10 obtained by dehydrating and drying the slurry after polymerization
0 parts, DOP 50 parts, dibutyltin dilaurate 1 part,
A mixture of 1 part of cetyl alcohol, 0.25 part of fermented titanium, 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. The number of fisheyes contained in the sheet per 100 cm was determined by the method.

Table 4 shows the results of the J [ll determination].

Note that the experiment numbers marked with 1 in Table 4 indicate that they are comparative examples. Experiment Nos. 18e and 182 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

□1 Example 5 As shown in Table 5, for each experiment, the internal volume was 5, 20
A stainless steel polymerization vessel of 100 mm or 100 mm was selected, and its inner wall surface was adjusted to the surface roughness Rmax) shown in the same table. 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. The blending ratio of the fifi compound and polymer compound and the dye Φ pigment concentration of the coating solution for each experiment are also shown in Table 5. It was applied to the areas that come in contact with monomers such as, dried at 80° C. for 10 minutes, and then thoroughly washed with water.

Next, 75 parts of styrene, 25 parts of acrylonitrile, 120 parts of ion-exchanged water, 0.5 parts of phosphorus tricalcium, 0.01 part of sodium dodecylbenzenesulfonate, and 0 parts of lauroyl peroxide were added to the polymerization vessel coated in this way.
．． 4 parts were charged and polymerized at 80°C for 8 hours. After the polymerization is completed, take out the polymerized material and adjust the inside of the polymerization vessel to 0.1m'/m''.
Washing was performed with water at a flow rate of hr for the time listed in Table 5. The above operations from coating and preparation to washing with water after polymerization were performed for each batch, and the batches with a maximum of 10 O were repeatedly performed.

Using the same method as in Example 1, the state of scale adhesion after each batch of 1.2.3.5 and 7th batch I was visually evaluated, and the amount of scale adhesion (g /rn') was also measured. These results are also shown in Table 5.

In Table 5, the experiment numbers with a written seal indicate that they are comparative examples. In particular, experiment numbers 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 sodium sulfide in 100 parts of water, adding 0.5 part of dye,
It was prepared by heating at C for 30 minutes.

Example 6 As shown in Table 6, for each experiment, the internal volume was 5 and 20.
A stainless steel polymerization vessel of fL or 1001 was selected, and its inner wall surface was manufactured the following day to the surface roughness Rmax) shown in the same table. 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. The blending ratio of inorganic compounds and polymeric compounds and the dye/pigment concentration of the coating solution for each experiment are also shown in Table 6. It was applied to the areas that come into contact with monomers such as, dried at 90°C for 10 minutes, and then thoroughly washed with water.

Next, 100 parts of styrene monomer, 250 parts of ion-exchanged water, 0.2 parts of polyvinyl alcohol, 0.75 parts of t-dodecyl mercaptan, and 0.5 parts of lauroyl peroxide were added to the polymerization vessel coated in this manner. After charging and stirring, the internal temperature was kept at 70°C for 5 hours, then the temperature was raised from 70°C to 80°C over 2 hours, and then polymerization was carried out at 80°C for 1 hour. After polymerization is complete, take out one polymer.

The inside of the polymerization vessel was washed with water at a flow rate of 0.1 m''/rn''-hr for the time shown in Table 6. The above-mentioned operations from coating and preparation to washing with water after polymerization were performed for each batch, and the batches with the highest 10O were repeatedly performed.

The operation up to washing with water after polymerization was performed for each batch, and the process was repeated for a maximum of 10 batches. - Using the same method as in Example 1, the state of scale adhesion after the completion of the 1st, 2, 3, 5th and 7th batches was visually evaluated, and after the completion of the final batch, the scale adhesion -1iE (g/
m') was also measured. These results are also shown in Table 6.

The experiment numbers marked on the back of Table 6 indicate comparative examples. In particular, experiment numbers 219 and 220 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

Example 7 As shown in Table 7, for each experiment, the internal volume was 5 and 20.
A stainless steel polymerization vessel of 100 mm or 100 mm was selected, and its inner wall surface was adjusted to the surface roughness Rmax) shown in the same table. 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. The blending ratio of inorganic compounds and polymeric compounds and the dye/pigment concentration of the coating solution for each experiment are also shown in Table 7. It was applied to the areas that come in contact with monomers such as, dried at 80° C. for 10 minutes, and then thoroughly washed with water.

Next, 148 parts of water, 1.85 parts of sodium oleate, 48 parts of polybutadiene Latin glass (solid content 45%), and 3311 parts of styrene monomer were added to the polymerization vessel coated in this way.
Part, Aga1). =1.1), monomer. f
ltl, t-door 7 □ Add 0.15 parts of Kabutane and 0.5 parts of cumene hydroperoxide, and bring the internal temperature to B5.
0.74 parts glucose at °C.

Ferrous Vε acid 0.0074 parts, pyrroline buty soda 0.3
7 parts were charged, and polymerization was carried out at 65° C. for 5 hours while stirring. After the polymerization is completed, take out the polymer and adjust the inside of the polymerization vessel to 0.1
Washing was performed with water at a flow rate of m''/m''·hr for the time listed in Table 7. The above operations from coating and preparation to washing with water after polymerization were performed for each batch, and the batches with a maximum of 10 O were repeatedly performed.

In the same manner as in Example 1, the state of scaling after the completion of the 1st, 2nd, 3.5th, and 7th batches was visually evaluated, and after the completion of the final batch, the scale adhesion amount (g/m '') were also measured. These results are also shown in Table 7.

The experiment numbers marked with a 1 in Table 7 indicate comparative examples. In particular, experiment numbers 248 and 249 are examples in which no compound was applied to the inner wall surface of the polymerization vessel.

[Effects of the Invention] As is clear from the above Examples and Comparative Examples, according to the present invention, the surface roughness of the portions that come into contact with monomers during the polymerization process, such as the inner wall surface of the polymerization vessel, is set to 5 mm or less.
By applying dyes and/or pigments to the surface, 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, if inorganic compounds are used in combination with dyes and pigments, the scale prevention effect will be improved, but in this case as well, the surface roughness of the inner wall of the polymerization vessel should be kept at 51L or less to ensure that the effect is effective and reliable. Therefore, the labor and time for scale removal can be saved, and the continuous use of the polymerization reactor becomes flexible, improving the operating rate.Also, the cooling capacity of the polymerization reactor can be maintained constant, and the scale can be removed. Since there is no risk of contamination with the product, the quality of the product polymer is improved.□

Claims (1)

[Claims] 1) A method of suspension polymerization or emulsion polymerization of one or more vinyl monomers in an aqueous medium, in which the monomers on the inner wall surface of the polymerization vessel and in the equipment attached to the polymerization vessel are A method for producing a vinyl polymer, characterized in that the surface roughness of the contacting portions is 5 μm or less, and the surfaces thereof are coated with dyes and/or pigments 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 in contact with the monomers. 5 μm or less, and the surface thereof is coated with (a) at least one of dyes and pigments and (b) at least one of inorganic compounds in advance.