SK277795B6 - Method of production of vinylchloride polymer - Google Patents

Abstract

Polymerization is realized in polymerization vessel, which internal walls and components of auxiliary equipment coming into contact with monomer at polymerization are beforehand covered with agent for prevention against incrustation. Agent contains at least one matter chosen from collection which comprises azo dyes and pigments, antraquinone dyesand pigments, phthalocyamine dyes and pigments, carbony dyes and pigments quinonemine dyes, nitrodyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes and pigments, perinone dyes, fluoroscence dyes, sulfide dyes, dissoluble azodyes and reactive dyes and incidentally additives, at which concentration of chloride ion in reaction mixture is kept on value maximum 100 ppm. Agent for prevention of incrustation cam contains azine dye and as additive inorganic compound, as silicate, colloid silicate acid or colloid hydroxide ferric. Next can agent contain fixating component for support of adhering of agent for incrustation preventing, as olefin, diene and acetylene polymers, alfatic vinyle or vinyldiene polymers, aromatic vinyl polymers, heterocyclic vinyl polymers, acryle or metacryle polymers, polyeters, polysulfides, polyesters, polyamides, condensated polymers, nature polymers, or modified, polysiloxanes, organometal and inorganic polymers.

Description

Technical field

The invention relates to a process for the production of vinyl chloride polymer, in particular to improving the prevention of the formation of incrustations on the inner walls of polymerization vessels in the polymerization of vinyl chloride.

BACKGROUND OF THE INVENTION

In the slurry polymerization or emulsion polymerization process of vinyl chloride monomer and other vinyl monomers in the presence of polymerization catalysts, the polymer adheres to the inner walls of the polymerization vessels or to the internal surface of the polymerization vessel auxiliary that comes into contact with the monomer during polymerization, e.g. The adherence of the polymer to the inner walls of the polymerization vessel and to the walls of the auxiliary device reduces the polymer yield, deteriorates the cooling capacity of the polymerization vessel, and can cause the formation of so-called polymerization. fish eyes by peeling the incrustations from the inner walls of the polymerization vessel and mixing them with the product, thereby reducing the quality of the product. In addition, the removal of stuck increments must not be laborious and lengthy; moreover, unreacted monomers (for example vinyl chloride) are absorbed on the injections and accidents dangerous to humans can occur.

In order to prevent the formation of polymer deposits, it is known in the prior art to coat a chemical agent (hereinafter referred to as an incrustation prevention agent) on the inner surface of the walls of the polymerization vessel: various such agents have been proposed. Of the various known methods, a method in which a dye or pigment is used to prevent the formation of encrustations is particularly well known (Japanese Patent Application Publication No. 30835/1970). However, this method is not always effective and safe in preventing incrustations and is not always satisfactory.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a process for the manufacture of a vinyl chloride polymer, wherein the polymerization is carried out in a polymerization vessel, wherein the inner walls and auxiliary components which come into contact with the polymerization monomer are pre-coated with an incrustation prevention agent containing at least one substance selected from , which includes azo dyes and pigments, anthraquinone dyes and pigments, indigo dyes and pigments, phlolocyanine dyes and pigments, carbon dyes and pigments, quinoniinine dyes, nitro-dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, dyes, sulphide dyes and pigments, , insoluble azo dyes and reactive dyes, and optionally additives, wherein the concentration of chloride ion in the reaction mixture is not more than 100 ppm.

It has been found that the formation of increments can be effectively and safely prevented by using a dye, pigment or specific compound having at least 5 conjugated n bonds and also by controlling the chloride ion (Cl) content of the reaction mixture during polymerization.

Accordingly, the present invention provides a process for the production of vinyl chloride polymer by suspension polymerization or emulsion polymerization of vinyl chloride monomer or a mixture of vinyl chloride monomer with vinyl monomer copolymerizable with vinyl chloride monomer in an aqueous medium.

The incrustation prevention agent may comprise an azine dye and, as an additive, an inorganic compound. The inorganic compound is selected from the group consisting of silicas and silicates, alkaline earth metal salts, zinc group metals, aluminum group metals, tin group metals, iron group metals, manganese group metals, copper group metals and platinum group metals and inorganic colloids .

The inorganic compound is preferably a silicate, colloidal silicic acid or colloidal ferric hydroxide.

The incrustation prevention agent of the method of the invention may preferably contain a fixative to promote adhesion.

As the fixing agent, at least one compound selected from the group consisting of olefin polymers, diene polymers, acetylene polymers, aliphatic vinyl or vinylidene polymers, aromatic vinyl polymers, heterocyclic vinyl polymers, polyethers, polysulfides, polysulfones, addition polymers, polyesters, , polyureas, linear condensed polymers, heterocyclic condensed polymers, natural polymers, modified natural polymers, polysiloxanes, organometallic polymers and inorganic polymers.

The parts of the system for recovering unreacted monomers, where they may adhere to the incrustations, are pre-coated with an incrustation prevention agent.

The inner surface of the walls and portions of the auxiliary device of the polymerization vessel that may come into contact with the monomer have a surface roughness of at most 10 microns.

The above-mentioned incrust prevention agent by the method of the present invention is safely effective so that incrustation can be effectively prevented. There is no laborious and time-consuming removal of incrustations, and the polymerization vessel can be used continuously to increase process efficiency. Also, the cooling capacity of the polymerization vessel is kept constant, eliminating the risk of encrustation in the product, thereby improving product quality.

During the polymerization of the vinyl chloride monomer or vinyl chloride monomer-containing composition, the chloride ion concentration in the reaction mixture generally increases sharply in the initial state of polymerization and then increases little or remains at the same level until the polymerization is complete. The concentration of chloride ions can be influenced by various factors such as the methyl chloride and hydrochloric acid content of the vinyl chloride monomer used as the starting material, the temperature of the water introduced, the degree of vacuum after metering and similar factors. It has been found that the preventive action on the formation of incubations that exhibit dyes, pigments and compounds defined herein having at least 5 conjugated n bonds can be safely induced by controlling the concentration of chloride ions in the reaction mixture during the polymerization process to be at most 100 ppm and preferably. 50 ppm or less. If the concentration of chloride ion in the reaction mixture during polymerization exceeds 100 ppm, even if an agent defined herein to prevent the incrustation is applied to the inner surfaces of the device in contact with the vinyl chloride monomer, the agent cannot be perfectly effective and cannot be effectively prevented.

According to the invention, one or more compounds from the group consisting of dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated n bonds (hereinafter referred to as conjugated n bonds) may be used singly or in combination with each other. However, it is preferred to use a dye or pigment and in particular an azine dye.

Examples of pigmentsain dyes that can be used as incrustation prevention agents in the process of the invention are:

azo dyes such as monoazo dyes and polyazo dyes and pigments, metal complex azo dyes and pigments, stilbene azo pigments, thiazole dyes and similar dyes;

anthraquinone dyes and pigments such as anthraquinone derivatives, anthrone derivatives and the like;

indigo dyes and pigments such as indigo derivatives, thioindigo derivatives and the like;

- carbonium dyes and pigments such as diphenylmethane dyes, triphenylmethane dyes and pigments, xanthene dyes, macridine dyes and similar compounds,

quinone imine dyes, such as azine dyes, oxazine dyes, thiazine dyes, and the like;

methine dyes such as polymethine dyes or cyanine dyes and the like;

quinoline dyes; Nitrodyes; benzocliinone and naphioquinone dyes; naphthalimide dyes and pigments; perinone dyes; sulfide dyes; fluorescent dyes; azo dyes and reactive dyes.

Single compounds or any mixture of at least two such compounds may be used. Among the examples of dyes and pigments mentioned, the aforementioned azine dyes are particularly preferred. The most suitable examples of such dyes and pigments are given below.

Preferred azo dyes and pigments include the following compounds:

Examples of monoazo dyes and polyazo dyes are basic yellow 32, 34 and 36; basic orange 2, 32, 33 and 34; alkaline 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 now 1,4, 11 and 12; basic black 8; azoic diaphragm 4, 21, 27 and 38; dispersion yellow 3, 4, 5, 7, 8, 23, 50, 60, 64, 66, 71, 72, 76, 78 and 79; dispersion orange 1, 3, 5, 13, 20, 21, 30, 32, 41, 43, 45, 46, 49, 50 and 51; disperse red 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 purple 10, 24, 33, 38, 41, 43 and 96; disperse blue 85, 92, 94 and 106; dispersible now 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 reds 1, 3, 23, 24, 25, 27 and 30; solvent blacks 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, 3, 2, 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 1 and 2;

pigment black 1; straight yellow 1, 8, 11, 12, 24, 26, 27, 28, 33, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, and 110; straight orange 1, 6, 8, 10, 26, 29, 39, 41, 49, 51, 57, 102, and 107; 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; straight purple 1, 7, 9, 12, 22, 35, 51, 63, 90, 94 and 98; direct blue 1, 2, 6, 8, 15, 22, 71, 76, 77, 78, 80, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 203,207, 225, 236,

246, 248 and 249; straight green I, 6, 8, 28, 30, 31, 33, 37, 59, 63, 64 and 74; 1A, 2, 6, 25, 27, 44, 58, 59, 101, 106, 173, 194, 195, 209, 210, and 211; straight 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; direct 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, 45, 43, 51, 56, 63, 65, 67 and 95; acid red 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; acid violet 7, 11, 97 and 106; acid blue 29, 60, 92, 113, 117 and 120; acid green 19, 20 and 48; 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; stain yellow 1, 3, 5, 23, 26, 30, 38 and 59; stained orange 1,4, 5, 6, 8, 29 and 37; stained red 7, 9, 17, 19, 21, 26, 30, 63 and 89; mordant violet 5 and 44; stained blue 7, 13, 44, 75 and 76; stained green 11,

15, 17 and 47; dressing immediately 1, 14, 15, 19, 21, 33, 38, 40, 52 and 87; stained 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.

Examples of complex metal azo dyes include: solvent yellow 61 and 80; solvent orange 37, 40 and 44; solvent reds 8, 21, 83, 84, 100, 109 and 121; solvent now 37; solvent black 23; sour red 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, 12, 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 violet 75, 76, 78 and 79; 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, 78 and 79; acidic 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; straight purple 47 and 48; straight blue 90, 98, 200, 201, 202 and 226; 95, 100, 112 and 170.

Stilbene azo dyes are exemplified by direct black 62, and examples of thiazole azo dyes are direct reds 9 and 11.

Anthraquinone dyes and pigments include the following compounds:

Examples of anthraquinone derivatives include basic violet 25; basic blue 21, 22, 44, 45, 47, 54 and 60; azo diazo components 36; vat yellow 2, 3, 10, 20, 22 and 33; vat orange 13 and 15; vat red 10, 13,

16, 31, 35 and 52; vat violet 13 and 21; vat blue 4, 6, 8, 12, 14, 64, 66, 67 and 72; vineyard 8, 13, 43, 44 and 45; kypová 1, 3, 22, 25, 39,41,44, 46, 57

68, 72 and 73; vat black 8, 14, 20, 25, 27, 36, 56, 59 and 60; dispersion orange 11; disperse red 4.9, 11, 15, 53, 55, 65, 91, 92, 100, 104, 116 and 127; dispersed violet 1,4, 8, 23, 26, 28, 30 and 37; disperse blue I, 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; dispersion 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; acid violet 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; acidic 27; acid black 48 and 50; stain red 3 and 11; stained blue 8 and 48; stained black 13; pigmented violet 5.

Examples of anthrone derivatives include vat yellow 1 and 4; vat orange 1,2, 3,4 and 9; vint violet 1,9 and 10; vat blue 18, 19 and 20; vat 1, 2, 3 and 9; vat black 9, 13, 29 and 57; vat red 13; acid red 80, 82 and 83.

Indigo dyes and pigments include the following compounds:

Examples of indigo derivatives include vat blue 1, 3, 5, 35 and 41; reduced vat blue 1; pigment violet 19 and 122; acid blue 74 and 102; soluble vat blue 5 and 41; soluble vat black 1; food blue 1.

Examples of thioindigo derivatives include vat orange 5; vat red 1, 2 and 61; vat violet 2 and 3; pigment red 87 and 88; kypová now 3.

Phthalocyanine dyes and pigments may include, for example, solvent blue 55; pigment blue 15, 16 and 17; pigment green 36, 37 and 48; direct fashion 86 and 199; blue blue 58.

Carbon dyes and pigments include the following compounds:

An example of diphenylmethane dyes is basic yellow 2.

Examples of triphenylniethane dyes include 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; pigmented violet 3; pigment blue 1, 2 and 3; pigment green 1, 2 and 7; straight 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; stained blue 1, 29 and 47; food violet 2; food blue 2; food greenery 2.

Examples of xanthene dyes include 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; stain red 15, 27; food red 14.

Examples of acridine dyes include basic orange 14 and 15.

Quinoimine dyes include the following compounds:

Examples of azine dyes include basic red 2; basic black 2; solvent black 5 and 7; acid blue 59; sour black 2.

Examples of oxyazine dyes include basic blue 3; straight blue 106 and 108;

Examples of thiazine dyes include basic yellow 1; basic blue 9.24 and 25.

Methine dyes include the following compounds: Examples of polymethine (cyanine) dyes include basic yellow 11, 13, 14, 19, 21, 25, 28, 33, and 35; basic orange 21 and 22; alkaline red 12, 13, 15, 14, 27, 29, 35, 36 and 37; alkaline purple 7, 15, 21 and

27th

Examples of quinoline dyes include basic greenery 6; dispersion yellow 54 and 56; solvent yellow 33; acid yellow 3.

Examples of nitro-dyes are dispersed yellow 1.33, 39.42.49 and 54; acid yellow.

Examples of benzoquinone and naphthoquinone dyes are dispersed blue 58 and 108; acidic 103, 104, 106, 160, 161, 165 and 188.

Examples of naphthalimide dyes and pigments include pigment red 123; vat violet 23 and 39; acid yellow 7.

As an example of perinone dyes, vat orange 7 and 15 are mentioned.

Examples of sulfide dyes include soluble sulfur yellow 2, silk yellow 4; seed orange 3; sulfur red 2, 3, 5 and 7; soluble sulfur blue 15; gray blue 2, 3, 4, 6, 7, 9 and 13; seed green 2, 3, 6, 14 and 27; soluble seed immediately 1 and 51; seed 7, 12, 15 and 31; Sulfur Black 1, 2, 5, 6, 10, 11 and 15; vat yellow 35, 42 and 43; vat blue 43 and 56.

Examples of fluorescent dyes include fluorescent brighteners 14, 22, 24, 30, 32, 37.45, 52, 54, 55, 56, 84, 85, 86, 87, 90, 91, 104, 112, 121, 134 135, 162, 163, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 and 177.

Examples of azo dyes are the azo diazo components 17, 20, 22, 24, 26, 31, 35, 41,47, 48, 109 and 121, the azo 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; 2, 7, 11 and 15; azure red 1 and 5, azure yellow 1 and 2; cyan orange 2, 3 and 7; azure red 1, 2, 6, 9, 16 and 24; azure purple 1, 2, 6, 7, 9 and 10; greenery 1.

Examples of reactive dyes are reactive yellow 1,2,3,4, 6,7, II, 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 red 1, 2, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 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 now 1,2, 5, 7, 8, 9, 10, 11, 14 and 16; Reactive Rings 1,3,4, 5, 6, 8, 9, 10, 12, 13, 14 and 18.

Examples of pigments are inorganic pigments such as clirome yellow, zinc yellow, zinc chromate ZTO, lead red, iron oxide powder, zinc bleach, aluminum powder and zinc powder.

Compounds with conjugated n bonds that can be used to prevent incrustations in the method of the invention may have at least two double and / or triple bonds in a conjugated relationship. Aromatic compounds having at least 5 n conjugated bonds that can be used in the method of the invention may include benzene derivatives, naphthalene derivatives, polynuclear aromatic compounds, quinones, non-benzene aromatic compounds and other compounds having at least 5 conjugated n bonds. On the other hand, heterocyclic compounds having at least 5 n bonds may include, for example, oxygen-containing heterocyclic compounds, nitrogen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, bicyclic compounds having a common nitrogen atom, alkaroids and the like having at least 5 conjugated n bonds. Specific examples of these compounds are the following compounds.

Aromatic compounds having at least 5 conjugated V bonds include the following compounds:

Particularly as benzene derivatives, they may include: phenols and phenol derivatives such as 2,6-di-tert-butylphenylphenol, catecholnaphialein, 2,2-diphenylolpropane, 3,7-dioxy-10-methylxanthene, phenolphthalein, 7-oxydimethylbenzopyrooxonium chloride, oxyantraquinone , purpurogallin, Gallein, diphenyl ether, α-methoxyphenazine, chloroglucide, 2,3-dioxyanthraquinone, 5,7-dioxy-4-methylcoumarin, dioxyacridone, salicylic acid, α-hydrindone, β-phenylbutyrophenyl, N-2,4-dinitrophenyl- N-phenylhydroxylamine, 1- (4-nitrophenyl) -3,5-dimethylpyrazole, 9,10-diphenylphenatrene, acetophenone;

aromatic amines and derivatives thereof such as N-phenyl-p-benzoquinone diamine, quinoline, Safranin B, Rosaniline, alcohol-soluble indiurine, aniline black, pararosaniline, methyl purple, methyl orange, methyl red, indigo, carbazole, inethylene blue, o- phenanthroline, p-phenanthroline, 3,6-diaminoacridine, indantrene red 2G, 4-aminodiphenylamine, acridine yellow, 3-aminophenothiazine, N'-diphenyl-p-phenylenediamine, rhodamine, 7-amino-4-methylcumatin, 2-aminophenazine, phenothiazine, diphenylamine, N-methylphenylamine, n-phenyltolylamine, ditolylamine, 2-oxy-4-methylquinoline, yellow Hansa G, N, N'-diphenylphonnamidine, phenanthrophenazine, Bisinark's oil G, 2,3-diaminophenazine, 2-aminododiphenylamine, R, 2,3,7,8-tetraaminophenazine, aminophenoxazone, oxyphenoxazone, tri phenylenedioxadine, 2,4-dinitrophenoxazine, 2,4-dinitro-4-oxy-3-aminophenylamine;

nitro derivatives and nitroso derivatives such as p-nitrosodiphenylhydroxylamine, phenazine, phenazine oxide, 1-phenylazo-2-naphiol, triphenylenedioxadine, 4-nitroxantone, 4'-nitroso-2-nitrodiphenylamine;

phenylhydroxylamine derivatives such as 4,4-dinitrodiphenylamine, bis (p-phenylhydrazine) oxalic acid, bis (β-phenylhydrazine) malonic acid, bis (β-phenylhydrazine) succinic acid, bis (β-phenylhydrazine) phthalic acid;

aromatic halides such as biphenyl chloride;

aromatic aldehydes such as 2-phenyl-1-benzylbenzimidazole, leukomalachite green, malachine green, tetrachlorohydroquinone monobenzoate, benzoflavin, 2-phenylbenzothiazole, 4-benzohydrylbenzaldehyde, bisphenylhydrazone, bis (4-nitrophenylhydrazone);

aromatic ketones such as triphenylisoxazole, benzophenone-calcium, 4-methylbenzophenone, p-toluic acid anilide, benzoic acid toluidide, durylphenyl ketone, 2,4,2 ', 4'-tetrainethylbenzophenone, calchonophenylhydrazone,

1,3,5-triphenylpyrazoline, dinitrobenzyl;

benzoic acids, phthalic acids and derivatives thereof such as quinizalin, nitrodiphenyl ether, benzene derivatives having an additional one substituent other than an aldehyde group such as disaiicylaldehyde, coumarin,

2-benzoylcoumarone, 1-oxy-2,4-dimethylfluorone, 3-phenylcoumarone, ethylcoumarin-3-carboxylate, 3-acetylcoumarin, hydrovaniloin, 4-oxy-3-methoxy-o-nitrostyrene, and- (nitrophenyl) -m- benzoylethylene oxide, dinitrophenylindazole, 5-chloro-3- (4-oxyphenyl) anthranyl, 3-nitroacridone, 6-nitro-3-phenylanthranyl, 2,8-dimethyl-1,9-anthrazoline, carbostyryl,

1,3-dioxyacridine, oxyquinacidine, florchinyl, n-methylquinazoline, 3-acetyl-2-methylquinoline, 2-oxy-3-phenylquinoline, 3-nitroquinoline, quinoline-2,3-dicarboxylic acid ester;

derivatives having one additional substituent other than an acyl group such as 7-oxyflavanone, 7-oxyflavone, 7,8-dioxyflavone, 7-acetoxy-4-methyl-3-phenylcoumarin, 7,8-diacetoxy-4-methyl-3-phenylcoumarin, o-oxybenzophenone, xanthone, 2-phenylbenzooxazole, m-oxybenzophenone, p-oxybenzophenone, 2-benzoylxanthone, 2,4-dioxybenzophenone,

2,5-dioxybenzophenone, 2,2-dioxybenzophenone, xanthene, aurine, trioxybenzophenone, 6,7-dimethoxy-3-phenylcoumarone, o-nitrobenzophenone, m-nitrobenzophenone, 4,4-dibenzoylazoxybenzene, 2- (2-aminophenyl) -4- metylchinón.

2-oxy-4-methylquinone, acridone, 2,4-dimethylquinazoline,

3-cyano-2-oxy-4-methylquinoline, fluorene, anhydro (2-aminobenzophenone dimer, 2-oxy-3-phenylindazole, 3-phenylindazole, 2-phenylbenzimidazole, 2-methyl-8-benzoylquinoline, 2-methyl-4 -phenylquinoline, 4-phenyl-2-quinazolone, aminobenzophenone, chlorobenzophenone, 4-phenylbenzo- 1,2,3-triazine-3-oxide, diaminobenzophenone, 7-methyl-3-phenyl-4,5-benzo-1,2 6-oxydiazine, 4,4'-bisdimethylaminobenzophenone, 4,4-bisdimethylaminobenzophenoneimide,

2,4-dinitro-9-phenylacridine, 4,4'-dibenzoyldiphenyl;

benzene and toluene derivatives having three or more different substituents such as tetramethoxyindigo, 5,6,5 ', 6-bismethylenedioxyindigo, 7-acetoxy-8-methoxy-3- (2-nitrophenyl) carbostyryl, 2,2-dinitrodiphenyldisulfide-4,4' dialdehyde 6-chloro-3-benzoylflavone, 1,3,8-trinitrophenoxazine;

acrylic compounds such as 9-benzylacridine;

diazo compounds and azo compounds such as azobenzene, azotoluene, 2,2-dimethoxyazobenzene, 4,4'-dichloroazobenzene, Ι, Γ-azonaphthalene, 2,2'-dioxyazobenzene, 2,2'-dioxy-5,5'-methylazobenzene, 2, 2'-dioxy-5,5'-methylazobenzene, p-bromoazobenzene, p-nitroazobenzene, phenoazoxide;

aromatic unsaturated compounds such as 2,3,4,5-tetrafenylcyclopentan-2-en-1-one, 1,2,3-triphenylene azulene, 2,2'-dimediphenylacetylene, 4,4'-diethyldiphenylacetylene, triphenylene azulene, 3,4, 3 ', 4-tetramethyldiphenylacetylene, 2,2'-dichlorodiphenylacetylene, 2-nitrophenylacetylene, 2,2'-dinitrodiphenyl acetylene, 2,2'-diaminodiphenylacetylene, 2,2'-dimethoxy-diphenylacetylene, stilbene, α-methylstilbene, α-Ethylilbene, α, β-Dimethylstilbene, α, β-Diethylstilbene, α, β-Dichlorostilbene, α, β-Dibromostilbene, 2-Chlorostilbene, 4,4'-Diiodo-stilbene, α-Nitrostilbene, α, β -dinitrostilben 2

4,6-trinitro-stilbene, 2-amino-stilbene, 2,2'-diaminostilbene, 4,4'-di (dimethylamino) stilbene, 2,2'-dicyanstilbene,

2-oxystilbene, 2-methoxystilbene, 2,2'-dioxystilbene, 2,2'-dimethoxystilbene, 4,4'-dialkoxystilbene, 3,5,2 ', 4'-tetraoxystilbene and polyphenyls and their derivatives such as biphenyl, terphenyl, quaterphenyl, quinophenyl, sexiphenyl, septphenyl, octyphenyl, noviphenyl, deciphenyl, etc.

Further, naphthalene derivatives include: alkylnaphthalenes, alkenylnaphthalenes, phenylnaphthalenes such as 1-methylnaphthalene, 2-methylnaphthalene, 1-ethylnaphthalene,

2-ethylnaphthalene, 1,2-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 1,7-dimethylnaphthalene, 2,3-diinetylnaphthalene, 2,6-dimethylnaphthalene, 2,7- dimethylnaphthalene, 1-propylnaphthalene, 1-isopropylnaphthalene, 2-isopropylnaphthalene, trimethylnaphthalene, diisopropylnaphthalene, 1-vinylnaphthalene, 1-propenylnaphthalene, 1-allylnaphthalene, 1-isopropenylnaphthalene, 2-isopropenylnaphthalenaphthalene, 4-diphenylnaphthalene, 1,2,4-triphenylnaphthalene;

difantyls such as 1,1'-difantyl, 1,2'-difantyl, 2,2'-difantyl;

naphthylarylmethanes such as 1-benzylnaphthalene, 2-benzylnaphthalene, 1- (α-chlorobenzyl) naphthalene, 1- (α, α-dichlorobenzyl) naphthalene, diphenyl-α-naphthylmethane, diphenyl-3-naphthylmethane, 1,8-dibenzylnaphthalene, di α-naphthylmethane, α-naphthyl-β-naphthylmethane, di-β-naphthylmethane, naphthylarylethanes such as 1-phenethylnaphthalene, 1,2-di-α-naphthylethane, 1,2-di-β-naphthylethane, 1,1-α -dinaflyletán;

hydroxynaphthalenes such as 1,2-dihydronaphthalenes, 1,4-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalene;

nitronaphthalenes and derivatives thereof such as dinaphthylpyridazine, 7,8-benzoquinone, 5,6-benzoquinone, naphthazarine, diperimidine, nitromethylnaphthalene, nitroalkylnaphthalene, nitrophenylnaphthalene, haloenitronaphthalene, chlorenedinitronaphthalene, nitrositoline benzinone, dinosinebenzoate, dinosinebenzoate .

1,2,3-triazafenarene, perimidone, perimidine, dibenzoacridine, benzophenazine-12-oxide, diaminonaphthalene, triaminonaphthalene, tetraaininonaphthalene, N-ethyl-α-naphthylamine, N-methylnaphthylamine, Ν, Ν-dimethylnaphthylamine, N-methyl-N- etylnaftylamín, trimetylnaftylamóniová salt, N-phenyl naphthylamines, N-benzylnaftylamin, N-naftyletyléndíamín, N-naphthylglycine, N-p-kyanometylnaftylamín, N-acetylnaftylamín, N-formylnaftylamín, N-benzoylnaftylamín, N-ftaloylnaftylamín, The aminomethyl, nitronaffylamín, dinitronaftylamín, halogénnitronaftylamín, aminotetralins , diamonotetralin;

halogenated naphthalenes such as 1-fluoromaphthalene, 1-chloronaphthalene, 1-chloro-3,4-dihydronaphthalene, 1-iodonaphthalene, 1-bromoimiaphthalene, 1-chloro-4-chloromethylnaphthalene, 1-bromo-2-bromomethylnaphthalene, 1,4-difluoro , 1,2-dichlorophthalene, 1,6-dichlorophthalene, 1,7-dichlorophthalene, 1,5-dichlorophthalene, 1,8-dichlorophthalene, 2,3-dichlorophthalene,

1,4-dibromonaphthalene, 1,4-diiodonaphthalene, perylene, 1,2,3-trichloraphthalene, 1,2,4-tribromonaphthalene, 1,2,3,4-tetrachloraphthalene, 1,4,5-tribromo-3, 8-dimethylnaphthalene, 1,3,6,7-tetrachloraphthalene, 1,3,5,8-tetrabromonflalene, 1,2,3,4,5-pentachloraphthalene;

naphthylhydroxylamines, naphthylpyrazines, and naphthylureas such as α-naphthylhydroxylamine, N ', - phenyl-Na-naphthyl-N-oxyurea, p-naphthylthiohydroxylamine, N-nitroso-α-naphthylhydroxylamine, Neokupferrone, 2-azonaphthalene, 1-oxyonal-l, 1-oxyonal, 1-oxyonal, naphthylhydrazine, 1,2-dibenzocarbazole, 4,4-diamino-1,1'-binaphthyl, 3,4-benzcarbazole, 2,2'-diamino-1,1'-binaphthyl, N-acetyl-Nβ-naphthylhydrazine, N - lauroyl-Nβ-naphthylhydrazine, N'-phenyl-Na-naphthylhydrazine, 2-α-naphthyl-5-nitrobenzotriazole, N, N'-di-α-naphthylhydrazine, 1,1'-diamino-2,2'-binaphthyl, N , N'-di-5-tetralylhydrazine, N- (2,4-dinitrophenyl) -NP-naphthylhydrazine, 2-p-naphthyl-5-nitrobenztriazole, N'-triphenylmethyl-NP-naphthylhydrazine, N, N'-di- Β-naphthylhydrazine, N-methyl-N- (2,4-dinitro-1-naphthyl) hydrazine, 2-amino (β-thio-1 ', 2', -: 4,5-triazole, 1,2: 5,6 -dibenzophenazine, 2-amino (naphtho-2 ', 1': 4,5-triazole), 2,3-dihydrazinaphthalene, 2-phenyl-1,3-bisbenzylidenamino (naphtho-2 ', 3': 4,5-imidazoline) ), N-acetyl-α-naphthylnitrosamine, N-ethyl-α-naphthylnitrosamine, N-phenylnaphthylnitrosamine, α, α'-di-naphthylnitrosamine, bis (β-naphthylnitrosamide) succinic acid, N-ethyl-β-naphthylnitrosamine, N-phenyl β-naphthylnitrosamine, N-acetyl-2-methyl-1-naphthylnitrosamine, 4,5-benzindazole, naphthylnitrosamine, 1-nitro-2-naphthylamine, α-naphthyl-urea, Ν, Ν'-dinaphthylurea, 4-chloro-1-naphthylcarbamoyl chloride, 2,4-dichloroalpha-1 ', 2': 4,5-thiazole], 2-mercapto (naphtho-1,2 '-: 4,5-thiazole), 2-chloro (naphtho-1', 2: 4,5-thiazole), 2-mercaptoalpha-2 ', 1': 4,5-thiazole], 2 chloro / naphtho-2 ', I': 4,5-thiazole /; N- (2,4-dinitrophenyl) N-a-naphthylhydrazine; naphthalenes of the aralkyl compound type such as dibenzoanthrene, acenaphthene, .alpha.-chloroethylnaphthalene, phenylnaphthylchloromethane, diphenylnaphthylchloronethane, nitromethylnaphthalene, aminomethylnaphthalene, (naphthylmethyl) naphthyl (n-phenyl) naphthylmethyl) ammonium salt, tri (naphthylmethyl) amine, di (naphthylmethylamine), [p-naphthylethyl] (alcohol, dimethylnaphthylcarbinol, phenylnaphthylcarbinol, diphenylnaphthylcarbinol, 9-phenylbenzofluorene, naphthylpropylene oxide acetyl, naphthyl methyl) ether (naphthyl methyl) ether (naphthyl methyl) ω-naphthylacetophenone, acenaphthone, dihydrophenarone, phenarone, benzoindanone, naphthylacetonitrile, 9,9-dichlorodibenzofluorene, α-nitro-β-naphthylethylene, γ-naphthylallyl alcohol, β-naphthylacrolein, methyl / naphthylic anhydride, ketyl naphthylic anhydride ;

naphthol, naphthalenesulfonic acids, such as 9-oxynaphthenquinone, 2'-naphthalene-2-indolindigo, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-phenoxynaphthalene, α-naphtholylicylic acid ester, β-naphthol, α-naphthol, α-naphtholic acid ester , α-naphtholeacetic acid ester, phenyl-β-oxynaphthylbenzaliminomethane, β-naphtholphenylmethylamine, methylene-di-β-naphthol, dinaphthopyran, 1'-naphthol-2-indolindigo, 2-methoxynaphthalene, 2-ethoxynaphthalene, N-poxyphenyl-2-N a base, β-naphtholsalicylic acid ester, 2-methyl-1-naphthol, 1,2-naphthamethylenequinone, 1,2-dioxynaphthalene, naphthalenindolindigo, α, Ρ-naphthophenoxazine, Ρ, γ-naphthophenoxazine, 4-oxy-10-methyl- 1 benzocarbazole, dioxynaphthalluoro, dinaphttoquinone, 2,6-naphthocliinone, oxybenzoacridine, 9-oxy-3-dimethylaminonaphthophenoxazine, 1,2,4-trioxynaphthalene, 1,4,5,6-traoxynaphthalene, thio-a-naphthol, 4-mercapto -1-naphthol, 1,5-naphthalenedithiol, methyl-α-naphthyl sulfide, 1,1'-naphthyl sulfide, 1,1'-thiodi-2-naphthol, 1,1'-naphthyl disulfide,,, Γ-thiodi-1-naphthol, thio -P-Naphthol, n aftothioindigo, 1-amino-2-naphthalenethiol, naphthothiantrene, 2-inercapto-1,2-naphthothiazole;

naphthaldehydes and derivatives thereof such as α-naphthoaldehyde, 2- (2,4-dinitrophenyl) -1- (α-naphthyl) ethylene, 2-methyl-1-naphthoaldehyde, 2,3-dimethyl-1-naphthoaldehyde, 4-bromo- 1-naphthoaldehyde, 4-nitro-1-naphthoaldehyde, 2,4-dinitro-1-naphthoaldehyde, 4-amino-1-naphthoaldehyde, 2-oxy-1-naphthoaldehyde, 1-naphthalene-2'-indolinindigo, 1,1 -bis (2-oxy-1-naphthyl) ethylene, 1,2: 7,8-dibenzoxantilium chloride, 2-oxy-1-naphthylethenylpyrylium salt, 5,6-benzocoumarin, bis-methyl-3-indolyl] / 2-oxy -1-naphthyl / methane, 4,5-benzindoxazene, 2-acetoxy-1-naphthalitrile, 4-methoxy-1-naphthoaldehyde, 1,4-bis (4-methoxy-1-naphthyl) -1,3-butadiene, 2-Naphthalene-2'-indolindigo, 3-acetyl-6,7-benzocoumarin, 4-chloro-1-oxy-2-naphthoaldehyde, naphthalenedialdehyde, 5-oxy-2-naphthalenindolinindigo, 5,6,7,8-tetrahydro -2-naphthoaldehyde, imichloride, naphthoamide, naphthoanilide, naphtonitrile, ethyl p-naphthoimidate, p-naphthoamidine, α-naphthoamidoxime, α-naphthohydrazine, naphthostyryl, oxynaphthonitrile, 1,2: 7,8-dibenzoxanthone, 1,2-henzoxanthone 1,1,1-binaphthylene-2,8 '-; 8,2'-dioxide, 2,3, 6,7-d ibenzoxanthone, 3-oxy-2-naphtananilide, 1,3-bis (3-oxy-2-naphthoyloxy) benzene, 2,4-dioxyphenyl-3-oxy-2-naphthyl ketone, 4-arylozo-3-oxy-2- naphthoanilide, 3,4-dihydronaphthalene-1,2-dicarboxylic acid anhydride, 2-aminonaphthalimide, naphthalohydrazine, α-pyridonaphthalone, N-methylnaphthalimide;

acetonaphthene, benzoyl naphthenes such as 1,2: 5,6-dibenzantracene, 2'-methyl-2,1'-dinaphthylketone, 2-methyl-1,1'-dinaphthylketone, styryl-2-naphthylketone, β-naphthoyl acetone, β-naphthoyl acetophenone , 1- (p-naphthyl) -1-chlorethylene, 2- | tris (p-cyanoethyl) acetyl] naphthalene, 1,3,5-tris (p-naphthyl) benzene, dimethyl-2-naphthylcarbinol, 4,5 : 4 ', 5'-dibenzothioindigo, styryl-1-naphthyl ketone, p-acetonaphthone, 1-propionyl-naphthalene, 1-butylnaphthalene, 1-isobutylnaphthalene, 1-stearoylnaphthalene, 1-benzoylnaphthalene, 1-o-toluylnaphthalene, p-b- -1-naphthylketone, 1,2,5,6-dibenzantracene, 1-acetyl-3,4-dihydronaphthalene, 1-acetyl-7-bromonaphthalene, Ι6

-aminoacetylnaphthalene, 2-aminobenzoylnaphthalene, 1-acetyl-2-oxynaphlanene, 1-acetyl-2-methoxynaphlanene, 1-acetyl-4-ethoxynaphlanene, 2-cinnamoyl-1-naphthol, 7,8-benzochromone, 3-acetyl-2-methyl -7,8-benzochromone, 3,4-dimethyl-7,8-benzocoumarin, 4-methyl-3-phenyl-7,8-benzocoumarin, 1-benzoyl-2-oxynaphlanene, 4-oxybenzantrone, 4-benzoyl-1 -naphthol, 3-oxy-1'-benzofluorenone, 2-acetyl-4-chloro-1-oxynaphthalene, α-naphthylglyoxal, β-naphthylglyoxal, 1,4-dibenzoylnaphthalene, phenyl-4-methyl-1-naphlyldiketone.

Polynucleic aromatic compounds include:

anthracenes and their derivatives such as anthracene, 1,1-dihydro-anthracene, 1-chloroanthracene, 1,4-dichloroanthracene, 1,2,7-trichloroanthracene, 1,2,3,4-tetrachloroanthracene, 1-nitroanthracene, 9,10 -dinitroanthracene, 1-aminoanthracene, 2-dimethylaminoanthracene, 2-anilinoanthracene, 9-methylaminoanthracene, 1,4-diaminoanthracene, 1-oxyanthracene, 9,10-dihydroantrol, 10-methylanthranol, 10-phenylanthranol, 10-nitroanthranol, 10-nitroantanol -1-anthranol, 1,2-dioxyanthracene, 9,10-dioxyanthracene diacetate, 1-methylantracene, 4-chloro-1-methylantracene, 1,5-dichloro-2-methylantracene, 9-ethylantracene, 9-vinylantracene, 9- propylantracene, 9-isopropylantracene, 9-butylantracene, 9-isobutylantracene, 9-isoamylantracene, 1,3-dimethylantracene, 9,10-diethylantracene, 1-phenylantracene, 9-phenylantracene, 1,5-dichloro-9-phenylantracene nitro-9-phenylantracene, 9-benzylantracene, 1-benzhydrylantracene, 9,10-diphenylantracene, 9,10-dibenzylantracene, 9,10-diphenyl-9,10-dihydroanthracene, 1- (β-naphthyl) anthracene, 9- / -naphthyl / 10-phenylenedioxy tracene, 9,10-di-a-naphthyl / anthracene, Ι, Γ-biantryl, 2,2'-biantryl, 9,9-biantryl, anthracene-9-aldehyde, 1-acetylantracene, 9-benzoylantracene, 10- ni-troantrafenone, 9,10-dibenzoylantracene, anthrone, 9-mercaptoanthracene, 9,10-disodium-9,10-dihydroanthracene, 10-bromo-9-antiylmagnesium bromide, anthryl mercuric chloride;

phenanthrenes and their derivatives such as phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydrophenylenitrene, 1-chlorophenanthrene, phenanthrene-9,10-dichloro, 1-bromophenanthrene, 1-iodophenanthrene, 9- (chloromethyl) phenanthrene, 1-bromomethyl / phenanthrene, 4,5-bis (bromoinetyl) phenanthrene, 1-nitrophenanthrene, 10-bromo-9-nitrophenanthrene, 1-aminophenanthrene, 9,10-diaminophenanthrene, 9,9'-azoxyphenanthrene, 9,9'- azofenantrén.

1-oxyphenanthrene, cholesterol, estrone, andosterone, 10-bromo-9-phenanthrol, 9-nitro-3-phenanthrol, 4-amino-1-phenanthrol, 10-benzoazo-9-phenanthrol, 1,2-dioxy phenanthrene, reten-3 , 8-diol, 2,3,5,6-tetraoxyphenanthrene, 1-methylphenanthrene, 1-ethylphenanthrene, 1-vinylphenanthrene, 1,2-dimethylphenanthrene, 9,10-diethylphenanthrene, 9,10-dipropylphenanthrene,

2-Ethyl-1-methylphenanthrene, 7-isopropyl-1-methylphenanthrene, 9,10-dihydroretene, aminoethorene, 3-acetoaminoettene, 6-acylaminoettene, 9-phenylphenanthrene, 9-benzylphenanthrene, 1- (a-naphthyl) phenanthrene, 1 1'-biphenanthryl, 9,9'-biphenanthryl, 1-phenanthraldehyde, 2-phenanthradiol, 9-phenanthraldehyde, 1-acetylphenanthrene, 2-propionylphenanthrene, 3-acetylretene, 1-benzoylphenanthrene;

phenanthrenones such as phenanthrene-1,2-quinone, phenanthrene-1,4-quinone, phenanthrene-3,4-quinone, phenanthrene-9,10-quinone, 2-phenyl-3-acetoxy-4,5-biphenylfuran, 7- isopropyl-1-methylphenanthrenone, 1-chlorophenanthrioninone, 2-bromophenanthrenequinone, 2-bromophenanthrenequinone, 2-iodophenanthrenequinone, 2,7-dibromophenanthrenequinone, 2,5-dinitrophenanthrenequinone, 2-aminophenanthanone, 2-oxyphenanthrene-1,4-quinone, 3-oxyphenanthrenequinone, 2-oxyretenequinone, 3-oxyretenequinone, 6-oxyrethenquinone, 2-oxy-3,4-dinitrophenanthrenone, 2-amino-3-oxy phenanthrenone; and polynucleic aromatic compounds and derivatives thereof, such as pentacene, hexacene, benzophenanthrene, benzo [a] anthracene, naphthol [2,1-a] pyrene, dibenzoyajjantracene, pyrene, coronene, 1,12-benzopyrene, ovalene, dibenzoanthracene, naphthacene, Terramycin, Aureomycin, rubrene, o-toluoyl-1-naphthalene, benzoanthraquinone, 5,6-dioxy-5,6-dihudrobenzoanthracene, chrysene, triphenylene, dibenzonaflacene, hexahydropyrene, perylene, 3,9-dichloropropylene, tetrachlerylene, tetrachleryl dibromoperylene, 3,10-dinitroperylene, 4,6-dibenzoyl-1,3-dimethylbenzene, 6,13-dihydropentacene, naphthol [2,3-a] anthracene, dispiran, dibenzo [a, h] anthracene, picene, picylene ketone , picene-5,6-quinone, dibenzo [c, gphenanthrene, benzo [a] pyrene, benzo [a] pyrene-1,6-quinone, mesobenzoantrone pericarboxylic acid anhydride, anthracenol [2, 1a] anthracene, dibenzo [a, 1-anthracene, phenanthrene [2,3-a] anthracene, naphtho [2,3-a] pyrene, dibenzo [a, h] pyrene, dibenzo [a, l] pyrene, zetrene, antantrene, benzo [1,11] perylene, heptacene, tetrabenzo [α, ω] -anthracene, tribenzo [α, 1,1] pyrene, tetrahydrodimethyldinaphthyl, mesonaphthodiantrene, mesoantrodiantrene, 2,3, 8,9-dibenzocorene, e, pyrantrene.

Quinones and derivatives thereof include, for example: benzoquinones and derivatives thereof, such as dibenzoquinoyl disulfide, 2,5-bis (phenylthio) -p-benzoquinone, bibenzoquinone, bitoluchinone, foenicin, Oosporein, indophenol, indoaninin, Hydron blue, indamine, Meldol blue , Wurster blue, Wurster red, 4,4'-diphenoquinone, 4,4'-stilbenchinone, 3,5,3 ', 5', - tetramethyl-4,4'-diphenoquinone, 3,5,3 ', 5, -tetra-tert-butyl-4,4'-diphenoquinone, 3,5,3 ', 5-tetramethyl-4,4'-stilbenchinone, 3,5,3', 5'-tetra-tert-butyl-4, 4'-stilbenchinón;

naphthoquinones and their derivatives, such as 1,2-naphthoquinone, S-oxy-2'-binaflyl-1''D'-dichinone, 5,6-benzoquinoxaline, 1,2-benzophenazine, 2-benzoazo-1- naphthol, 4-Z2,4-dioxyphenyl] -1,2-dioxynaphthalene, 4- (3,4,5-trioxyphenyl) -1,2-dioxynaphthalene, 1,2-naphthoquinone-1-phenyl-itnide, 1,2 -benzophenoxazine, 1,2-naphthoquinone-2-chloroimide, 1,2-naphthoquinium-bis-chloroimide, 2-anilino-1,4-naphthoquinone-4-anil, 2-oxy-1,4-naphthoquinone-4-anil 1,2-naphthoquinone-1-oximbenzoate, 1,2-naphthoquinone-1-oximethyl ether, 1-notroso-2-naphthol, 2-nitroso-1-naphthol, naphtho [1 ', 2': 3,4] furuzan, 1,2-naphthoquinone-2-oximezoate, 1,2-naphthoquinone-2-oximethyl ether, 3-anilino-1,2: 8,9-dibenzophenazine, naphthyl blue, naphthyl violet, 1,2; 5,6-dibenzophenazine, naphlo [1 ', 2': 3,4] furuzan-2-oxide, triflaloylbenzene, hexaoxynaphthalene hydride, 2,2'-binaflyl-1,4; 1 ', 4'-dichinone, 1', 4 ', - dioxynaflo [2', 3 ': 3,4] pyrazole,

4,7-dioxy-3,3-diphenyl-5,6-benzenediazene, 2-diphenylmethyl-1,4-naphthoquinone, methylnaphtho [2 ', 3': 4,5] triazol-1 ', 4-quinone, 1,2,4-triacetoxynaphthalene, 1,4-naphthoquinone-phenylimide, 1,4-naphthoquinone-mono (p-dimethylamino) anil,

1,4-naphthoquinonealkylimide, 4-nitroso-1-naphthol, phenylcarbamate, 4-nitroso-1-naphthylamine, 4-benzhydryl-1,2-naphthoquinone, 2-benzhydryl-1,4-naphthoquinone, 3-benzhydryl-2- methyl-1,4-naphthoquinone, 3-geranyl-2-methyl-1,4-naphthoquinone, 3-famesyl-2-methyl-1,4-naphthoquinone, 2-methyl-3-phytyl-1,4-naphthoquinone, vitamin K1, vitamin K2, 3-allyl-2,6-dimethyl-1,4-naphthoquinone, 2,6-dimethyl-3-phytyl-1,4-naphthoquinone, 2,3-diallyl-6,7-dimethyl- 1,4-naphthoquinone, 2-phenyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2,6-dimethyl-3-phenyl-1,4-naphthoquinone, 3-benzyl-2-methyl- 1,4-naphthoquinone, 2-methyl-3- (4-phenylethyl) -1,4-naphthoquinone, 3-cinnamyl-2-methyl-1,4-naphthoquinone, 2-benzliydryl-1,4-naphthoquinone, 4,7-diketo -8-diphenylmethyl, 7,8,9, tetrahydro-5,6-benzindiazone, 2-ethyl-3-diphenylmethyl-1,4-naphthoquinone, 2,3-diphenyl-1-naphthol,

2 ', 3': 3,4] -pyrazol-1 ', 4'-quinone, 3,4-dichloro-1,2-benzophenazine, 2-iodo-1,4-naphthoquinone; 4,5,8-tetraoxy-2,3,6,7-dibenzothiantrene, 5,8-dioxa-2,3,6,7-dibenzothiantrene-1,4-quinone, 2,3-diphenoxy-1,4 naphthoquinone, dinaphtho (2 ', 3': 2,3] [1 ', 2: 5,4] -furan-1', 4'-quinone, 2,3,5,8-tetrachloro-1,4-naphthoquinone, N, N'-bis- [1,4-naphthoquinon-2-yl] benzidine, 2-aniline-1,4-naphthoquinone-4-anil, 4-anilino-1,2-naphthoquinone-2-anil, phenylrosindarin, 2- anilino-1,4-naphthoquinone-4- (p-dimethylamino-anil), 2-anilino-1,4-naphthoquinone dianil, 2-anilino-3-phenyl-1,4-naphthoquinone, 2-aniline-3-bromo-1, 4-naphthoquinone, 2-aniline-4-chloro-1,4-naphthoquinone, 2,3-diaililin-1,4-naphthoquinone, 2,3-dianiline-1,4-naphthoquinone dianil, nitrosoamino-naphthoquinone, 3-chloro-2- Phenylnitrosamino-1,4-naphthoquinone, phenyl-bis- [3-anilino-1],

4-naphthoquinon-2-yl] -amine, 3-chloro-2- (p-tolylnitrosoamino) -1,4-naphthoquinone, 2,7-dioxy-1-nitrosonaphthalene, 4-benzenesol-1,3-dioxynaphthalene di- [3-oxy-1,4-naphthoquinonyl-2-methane, anhydroalkannin, dichinoxalino [2 ', 3': 1: 2, 3: 3,4] naphthalene, 3,4-phthaloylfurazane; and anthraquinones and derivatives thereof such as 1,2-anthraquinone, 2,3-anthraquinone, 1,4-anthraquinone, 9,10-anthraquinone, 1,5-anthraquinone, 2,6-anthraquinone, 1,10-anthraquinone, 9,9-bis / p-oxyphenyl / anthrone, anthraquinone bisdiphenylmethide, bisphenylhydrazone, benzantrone, anthrahydroquinone, β-ethylanthraquinone, 1,3,5,7-tetramethylanthraquinone, 2,2-diantraquinonylethane, 2,2'-diantraquinonylethylene, 1,2 , 3-trioxyanthraquinone, anthracryzone, erythrooxyanthraquinone, alizarin, quinizarin, antrarufm, chrysazine, hystazarin, antraflavin, isoantraflavin, anthragallol, purpurine, oxyantrarufin, antrapnpurpurin, oxychrysazine, oxychrysazine, 2-chloroquinizarin, 1-nitroanthraquinone, purpurine, 2,4,6,8-tetrabromantrachrysone, 3-aminoantrapurpurine, 1,8-dinitroanthraquinone, α-aminoanthraquinone, 1,1'-dianthraquinonyl, dianthraquinoneimide, 1,4-methylaminoanthraquinone, 5 amino-l-nitro-6,8-dibromo moantraquinone, 1,5-tetramethyl diamino-

4,8-dinitroanthraquinone, anthraquinoneacridone, bis-N- (2-oxyanthraquinolyl) -p-phenylenediamine, leucochinazarine, quinazarine green, 1-amino-2,4-dibromo-anthraquinone,

1,4-dialcylamino anthraquinone, anthraquinone-β-aldehyde, odiazine, 6,7-phthaloyl-1,9-benzantrone, oxynitrosoanthraquinone, 1,1-dianthraquinolyl, azoxyanthraquinone, 8-chloropyrazolantrone, 2,6-dihydrazinoanthraquinone, anthraquinone, anthraquinone anthraquinonehydrazine, azoxyantraquinone, pyrazolantrone, 1- (anthraquinolyl-2 / -3-methylpyrazolone, 1-hydroxylaminoantraquinone, 1,5-dihydroxylaminoanthraquinone, 1-nitrosoanthraquinone, 1-hydrazinanetraquinone, 1,

5-dihydrazinanthraquinone, 1-azidoanthraquinone, 2-azidoanthraquinone, anthraquinone methylsulfoxide, 1,4-dirhodananthraquinone, β, β'-dianthraquinolylsulfide, anthraquinonesulfenyl chloride, 2,2'-dianthraquinonyl, 1,1-dianodroquinone, 2-dianodianotianone, heliantrianinone, heliantrianin, 2'-diamino-1,1'-diantraquinolyl, flavantrone, 2,2'-diantryl, mesonaphthodiantrone, 1,1'-dianthraquinolylamine, quinizarinquinone, hystazarinquinone, alizarinquinone, 6-oxyquinoline quinone.

Non-benzene-type aromatic compounds include, for example, azulene, cyclodecapentane, cyclotetradecapentane, cyclooctadecanone, cyclotetracosadodekaene, heptalene, fluvalene, sesquifluvalene, heptafluvalene, perinaftene, indeno (2,1a) perinaphene, dibenzo [dibenzo [dibenzo] dibenzo [dibenzo] cyclo- [3,2,2] azine, 4,5-benzotroporone, 3,4-benzotroporone, 5H-benzocycloheptene, 7H-benzocycloheptene, colchicine, colchicein, colchinol methyl ether, ditropylether, ditropylsulfide, cyclopentadienyltropylidene, benzoazulene, -benzotropone, 2-phenyltropone, naphthycycloheptadienone, naphthropropone, three benzotropone, 1-amino-1,3-dicyanoazulene, benzoylhydrazone, 3-phenyl-1-oxaazuranone-2,2-benzyltropone, 3-methyl-2-phenyltropone, 2 , 7-diphenyltropone, 2- (a-naphthyl) tropone, 2,7-tetramethylene-4,5-benzotropone, naphtho [2 ', 3-4, S] tropone, naphthol [2', 1'-2,3] tropone, dibenzosuberan, naphtho [1,2'-2,3] tropone, dibenzosuberol, 4-oxy-2-phenyltropone, 4 _> 5 _> 7-tribromo-2-phenyltropone, 3,5'-di troporón.

3- (p-methoxyphenyl) troporone, 4-oxy-2-phenyltropone, 3- (a-naphthyl) troporone, 3,4-diphenyltroporone, 3,7-dibenzyltroporone, 4- (1'-phenylpropylhroporone), 3,5 ' -bitroporonyl, 4-p-nitrostyryl-aminopropionyl ether, 2-amino-1,3-dicyanoazurene, benzo [b] tropothiazine, 5-bromo-2-phenyltropone,

4-bromo-2,7-diphenyltropone, diphenylbiphenylcarbinol, thiazinotropone.

Examples of heterocyclic compounds with at least five conjugated linkages include the following:

Examples of oxygen-containing heterocyclic compounds are:

furan and its derivatives such as 2,5-diphenylfuran, 2-phenylfuran, 3-methyldiphenylfuran, lepidene, pyridoxine, 2,4-diphenylfuran;

benzofuran, isobenzofuran, dibenzofuran and derivatives thereof, for example dibenzofuran, furano [2 ', 3'-7,8] flavone, egonol, Euparin, 1,3-diphenylisobenzofuran, tetrafenylglycol, tetrafenylphthalane, 9-phenylantracene, o-oxymethylbinol triphenyl 3'-diphenylphthalide, 1-phenylphthalane, 1,1-phenylflalan, 3,3-diphenylphthalide, rubrene, α-sorinine, dibenzofuran, 2,2'-dioxybiphenyl, 2,2'-diaminobiphenyl, phenazone, dibenzoquinone, 2-hydroxybenzofuran 2-methylbenzofuran, benzo [a] benzofuran, benzo [b] benzofuran, dibenzo [a, f] dibenzofuran, dibenzoyl dibenzofuran, dibenzo (c. Dibenzofuran, bis (2-dibenzofuryl), bis / 3-dibenzofuran;

pyran and pyrone derivatives such as 2-p-oxyphenyl-4,6-diphenylpyryliumferrichloride, anhydrobase, benzopyran, 4-p-oxyphenyl-2,6-diphenylpyliumferrichloride, 6-phenylcoumarin;

Chroinenol and chromene derivatives such as 6-methyl-2,3-diphenylchromone, 6-methyl-2,3-diphenyl-4- (p-tolyl) -1,4-benzopyran-4-ol, cliromanol, γ-chromene, oxychroman , chromene, cyanisine chloride, fisetine, 6-oxy-3-inethoxy-5,7-dimethylflavium chloride, 4,4'-diflavilene-3,3'-oxide, chrysinidine, apigenidine, rotoflavinidine, lutosonidine, galanginidine, fisenidine, molinidine, flavoneimine , pelargonidine, cyanidine, delfinidine, pentunidine, syringidine, hirsutidine, apigeninidine, carajurine, dracorhodin, dracorubin;

flavone, flavonol and isolavone derivatives such as llavonol, flavone, fukugetin;

coumarin and isocoumarin derivatives, for example 7-oxy-3,4-benzocoumarin, dicoumarol, angelicin, psoralen, bergapten, bergaptol, xantotoxin, xantotoxal, isopimpinellin, pimpinellin, oroselol, oroselon, peucedanin, oxypeucedanin, ostutel, medutol, medutol, medutol, medutol xanthyletin, santoxyletin; and xanthone and related compounds such as dixanthylene, 9-phenylxanthene, isoxanthone, 1,2,7,8-dibenzoxanthene, 3,9-diphenylxanthene, 9,9-diphenylxanthene.

Examples of nitrogen-containing heterocyclic compounds are:

pyrroles such as 1-phenylpyrrole, 5-phenylpyrrole-2-aldehyde, phenyl-2-pyrrylketonoxime, 2-phenylpyrrole, 2-methyl-1-phenylpyrrole, 2-methyl-4-phenylpyrrole, 2-methyl-5-phenylpyrrole, 3 -methyl-5-phenylpyrrole, 2,4-diphenylpyrrole, 2,5-diphenylpyrrole, 2,3-diphenylpyrrole, 2,3,5-triphenylpyrrole,

1,2,3,5-tetrafenylpyrrole, 2,3,4,5-tetrafenylpyrrole, 2,3,4,

5-tetrafenylpyrrole, diphenyl-2-pyrrylcarbinol, pyrrolocyclotrimethine dye, pyrrolpolmethylene dye, biliverdine, bilirubin, prodigiosin, stercobilin;

indoles such as 5,7-dichloro-2-phenylindole, 7-chloro-2-phenylindole, 5,7-dibromo-2-phenylindole, 7-bromo-5-chloro-2-phenylindole, 2- / 3'-indolyl -3-Isonitroindolenine, Roseindol, Triptophan blue, indole [3,2-c] quinoline, indole [1,2-c] quinazoline, 2-phenylindole, 3-nitro-2-phenylindole, 3-phenylindole, N-methyl 3-phenylindole, 3- (o-nitrophenylAndole),

2,3-diphenylindole, 3-triphenylmethylindole, 2-methyl-3-triphenylmethylindole, 2-phenyl-3-triphenylmethylindole, 2- (1-naphlyl) -3-triphenylmethylindole, 2- (2-naphthyl) -3-triphenylmethylindole, 3,3'-diindolyl, 3,2'-diindolyl, 3,3'-dehydrodiindole, Roseindol, 3-nitroso-2-phenylindole, 3-nitro-2-phenylindole, 2-methyl-3-phenylazoindole, 2-phenyl -3-phenylazoindole, 6-oxy-3-phenylindole, triptophan, 4,5-benzotriptophan, 6,7-benzotriptophan, violasein;

indole oxoderivatives such as 3- (4-ethoxy-1-naphthyl) oxyindole, indophenine, indigoazine, indigo yellow 3G;

isoindoles such as 1-chloro-4-melylflalazine, 1-benalidene-phthalimidine, 2-methyl-3-phenyl-phthalidinidine, 2-methyl-1,3-diphenyl-isoindole, 2,5-diphenyl-isoindole, β-isoindigo, dimethylimno-β-isoindigo;

carbazoles such as 1-phenyl-1,2,3-benzotriazole,

2,2-diaminodiphenyl, 1,1-dicarbazole;

porphyrins such as porphyrazine, magnesiumoctainethyltetraazaporphyrin, azadipyromethine, phthalocyanine, diazacoproporphyrin, porphyrin, mesotetrafenylporphirine, chlorophyll-b, chlorophyll-a;

oxazoles such as 2-phenyloxazole, 4-phenyloxazole, 5-phenyloxazole, 2-methyl-4-phenyloxazole, 2-methyl-5-phenyloxazole, 4-methyl-2-phenyloxazole, 5-methyl-2-phenyloxazole,

4,5-dimethyl-2-phenyloxazole, 2,4-diphenyloxazole, 2,5-diphenyloxazole, 4,5-diphenyloxazole, 2-methyl-4,5-diphenyloxazole,

2.4.5-triphenyloxazole, 2- (o-nitrophenyl) oxazole, 2- (p-nitrophenyl) oxazole, 2-amino-5-phenyloxazole, 2- (p-aminophenyl) oxazole, 2- (o-aminophenyl) oxazole, 4,5-dimethyl-2-phenyloxidooxazole, 4-methyl-2,5-diphenyloxidooxazole, 2,4,5-triphenyloxidooxazole, 4- (o-methoxycarbonylbenzal) -2-phenyl-5-oxazolone, oxacarbocyanine dye, phenantrooxazole;

isoxazoles such as 4-nitro-3-phenylisoxazole, 5-amino-3-methyl-4-phenylisoxazole, 5-benzoyl-3,4-diphenylisoxazole;

thiazoles such as 4-phenylthiazole, 5-phenylthiazole, 5- / p-fluorophenylthiazole, 2-methyl-4-phenylthiazole, 4-ethyl-5-phenylthiazole, 5-methyl-4-phenylthiazole, 4,5-diphenylthiazole, 2-methyl- 4,5-diphenylthiazole, 1,4-bis (4-methyl-2-thiazolyl) benzene, p, p'-bis (4-methyl-2-thiazolyl) biphenyl, 2-amino-4-phenylthiazole, 2-amino -5-Phenylthiazole, 2-amino-4,5-diphenylthiazole, 2-phenylazothiazole, 2-amino-4-methyl-5-phenylazothiazole, 4-methyl-2-phenylazothiazole, β-naphthothiazole, α-naphtothiazole, naphthol | [3] thiazole, naphthoyl 1,2-thiazole, 2-methyl-1,2,2-thiazole, 2-phenyl-naphtho 1,2-thiazole, 2-methyl-naphtho [2,1] thiazole, 4-bromo-2-phenyl-naphtho [2,3] thiazole, 2-oxynaphtho [2,1-thiazole, 2-aminonaphtho [1,2] thiazole, 2-aminonaflo [2,1-thiazole, 2-mercapto-naphtho11,2] thiazole, 2-mercapto-naphtho [2,1-thiazole;

imidazoles such as 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2-phenylimidazole, 2,4-diphenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-bromo-4-phenylimidazole, 5-chloro -1-ethyl-2-phenylimidazole, 5-chloro-1,2-diphenylimidazole, 2-phenylazo-imidazole, 2-methyl-4-phenylazoimidazole, 2- (o-aminophenyl) -benzoquinidazole;

pyrazoles such as 3-phenylpyrazole, 5-phenylpyrazole, 4-phenylpyrazole, 1-methyl-3-phenylpyrazole, 1-methyl-5-phenylpyrazole, 3-methyl-5-phenylpyrazole, 1,3-diphenylpyrazole, 1,5-diphenylpyrazole 1,3,4-triphenylpyrazole, 1,3,5-triphenylpyrazole, 1,4,5-triphenylpyrazole, 5-amino-3-phenylpyrazole, 3-amino-5-phenylpyrazole, 5-methyl-1,3- diphenylpyrazole-4aldehyde, 3,5-diacetyl-4-phenylpyrazole, 4-benzoyl-1,5-diphenylpyrazole;

oxadiazoles such as 3-phenylfurazan, 3,4-diphenylfurazan, naphtha [1,2] furazan, phenylfuroxane, 3-methyl-5-phenyl-1,2,4-oxadiazole, 2,5'-diphenyl-1,3, 4-oxadiazole;

thiadiazoles, e.g. 5-phenyl-1,2,3-thiadiazole, 2-phenyl-1,3,4-thiadiazole, 5,5-diphenyl-2,2'-bis (1,3,4-thiadiazole), 2 -oxy-5-phenyl-1,3,4-thiadiazole, 2-methylsulfonyl-5-phenyl-1,3,4-thiadiazole;

triazoles such as 2-phenyl-1,2,3-triazole, 5- (p-aminophenyl) -3-mercapto-1,2,4-triazole;

tetrazoles such as 5-phenyltetrazole, 1,5-diphenyltetrazole, 1-oxy-5-phenyltetrazole, 1-amino-5-phenyltetrazole;

pyridine and related compounds such as 2-phenylpyridine, 2,2'-dipyridyl, 2-chloro-6-phenylpyridine, 2,6-dichloro-3-phenylpyridine, 2,2-azopyridine, 3,3-azopyridine, benzene-4 -azopyridine, 5-chloro-2,2'-azopyridine, 5,5'-dichloro-2,2'-azopyridine, 4-pyridylazoresorcin, 4-pyridyl-m-phenylenediamine, 1-pyridyl-m-phenylenediamine;

quinoline and the like, such as quinoline, quinaldine, quinaldine N-oxide, ethylquinoline, 2-phenylquinoline, 3-methylquinoline, 3-phenylquinoline, 4-methylquinoline, 4-phenylquinoline, 6-methylquinoline, 6-ethylquinoline, 6-phenylquinoline, 6-phenylquinoline 2,4-dimethylquinoline, 2,4-diphenylquinoline, quinoline-4-methanol, quinoline [6,5-quinoline, quinophthalone, flavaaniline, cliinoline blue, ethyl red, pinacyanol, naphthoanol, cryptocyanine, xenoocyanine, azacyanine, 6, 6'-octahydroquinone, Bestlioma red, 2,3-quinoline, 2,5'-quinoline, 2,6'-quinoline, 2,7-quinoline, 3,3'-quinoline, 4,5'-quinoline, 4, 6'-quinoline, 5,5'-quinoline, 6,6'-quinoline, 6,7'-quinoline, 6,8'-quinoline, 7,7'-quinoline, 8,8-quinoline, 2-fluoroquinoline, 3-fluoroquinoline, 4-fluoroquinoline, 5-fluoroquinoline, 6-fluoroquinoline, 7-fluoroquinoline, 8-fluoroquinoline,

3-bromoquinoline, 4-chloroquinoline, 2,4-dichloroquinoline,

3-nitroquinoline, 4-nitroquinoline, 2,3-quinolinediol, quinoline-2-thiol, 2-oxy-quinoline-3-thiol, 2-aminoquinoline, 8-aminoquinoline, 2-hydrazinoquinoline, pyrroloquinoline, thiazoloquinoline, pyriinido [4, 5-b] quinoline, benzoquinoline;

isoquinoline and related compounds such as 1-methylisoquinoline, 3-bromomethylisoquinoline, 1-phenylisoquinoline, 4-phenylisoquinoline, 1,1'-biisoquinoline, 5,5'-biisoquinoline, 1-chloroisoquinoline, 5-iodoisoquinoline, 5-bromoisoquinoline, 5-bromoisoquinoline nitroisoquinoline, isoquinoline-1,3-diol, 6,7-methylenedioxyisoquinoline, 1-aminoisoquinoline, 1-cyanoisoquinoline, 1-phenylbenzo [g] 3,4-dihydroixoquinoline, 3- (p-aminophenyl) -5,6-dihydro- 8,9-dimetoxyiinidazol | 5-a] isoquinoline;

acridine and related compounds, for example: acridine, 1-methylacridine, 9-phenylacridine, 9- (3-pyridinyl) acridine, 2-chloroacridine, 2-bromoacridine, 2-acridinol, acridine-2,6-diol, 4-methoxyacridine, 9-phenoxyacridine, 1-nitroacridine, 4-aminoacridine, 1-aminoacridine, 9-phenylaminoacridine, 9-oxyacridine, chryzaniline, acrriflavine, 3,6-diamino-4,5-dimethylacridine, acrynol;

phenanthridines such as 3,4-benzoquinoline, 6-methylphenanthridine, 6-aminomethylphenanthridine, 6-phenylphenanthridine, 6-chlorophenanthridine, 6-bromophenanthridine, 6-nitrophenanthridine, 1-aminophenanthridine, 3-oxyphenanthridine;

anthrazolines such as pyridole [2,3-g] clioquinoline, 2,7-diphenyl- [2,3-g] quinoline, 2,8-diphenylpyrodolo [3,2-g] quinoline, phenanthrolines, and related compounds such as 1, 7-phenanthroline, 1,10-phenanthroline, 4,7-phenanthroline, 8-me

276 Tyl-1,7-phenanthroline, 4,10-dioxy-1,7-phenanthroline, 3,5-dichloro-1, 10-phenanthroline, 2-amino-1, 10-phenanthroline, 5-oxy4,7 - phenanthroline, 5-amino-4,7-phenanthroline;

pyridoindoles such as 1,9-pyridoindole, 2,9-pyridoindole, 4,9-pyridoindole;

naphthylidine, and related compounds such as 1,5-naphthylidine, 1,7-naphthylidine, 1,8-naphthylidine, 1,6-naphthylidine, 2,6-naphthylidine, 2,7-naphthylidine, 1,5-naphthylidine-4 -ol, 3-amino-1,5-naphthylidine, 1-aino-1,5-naphthylidine, 2-oxy-1,7-naphthylidine;

oxazine and related compounds such as Cenoxazinone, resazurin, carocyanine, Nile blue. A, Meldor blue, brilliant cresyl blue;

thiazine and related compounds such as o-benzaminophenyl-β-phenoxycarbonylethylsulfide, phenothiazine, nitrophenothiazine, 3-chloro-10-ethylphenothiazine, 4-amino-4'-anilino-diphenylsulfide, 2-chloro-10- (3-dimethylaininopropyl) phenothiazine, 10- [2-dimethylamino-1-propyl] phenothiazine hydrochloride, 10- [2- / 1-pyrrolidyl / ethyl] phenothiazine hydrochloride, 10- [1-methyl-3-piperidylmethyl] phenothiazine, 2-acetyl-10- / 3-dimethylaminopropyl / phenothiazine, methylene blue;

pyridazine and related compounds such as cinnolin,

3-methylcinnoline, 4-chlorocinoline, 3-bromocinoline, 4-cinnolinol, 4-aminocinnoline, phthalazine, 4-ethyl-2-phenylphthalazinone, phthalazinethiol, 1 / 2H / phthalazinone, 3-phenyopseudophthalazine,

4-methyl-3-phenylpseudophthalazine, 2,3-dihydro-1,4-phthalazinedione;

pyrimidine and related compounds such as 2-trifluoromethylpyrimidine, 4,6-dimethyl-2-phenylpyrimidine, 2,4,6-triphenylpyrimidine, alloxanthin, 2,6-dioxy-4-phenylpyrimidine, 4,6-dioxy-2- phenylpyrimidine, 5-chloro-4,6-dioxy-2-phenylpyrimidine, sulfadiazine, sulfisomidine, tonzylamine hydrochloride, vitamin B1, thiochrome, co-carboxylase, allomycin,

6- (2-furfuryl) -aminopurine, pteridine, 2,4-pterindiol, 2-amino-6-methyl-4-pterindiol, xantopterin, leukopterin, isoxantopterin, quinazoline, 4-chloroquinazoline, 2,4-dichloroquinazoline, 4- quinazoline, 2,3-diphenyl-4-quinazoline;

pyrazine compounds such as 3,6-diphenylpyrazole, quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline,

2-chloroquinoxaline, 2,3-dichloroquinoxaline, 2- (o-aminoaniline) qumoxaline, N, N'-diphenyl-2,3-piperazine, 2-quinoxalinol, 2,3-quinoxalinediol, 2-aminoquinoxaline, 2,3- diaminoquinoxaline, methylquinoxaline-2-carboxylic acid ester, 2- (d-arabotetraoxybutyl) quinoxaline, flavazo, glucasidone, phenazine, phenazine-5-oxide, phenazine-5,10-dioxide, 5-methylphenadienium methyl sulfate, 10-methyl-5,10 -dihydro-2-phenazinecarbonitrile, 2-phenazinecarbonitrile, 1-phenazinol, 1-methoxyphenazine, 2-phenazinol, 1,6-dioxyphenazine-5,10-dioxide, 1-aininophenazine, 2-aminophenazine, 2,3-diaminophenazine, neutral red, 5,10-dihydrophenazine, 5-methyl-5,10-dihydrophenazine, 1,2,3,4-tetrahydrophenazine;

tri- and tetra-hetero six-membered cyclic compounds, for example 2,4,6-triphenyl-s-triazine, 2,4-dichloro-6-o-chloroaniline-s-triazine, 5,6-diphenyl-as-triazine, 2 , 6-diphenyl-2,3,4,5-tetrahydro-as-triazine, 5,6-diphenyl-as-triazin-3-ol, 1,2,

4-benzotriazin, 1 J, 4-benzotriazin-3-ol, 3-phenyl-1,2,3-benzotriazin-4- (3H) -one, 1,2,3-benzotriazin-4-ol, 1,2 3-benzotriazine-4-thiol, 3-amino-1,2,3-benzotriazine, 2,3-diphenyloxotetrazine, 5,6-dimethyl-2,3-diphenylozotetrazine, 5-cyano-2,3-diphenylozotetrazine, , 6-dibenzoyl-2,3-diphenylozotetrazine, 2,3-dibenzoyl-5-methylozotetrazine, 2,3-dibenzoyl-5,6-dimethylozotetrazine, 2,3-dibenzoyl-5,6-diphenylozotetrazine, 2,3-bis / 2,4-dichloro-phenyl / -5,6-diphenyl-2,

3,4-tetrahydro-v-tetrazine, 1,2,3,4-tetraethoxycarbonyl-5,5-diphenyl-1,2,3,4,5,6-hexahydro-v-tetrazine, 7-methyl-2- (4-Methylphenyl) -1,2-dihydrobenzotetrazine, 3,6-diphenyl-

1,2-dihydro-s-tetrazine, 1,3-diphenyl-1,4,5,6-tetraliydro-s-tetrazine, 3,3,6,6-tetraphenyl-1,2,3,6-tetrahydro-s- tetrazine.

Sulfur containing heterocyclic compounds include:

sulfur-containing heterocyclic compounds, for example, 2-phenylthiophene, 2,4-diphenylthiophene, 2,3,4,5-tetrafenylthiophene, metaphenylenelihydrochloride, metapyrylene hydrochloride, chlorotencitrate, thenyldiamine hydrochloride, α-quinothienyl, α-sexytientyl;

thiophene compounds such as 3,3'-diminothioindigo, indigorone, dihydronaphio [2,1b] thianaphthene _>

1,3-diphenylisothianaphthene, dibenzothiophene, 2-nitrobenzothiophene, amine-dibenzothiophene, 2,8-diaminodebenzothiophene, dibenzothiophene-5-dioxide, 4-oxydibenzothiophene, 2,8-dioxydibenzothiophene, 2-chlorodibenzothiophene, 2,8-dibromibenzene, 1-bromodibiibene iodo-dibenzothiophene, 2-acetyldibenzothiophene, 2,8-diacetyldibenzothiophene, naphthothiophene, 3-oxytiophantrene, 2,3-thiophantrene, naphtho [2,3-c-thiophene, naphtho [1,2-b] liophene, naphtho [2, 1b] thiophene, naphtho [1,2-c] thiophene, 1,2-naphtho [2,1b] thiophenquinone, 1-oxy-2-naphtho [2,1-b] thiophenaldehyde, naphtho [1,2-c] thiophene, 2H-naphtho [1,8] thiophene, benzo [b] thiophantrene, 6,11-benzo [b] thiophanthraquinone, benzo [thi] gthiophantrene, 4,5-benzothiophantrene, 8,9-benzothiophantrene;

five-membered monocyclic compounds containing two heteroatoms, for example 5-phenyl-1,2-dithiol-3-thione, 3,4-dihydronaphtho-2,1-trition, thiaflavone, thiacumarin, thiaxanthene, thiaxantohydrol, thiaxanthone, Milacil D, bistiaxanthylene;

six-membered cyclic compounds with at least two heteroatoms, for example 2,5-diphenyl-1,4-dithiadene, thiophenaldehyde, thiantrene, 2,7-dimethylthiantrene, 1-thiantrenyllithium, 1-chlorothiantrene, phenoxatin, 2-vinylphenoxatin, 2-aminophenoxatin -nitrophenoxatin, 3,7-dinitrophenoxatin, 10,10-diphenylphenoxatin, 2,5-diphenylthiophene.

Other suitable compounds include, for example:

dicyclic compounds having usually a nitrogen atom, for example cinchonine, 2-phenylpyrrocoline, 3-ethyl-2-phenylpyrrocoline, 3-benzyl-2-phenylpyrrocoline, 3-nitroso-2-phenylpyrrocoline, 2: 3-benzopyrrocoline, 1,5,8- trimethyl-2: 3-benzopyrrocoline, 1-ethyl-5,8-dimethyl-2: 3-benzopyrrocoline, 1,8-diinetyl-2: 3-benzopyrrole, 3-phenyl-7: 8-benzopyrrocoline, cyclo [3,3, 3] azine, cyclo [3.2.2] azine, 2-phenylcyclo | 3.2.2 | azine, 2,3-diphenylcyclo [3.2.2] azine, tricycline, 7-methylbenzo [a] quinolinium bromide, 7-phenylbenzo [a] quinolidinium bromide, benzo [b] quinolidinium salt, tetrahydro-β-berberine, tetrahydroberberine, laudanosoline, tetrahydro-2,3,9,10-tetraoxy-7-methyldibenzopyrrocolium chloride, hoinolaudanosoline, octadehydromatrin, canadinemetododine, tetrahydropalodiodine, tetrahydropalodiodine, tetrahydropalodiodide, tetrahydropalodiodide, tetrahydropalodiodide, tetrahydropalodiodide, tetrahydropropanediodide;

alkaroids such as nicotyrin, 3 ', 2-dipyridyl, cusparine, galipoline, 1-methyl-2-quinolone, casimiroin, 2-pentylquinoline, 4-oxy-2-pentylquinoline, 4-methoxy-2-pentylquinoline, 1-methyl- 2-pentyl-4-quinoline, 4-methoxy-2-phenylquinoline, 7-methoxy-1-methyl-2-phenyl-4-quinoline, kusparein, dictanin, skimmianin, evolitrin, maclurin, coccaginin, coccaginin, maculosadine, flundersiamine, evoxoidin, evoxin, evolatine, acronycidin, medicosmin, acrronidine, γ-fagarine, cinchonine, quininone, quinotoxin, N-bromoquinotoxin, dihydrocinchonicin, heteroquinine, evoxantidine, xantochinoline, 1,3-dimethoxy-10-methylanthridine, x-methylanridine, melicopidine, inelicopicin, acronycin, flindersin, papa verapine, papaveraldine, laudanosine, laudanine, codamine, protopapaverine, almepavine, 4,4 ', 5-trimethoxy-2-vinylstilbene, coclaurin, d-isococlaurin, nepotin, magnendaverine, corendaverine, corendaverine, corendaverine , coclanoline, narcotine, narcotoline, aponarcein, cinchonine, cinchotoxin, dihy drohydrastin, bicuculline, adlumidine, corltunidine, cordrastin, magnolamine, berbamine, o-methylberbamine.

Of these n-bonded compounds, at least one amino acid compound is preferred. Particularly preferred compounds are, for example, aminonaflanenes such as diaminonaphthalenes, triaminonaphthalenes and tetraaminonaphthalenes, 1,4-diaminoanthracenes, 9,10-diaminophenanthrenes, 2,2-diaminodiphenyl, 1,1'-diamino-2H-dinaphthyl, 2-amino-5- phenyloxazole, 1-aminophenanthridine, 2-amino-4-phenylthiazole, 2-amino-5-phenylthiazole, 3-amino-1,5-naphthyl,

1-aminophenanthridine, aminoacridines such as 4-aminoacridine,

2-aminoacridine, 1-aminoacridine, 3,6-diaminoacridine and aminophenazines such as 1-aminophenazine, 2-aminophenazine and 2,3-diaminophenazine.

In a preferred embodiment of the method of the invention, the incrustation prevention composition may comprise at least one inorganic compound in addition to at least one dye, pigment and conjugated π-bonded compound. Any inorganic compound alone does not prevent the formation of incrustations, and unexpectedly, the anti-destructive effect of dyes, pigments or n-conjugated compounds is promoted when used in conjunction with the inorganic compound. This phenomenon is more secure when the concentration of chloride ions in the reaction mixture is controlled to be no more than 100 ppm. If the concentration of chloride ions is above 100 ppm, the action of the composition is not sufficient to prevent the formation of incrustations.

When a mixture of a dye, pigment or n-conjugated compound with an inorganic compound is applied in the form of a coating, for example, to the inner wall of the polymerization vessel, the proportion of both components may preferably be 0.1 to 2000 parts by weight, inorganic compound preferably 1 to 1000 parts by weight. per 100 parts by weight of dye, pigment or conjugated compound.

Inorganic compounds include, for example, silicas or silicates such as orthosilicic, metasilicic, mesodicinicic, mesosilicic, sodium metasilicate, sodium disilicate, sodium disilicate, sodium tetrasilicate, potassium metasilicate, potassium metasilicate, potassium metasilicate, potassium metasilicate, potassium metasilicate, potassium metasilicate, -12-silicotungstic acid, 10-silicotungstic acid, potassium-12-silicotungstate, potassium-12-silicotungstate, potassium-12-silicotungstate, sodium-12-silicotungstate, siliconium borate, silicomolybdate, silicomide borate, silicomolybdate;

metal salts such as oxyacid salts, acetates, nitrates, hydroxides or halides of metals selected from the group consisting of alkaline earth metals such as magnesium, calcium, barium, aluminum group metals such as aluminum, tin group metals such as titanium, tin, metals iron, such as iron, nickel, chromium, such as chromium and molybdenum, manganese, such as manganese, copper, such as copper, silver, platinum, such as is, for example, platinum;

inorganic colloids obtainable by mechanical comminution, irradiation, exposure to ultrasonic wines, electrical dispersion or chemical methods such as colloidal gold, colloidal silver, colloidal sulfur, colloidal ferric hydroxide, colloidal silicic acid, colloidal silicic acid, colloidal manganese colloidal, colloidal manganese colloidal , colloidal barium sulfate, colloidal vanadium dioxide, colloidal aluminum hydroxide, colloidal lithium silicate.

Of the inorganic compounds mentioned, silicates, silicic acid and colloidal ferric hydroxide are particularly preferred.

In the coating, the anti-encrusting agent can be applied to the inner walls of, for example, the polymerization vessel itself or in the form of a coating solution prepared by dissolving or dispersing in a suitable solvent. The concentration of the solution to prevent intentions is generally at least 0.01% by weight.

The solvent which may be used in the preparation of the coating solution may be water or may be various organic solvents. Examples include:

aliphatic hydrocarbons such as petroleum ether, petroleum, gasoline, mineral gasoline, ligroin, petroleumV.M. & P., decalin, tetralin and p-cymene;

aromatic hydrocarbons such as benzene, toluene, xylene;

halogenated hydrocarbons such as trichlorethylene, perchlorethylene, chloroform, carbon tetrachloride, ethylene trichloride, benzene monobromide, benzene monochloride, benzene dichloride;

alcohols such as amyl alcohol, ethyl alcohol, isopropyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, methylamyl alcohol, benzyl alcohol, butyl alcohol;

ketones such as acetone, acetonylacetone, diisobutylketone, diethylketone, dipropylketone, methylamylketone, methylbutylketone, methylcyclohexanone, methyldipropylketone, methyl ethyl ketone, methyl-n-hexylketone, methylisobutylketone, methylpropylketone, mesityloxide;

esters, for example acetates, butyrates, propionates, formats;

alcohol esters, for example butyl lactate, isopropyl lactate, ethyl lactate, ethyloxypropionate, diethyl maleate;

ketone esters such as ethyl acetoacetate, ethylpyruvate;

ethers such as isopropyl ether, ethyl ether, diethylcarbitol, diethylcellosolve, butyl ether;

ketone alcohols such as acetonylmethanol, diacetone alcohol, dihydroxylacetone, pyruvyl alcohol;

tert-alcohols such as isopropylcellosolve, carbitol, glycidol, cellosolve, glycoether, benzylcellosolve, butylcarbitol, butylcellosolve, methylcarbitol, methylcellosolve, triethylene glycol monoethyl ether;

a ketone ether, for example acetalethyl ether, acetonylmethanol ethyl ether, methylethoxyethyl ether, ester esters such as butylcarbitol acetate, butylcellosolvacetate, carbitol acetate, cellosolvacetate, 3-methoxybutyl acetate, methylcarbitol acetate, methylcellosolvacelate.

When highly water-miscible organic solvents are used, water may be added to the coating composition in an amount that does not interfere with the solubility or dispersibility of the composition that is incrusted, thereby simplifying the cost and safety of transporting and storing the coating composition. Examples of such solvents are:

alcohols such as methanol, ethyl alcohol, allyl alcohol, n-propyl alcohol, isopropyl alcohol;

ketones such as acetone, acetonylacetone, diacetone 11

Alcohol, esters such as ethylene glycol monoethyl ether acetate, diethylene glycol ethyl acetate, monoethyl ether acetate;

ethers such as dioxane, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, furans such as tetrahydrofuran, furfuryl alcohol;

aprotic solvents such as acetonitrile, N, N-dimethylformamide, Ν, Ν-dimethylacetamide.

Where the anti-incrustation agent used is a water-soluble dye of the sulfonic acid or carboxylic acid type having sulfonic acid or carboxylic acid groups in the form of an alkali metal salt or an ammonium salt, water may be used as the solvent, and dissolves in water as described in Japanese Patent Specification No. 5442/1981; this has advantages in terms of safety and hygiene at work, since the solvent is non-toxic and harmless. When water is used as the solvent as described above, the wettability of the inner walls of, for example, a polymerization vessel, can be improved by the addition of an alcohol, preferably monovalent alcohols having 3 to 6 carbon atoms such as n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, sec-hexyl alcohol, as described in Japanese Patent Specification No. 5444/1981. Similarly, as described in Japanese Patent Specification No. 5442/1981, water-compatible organic solvents such as alcoholic solvents, ester solvents and ketone solvents may be added to the coating composition to improve drying of the coating composition.

When coating the inner walls of, for example, a polymerization vessel with a coating solution containing the anti-fouling agent using the method of the invention, various fixing agents may optionally be added to promote adhesion of the composition. The fixing agents can be used in a variety of ways, for example, they can be incorporated into the coating solution containing the anti-incrustation agent, or the fixing agent or its solution is applied to the walls before the anti-incrustation agent is applied, whereupon the anti-incrustation agent solution is applied. the appropriate method is chosen according to the type of anti-incrustation agent used and the type of fixative.

Examples of fixing agents are polymeric compounds:

olefin polymers, for example polyethylene, polyethylene sulfonic acid, polypropylene, poly (1-butane), polyisobutane, polycyclopentene, polycyclopentylethylene, polycyclohexylethylene, poly (3-cyclohexyl-1-propene), poly (4-cyclohexyl-1-butane), 5-cyclohexyl-1-pentene (poly) (cyclotrifluoroethylene), poly (cyclotrifluoroethylene), poly (Aetrafluoroethylene);

diene polymers such as polyallene, polybutadiene, polyisoprene, polychloropyrene, poly (1-methoxybutadiene), poly (2-tert-butyl-1,3-butadiene), poly (cyclopentadiene), poly (1,3-cyclohexadiene), poly) dimethyllulvine (poly), 4-vinyls-1-cyclohexane (poly), 1,5-hexadiene (poly), 1,5-cyclooctadiene (poly), bicyclo-22,1-hepta-2,5-lien) poly (5,7-dimethyl-1,1,6-octadiene), poly (diallyl phthalate), poly (diallylmethylsilane), poly (diallylphenylphosphine oxide);

acetylene polymers, for example polyacetylene, polycyanoacetylene, poly (hydroxymethyl) acetylene, polybutoxyacetylene, poly (phenylacetylene), poly (diphenyldiacetylene), poly (pyridylacetylene);

aliphatic vinyl polymers and vinylidene polymers, for example polyvinyl alcohol, polyallyl alcohol, poly (vinylfloral), poly (vinyl acetate), poly (vinylbutyral), poly (vinylisobutyral), poly (vinylcyclohexanone ketal), poly (vinyl acetate, poly (vinyl chloroacetate), poly (vinyl chloroacetate), poly) /, poly (vinyl pivalate), poly (vinyl n-caproate), poly (vinyl caprylate), poly (vinyl laurate), poly (vinyl palmitate), poly (vinyl benzoate), poly (vinyl sulfate), polyvinyl 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 (vinylcarbomethoxymethyl ether), poly (vinyl-2-methoxyethyl ether), poly (vinyl-2-chloroethyl ether), poly (vinyl-2,2,2-trifluoroethyl ether), poly (vinylbenzyl ether), poly (vinylmethylketone), poly (methylisopropenylketone) (poly (1-nitropropylene), poly (vinylsulfofluoride), poly (vinylsulfonic acid), poly (vinyldirenylphosphine oxide), poly (vinyldiphenylphosphine oxide), poly (vinyldiphenylphosphine sulfide), poly (dimethyl 2-cyano-2-propene-1-phosphonate), poly (diethyl 2-cyano-2-propene-1-phosphonate), poly (maleic acid anhydride);

aromatic vinyl polymers, for example 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-vinylphthalic acid), poly (4-vinylphenylboronic acid), poly (diphenyl-4-styrylphosphine oxide), poly (diphenyl-4-styrylphosphine sulfide), poly (9-) vinylantracene (), poly (4-vinylbiphenyl), poly (acenaphthylene), polyindene;

heterocyclic vinyl polymers, e.g., poly / N-vinylpyrrolidone /, poly / 9 ^A-5 -pentanylkarbazol /, poly / 9-Δ ⁵ -hexenylkarbazol /, 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-morpholinone-), polycoumarone;

acrylic and methacrylic polymers, for example polyacrylic acid, polymethacrylic acid, poly (methyl acrylate), poly (ethyl acrylate), poly (butyl acrylate), poly (5-cyano-3-thiaphenylacryl), 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 / di-lauryl methacrylate / poly / 4-tert-butyl / phenyl methacrylate, poly (bomylmethyl acrylate), polyP- (N-carbadyl) ethyl methacrylate, poly tert-butyl crotonate, polyacrylinitrile, polymethacrylonitrile, polyacrylamide, poly (N-dimethylacrylainide), poly (N-) 1,1-dimethylbutyl-3 (acrylamide, poly (acrylicopiperidine), poly- (acrylomorpholide), poly (9-acryloylcarbazole), polymethacrylamide, polyacrolein, poly (α-methylacrolein), poly (diacryloylmethane), poly (acrylic anhydride), poly (methacrylic anhydride) polymers, for example polyformaldehyde, polyacetaldehyde, poly (mono-chloroacetaldehyde), polychlorine a1, polypropionaldehyde, polyacrolein, poly (2-formyl- ^{3 3} -dihydropyran), poly (trans-1,2-cyclohexanedicarboxyaldehyde), poly (glutardialdehyde), poly (p-methylglutardialdehyde), poly (p-phenylglutardialdehyde), poly ( dimethyl ketene (), polyacetone, poly (monobromoacetone), poly (7-oxabicyclo [2.2.1] heptane, poly (3-phenoxylene), poly (2,6-xylenol), poly (ethylene oxide), poly (propylene oxide), poly (cyclopentene oxide), poly (cyclohexene oxide), poly (phenylglycidyl ether), poly (1,2-diepoxyethyl) benzene, poly (3,3-bis (chloromethyl) oxetane), poly (tetrahydrofuran);

polysulfides, polysulfones, for example polyAiocarboxylfluoride (poly), ethylene dichloride sodium tetrasulfide (polydichlorodiethylethyl disulfide), poly (dichlorodiethylenetetrium tetrasulfide), poly (phenylene sulfone (poly) ethylene sulfone), poly (ethylene sulfone), poly (ethylene sulfone), poly (ethylene sulfone), poly (ethylene sulfone); poly (styrene sulfone), poly (1-pentylsulfone), poly (1-hexylsulfone), poly (1-heptylsulfone), poly (butadiene sulfone, poly (isoprene sulfone), poly (dimethylbutadiene sulfone), poly (1,5-hexadiene sulfone), poly (cis, cis-cyclooctadiene sulfone), poly (norbomadiene sulfone);

various addition polymers, for example, poly (methylene diisocyanate), poly (ethylene diisocyanate), poly (trimethylene diisocyanate), poly (tetramethylene diisocyanate), poly (5-iminohydantoin), poly (perfluoroglutarodinitrile), polyl (1) perilide;

formaldehyde resins, for example phenol-formaldehyde resin, melamine-comfortable-aldehyde resin, urea, formaldehyde resin, aniline-mono-aldehyde resin, p-toluenesulfonamide formaldehyde resin, polyesters, for example poly (11-oxyundecanoate), poly (hexamethylene succinate), poly (hexamethylene succinate) hexamethylene-α, α'-dibutyl sebacate (poly), octamethylene cis-hexahydrotereilate (poly), octamethylene transhexahydroterephthalate (poly), hexamethylene maleate (poly), hexamethylene fumarate (poly), hexamethylene acetylene poly (ethylene terephthylene) polyethylene terephthalate (ethylene) ethylene diisate) , poly (4,4-biphenylene isophthalate), poly (hexamethylene carbonate), poly (p-phenylene carbonate), poly (m-phenylcarbonate), poly (4,4-isopropylidene diphenylene carbonate, poly (4,4 '- / 2-pentylene) - diphenylene carbonate /, poly (1,2-bis (hydroxamethyl) carboranadipic acid), poly (allylsulfonate), poly (hydroquinone-aryloxyphosphoryl dichloride), poly (hydroquinone- / chloromethyl) phosphoryl their chloride), polydichloro (hydroquinone- (N-dimethyl) phosphoramidic acid);

polyamides such as poly (isocyanate), poly (vinyl isocyanate), poly (butalisocyanate), poly (3-aminopropionic acid), poly- (6-aminopropionic acid), poly (11-aminoundecanoic acid), polydiexamethylene adipamide / poly (decamethylene adipamide) poly (3,3'-methylimino (bistrimethylene adipamide), poly (benzidinisophthalic acid), poly (aromatic diamine pyrromellitic dianhydride), poly (1,6-hexamethylene-bi) carboxyethyl (sulfide), poly (chloride-1,6-) hexamethylenediaminobenzene-1,3-bis-sulfonic acid /, poly (trans-2,5-diinetylpiperazine-4,4-sulfonyldibenzoyl chloride), poly / bis / 3-aminopropyl / phenylphosphinadipic acid, poly / bis / 3-aminopropyl / phenylphosphine terephthalic acid acid (), poly (bis) 3-aminopropyl-2-methylphosphinoxidadipic acid], poly (bis (3-aminopropyl) -n-octylphosphinnadipic acid), poly (bis) -

3-aminopropyl (phenylphosphinoxidadic acid), poly (hexamethylenediamine-bis (2-carboxyethylene) phenylphosphine oxide), poly (hexamethylenediamine-bis (p-carboxyphenyl) phenylphosphine oxide), poly (piperazine-bis (2-carboxyethyl) phenylphosphine oxide);

polyureas, polyurethanes, for example polyureas, poly (1,10-decamethylenediainine-1,6-hexamethylene-bis-ethylurethane), poly (diphenylmethane-4,4'-diisocyanate-4,4'-diphenylmethane), polyololuene-2,4 -diisocyanate-N, N'-bis (trimethylsislyl-β, P'-diaminodiethyl ether), polyurethane, polyurethane poly (propylene oxide) base;

various linear condensed polymers, for example poly (diethylcarbodiimide), poly (diallylcarbodiimide), poly (di-n-butylcarbodiimide), poly (methylisopropylcarbodiimide), poly (di-n-hexylcarbodiimide), poly (di-phenylcarbodiimide), poly (4,4) poly (1,3-xylylenecarbodiimide), poly (1,3-xylylenecarbodiimide), poly (3-methyl-1,4-phenylene-carbodiimide), poly (2,2'-dimethylbiphenylenecarbodiimide), poly (2,2'-dimethoxybodiimide) poly (1,5-naphthylenecarbodiimide), poly (adipyldihydrazide succinoyl chloride), poly (adipyldihydrazide isophthaloyl chloride), poly (isophthalenedihydrazide terephthaloyl chloride), poly (2,5-dimethylbenzylene), poly (p-xylylene), poly (p-xylylene), 2,5-dimethoxy-p-xylylene (poly), p-xylydene, poly (α-cyano-m-xylylidine), poly (α-cyano-p-xylylidine), poly (nitrophenylene), polyAetramethyl-p-phenylenedimethylene, poly (2,5-dihydroxy-p-phenylenedimethylene), poly (4,4'-oxydiphenylenedimethylene), poly (2,5-dimethoxy-p-phenylenedimethylene);

heterocyclic fused polymers such as poly (benzoimidazole), poly (alkylene-5,5-dibenzoimidazole), poly (allylene-5,5'-dibenzoimidazole), poly (pyromellitimide), poly (benzooxazole), poly (oxadiazole), poly (oxadiazolidine) (poly) (dithiazole), poly (benzothiazole), poly (1,4-xylenyl) 2-methylpyperazine (poly) quinoxaline (poly) 3-triazinyleneimide);

natural polymers, modified natural polymers, for example, natural rubber, cyclized rubber, chlorinated rubber, gutta-percha, cellulose, methylcellulose, ethylcellulose, propylcellulose, butylcellulose, allylcellulose, benzylcellulose, hydroxyethylcellulose, carboxymethylcellulose, cellulose triacetate, cellulose triacetate, cellulose triacetate, cellulose tricaprate, cellulose tricarbanilate, cellulose tributyrate, cellulose nitrate, cellulose trinitrate, starch, amylose, amylose acetate, amylose carbanilate, arnylopectin, alginic acid, quinine, glycogen, arabic oil, tragacanth oil, heparin, pectin, pectin, pectin casein, collagen (calf leather), collagen (ichthyol), gelatin, groundnut protein, salt protein, nuclein protein (veal thymus), nuclein protein (sea urchin sperm), polysarcosine, sericin, silk, wool, zein, polyadenylic acid, deoxyribonucleic k acid, ribonucleic acid;

polysiloxanes, for example polysiloxane, polydimethylsiloxane;

organometallic polymers such as poly (bis) divalent metal imidazolate, poly alummium triisopropylate ethylenediamine) and inorganic polymers such as polymetaphosphates and the like.

According to the method of the present invention, said incrustation prevention substances are applied to the inner surface of the walls of the polymerization vessel and to the internal parts of the auxiliary devices of the polymerization vessel where they could adhere to the incrustations, in particular applied to the internal parts of the device which may come into contact with the monomer They are also applied to the inner surface of the device where contact with the monomeric is possible, for example applied to the stirrer blades, the stirrer shaft, the condenser and the like. Preferably, the incrustation prevention agent is further applied to unreacted monomer parts of the regeneration system, where the incrustation could also adhere, for example, to the inner surface of the monomer distillation columns, capacitors, monomer storage tanks, valves and the like.

There are no particular restrictions on the construction materials of the polymerization apparatuses and on the parts of the auxiliary equipment of the polymerization apparatus, but materials such as stainless steel or glass lining materials are suitable. parts,

The surface to be coated should preferably have a roughened surface (Rmax, defined according to JIS B 0106) of ΙΟμιη or otherwise, preferably not more than 5 micrometers.

There is no particular restriction on the methods of applying the incrustation prevention agent to the inner surface of the polymerization apparatus and the auxiliary equipment of the polymerization apparatus: the incrustation prevention agent may be applied by brush, spraying, filling the polymerization vessel with coating solution and subsequent draining and other automatic coating methods that are No. 61001/1982, 36288/1980, Japanese Patent Application Publication (Kohyo) No. 501116/1981, 501117/1981 and Japanese Patent Application Publication (Kokai) No. 11303/1984.

The process of the invention is applicable to the homopolymerization of a vinyl chloride monomer and to the copolymerization of a vinyl chloride monomer with other vinyl monomers in an aqueous medium. It is suitable for either suspension or emulsion polymerization. Vinyl monomers which can be used for copolymerization are, for example, vinyl esters, for example vinyl acetate, vinyl propionate, acrylic acid, methacrylic acid or their esters and salts, maleic acid or phthunaric acid and their esters or salts, diene monomers, for example butadiene, cliloprene or isoprene, further styrene, acrylonitrile, vinylidene halide, vinyl ether.

In suspension and emulsion polymerization, compounds such as organic peroxides are used as polymerization catalysts, for example tert-butyl peroxyneodecanate, di-2-ethylhexyl peroxydicarbonate, 3,5,5-trimethylhexanoyl peroxide, α-cumyl peroxyneodecanate, cumene peroxide peroxoperoxide, cyclohexyl peroxide peroxide, cyclohexene. di-2-ethoxyethylperoxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropylperoxydicarbonate and acetylcyclohexylperoxide, as well as azocatalysts, for example, α, α'-azobisisobutyronitrile, <x, α-azobiser 2,4-dimethylsulfonate for example potassium persulfate and ammonium persulfate. As dispersants, for example, suspending agents such as natural or synthetic polymer compounds can be used, for example, a partially saponified polyvinyl acetate product, a polyacrylic acid, a vinyl acetate / maleic anhydride copolymer, a cellulose derivative such as hydroxypropyl methylcellulose and gelatin;

emulsifiers include, for example, nonionic emulsifiers, for example sorbitan monolaurate, sorbitan trioleate, anionic emulsifiers, for example sodium lauryl sulfonate, sodium alkylbenzene sulfonate. Other additives may be added to the polymerization system, such as fillers such as sodium carbonate, titanium dioxide, stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin laurate, dioctyltin mercaptide, lubricants such as wax, stearic acid, cetyl alcohol, plasticizers such as DOP, DBP, chain extenders such as trichlorethylene, mercaptans and pH-controlling agents. The process of the invention effectively prevents the formation of incrustations, no matter which catalyst, dispersant or other additive is used. The process according to the invention is explained in more detail by the following non-limiting examples.

(Note: Examples 218-300 are skipped in the following examples).

DETAILED DESCRIPTION OF THE INVENTION

Example 1

As shown in Table I, in each example a coating solution prepared using a dye or pigment soluble or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymer compound, is used. The amount of inorganic compound or polymer compound used is also shown in Table I, and the concentration of the dye or pigment in the coating solution is always given. The coating solution is applied to the polished internal walls of a 1000-liter stainless steel polymerization vessel and to parts of the equipment that may come into contact with monomer such as stirrers, the coating is dried at 80 ° C for 10 minutes and then rinse thoroughly with water.

The internally coated polymerization vessel is then charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 44 g of partially saponified polyvinyl alcohol Palo, 56 g of hydroxypropylmethylcellulose and 60 g of t-butyl peroxyneodecanate, and the polymerization is carried out at 52 ° C for seven hours. Upon completion of the polymerization, the polymer is removed and the polymerization vessel is washed inside with water at a flow rate of 0.1 m ³ / m ² h as shown in Table 1. The above operations from coating and filling the poleinerization vessel to water washing are performed for each batch and the procedure is repeated a maximum of 200 times.

The concentration of chloride ion in the reaction mixture during polymerization in each test is controlled by varying the methyl chloride and hydrochloric acid content of the starting vinyl chloride monomer, the feed water temperature (from 10 to 80 ° C), and the degree of vacuum after deionized water (-100 to -13 kPa) ). Different vinyl monomer materials with different contents of methyl chloride and hydrochloric acid are prepared by mixing two types of vinyl monomer (1), especially a vinyl monomer containing 40 to 50 ppm methyl chloride and up to 2 ppm hydrochloric acid and (2) a monomer containing 1000-3000 ppm methyl chloride and 1 to 10 ppm of hydrochloric acid at varying weight ratios from 80. 100 to 20: 0.

After polymerization of each batch, the chloride ion concentration is measured as defined in JIS K 0102 (1974). For each test, Table I shows the mean value and the maximum and minimum values of the measured amount of chloride ion concentration.

At the end of each test, incrustations after the 10th, 30th, 50th, 150th and 200th doses are also assessed visually by comparison with the standard below and the amount of increment adhered (g / m ² ) after the last batch polymerization is measured. The results are also shown in Table I.

Standard scales:

A: no adherence adherence

B: a few percent of the adhered sand sands of those incrustations

C: incrustations coat part of the surface in a thin layer (about 10% of the surface)

D: incrustations coat the surface in a thick layer (about 10% of the surface)

E: incrustations coat part of the surface in a thin layer (approximately 50% of the surface)

SK 277795-6

F: incrustations coat part of surface in rough layer (approximately 50% of surface)

G: incrustations coat the entire surface in a thin layer H: incrustations coat the whole surface in a thick layer

In Table I, the asterisks are marked with an asterisk. In the case of Examples 1 and 2, the surface of the inner walls of the polymerization vessel is not coated

T.bulk · 1111 compound and is not treated in any way. For Examples 33 and 34, the surface of the inner walls of the polymerization vessel is treated with a coating solution prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 parts of dye to the resulting solution: the coated surface is heated to 80 ° C for 30 minutes.

Povlattový rortok

<1) Ex. Dye or pigment («) inorganic (Al / (b) Polysérna (a) / (c) (2) solvent No. weight compound 2lúčrnina weight horses Species Ratio miefiariia (B) ratio <C> ratio X type Mixing ratio * 1 - - - - 2 * - - - - 3 * Solvent Drain 5 - 0.5 Hetan 4 * - - 5 * · - - · · · 6 * · colloidal Si0 ₃ 100/50 - 0.9 7 * · 100/150 Lacquer 100/50 1> 5 · · e * ' CuCls 100/2 - 0.5 - Colloidal SiOq O / 1OO - 0.5 1O * Solvent CerA 7 FeCl 100/5 - 0.5 * 11 Sour Red 2 Colloidal SiOa 100/200 - 0.9 12 » alkaline Water glass 100/150 1.0 Water / 90/100 orange 14 Isobutyl and cobal

Table 1 (1) (continued)

<1) Pr. e. (3) Cl ^- horses. upper * middle loweri max.-min. ppm (4) Water wash time after min. VIžiAIm hnflnntwip 1 Batch C direct mnn!>, t, vp -aZjB'l 10 30 50 100 150 200 * 1 300 350-280 60 H (1000) 2 » 15 17-12 H (900i 3 * 300 350-270 B F HÍ800) 4 ' 200 250-1Θ0 · ' B F H (500> 5 » 150 180-130 B C F H (300> 4 ' 250 280-200 B D F H <300) 7 * 300 340-270 B C F H (200) e * 280 310-250 · · B C F H <350) 9 * 15 17-12 · H (900) * 10 230 200-200 B C F H (250) * 11 250 290-210 · · 0 C F H (220> * 12 250 280-200 B C F H <400>

SK 277795-6

Table 1 (2)

<1) Ex. no. Coating solution Dye or pigment <a) Inorganic compound h (b) (a) / (b) weight ratio Polymer compound (C) (a) / (c) weight ratio (2> horses. X solvent Kind of Mixing species Pomer mixing * 13 Acid blue 102 70/30 Ortekremic and she 100/200 1.5 Water (alkaline plowing 14) acid 14 « Alkaline red 2 FeiOHH salt 100/50 - 1.0 methanol 15 » Basic 2 FeCl ₃ 100/3 - 0. 5 * 16 Basic plowing 2 Colloidal · SiOe 100/100 - L. 0 Water * 17 Basic now 1 FeíQHÍa. salt 100/10 - 0.5 IB * Acid ČerA 2 - - 0.5 * 19 Disperse Black 29 - - 0.7 acetone * 20 Moridlová ČerA 9 - - 0.5 Water 21 Basic Black 8 - - 0.5 - 22 Basic now 1 - - 0, 6 Water / I frogs L alcohol 90/10 23 Basic now 1 Fe (OH) j salt 10 (.1 / 10 - 0.6 90/10 24 Basic plowing 2 Colloidal äiC_ 1MU / 100 - 0.8 Water

Table 1 (2> (continued)

(1) Ex. e. t3) Cl “horse, upper: medium lower: max.” min. pprn <4 1 Water wash time after min. Viauáinír inlay rating (too many) n / tf> Batch no. 10 30 50 100 150 200 * 13 260 290-230 60 B C F H (350) * 14 270 320-250 · · B C G HÍ400) 13 « 230 290-210 · · B C F H (300) * 16 250 300-220 B C F H <450) * 17 500 350-280 B F H (400) 19 « 310 370-290 · · B F H (600 J 19 « 265 315-245 · B F H t 700) * 20 285 335-265 B F Hí 500) 21 15 18-13 10 A A A B C D (15) 22 19 21-16 · · A A A B C 0 (16) 23 16 18-15 · A A A A A A (0,2) 24 13 15-10 A C A A A A (0,5)

Table 1 (3)

Coating rortok

(1> Ex. Dye or pigment <a> Inorganic (A) / (b) Pol ymárna (A) / (c) (2) solvent e. Kind Ratio of 1ucenini (b> weight ratio compound <c> weight ratio horses. 1 species Pomer mieftenj 2S Alkaline Red 32 - - 0.3 Water 26 Dispersion plowing 5 - - 0.5 acetone 27 Dispersion purple 10 - - 0.9 - 28 Disperse Black 29 - - 1.0 29 Pigment now 4 - Polycycles for 1-hexylethylene 100/50 1.5 methanol 30 Solvent 21 'bi / alkaline blue 44 S * '/ 50 - - 0.8 Water / Methanol 70/30 31 Start up now 37 / vat blue 6 40/60 - - 0, b · ' 50/50 32 Vip plowing 15 - - 0, 7 xylene 33 Kypová zeleA 44 - - 0, 5 Water 34 Kypová now 22 - - 0, 5 35 Vip plowing 1 / vip blue 19 30/70 - 1. about xylene 3b Alkaline blue 7 NiCl _s 100/20 - 1, o Water / n- 80/20

Amy 1 and I whom!

Table 1 (3) <continued J

<1) Pr. no. <3 i Cl ~ kone. upper middle lower: max.-min. ppm <41 Water wash time after completion min. Viiu61ne Intrmtäcia mnri? st-vn gZin2 1 e dose ČρπΓηιιΙέ č. 10 30 50 100 150 200 25 14 16-13 10 A A A B C D (18) 26 10 12-Θ A A A A B C <?. 5> 27 11 13-9 A A A B C D (20) 28 12 14-10 A A A A B C (7> 29 18 20-16 A A A A B C (91 30 16 18-14 15 A A A A B CÍ9) 31 20 22-10 A A A A B C C 1O) 32 9 11-7 « A A A A B C (7.5) 33 5 7-3 A A A A B Ct6,4) 34 15 1 7-13 A A A B C DC 18> 35 13 15-10 · ' A A A A B C t 10) 36 14- ² 11 A A A A A A {0,7>

Table 1 <4>

C1J Pr. e. Coating solution Dye or pigment (al Inorganic compound (B) (a) / <b) Polymer weight compound ratio (c> (a) / (c) by weight ratio (2) kane, X solvent Species Ratio mie Lania species Pomer mixing 37 Basic plowing 14 Water glass 100/150 0.9 Water 38 Pigment Blue 15 - Polycyk 1opentadiene 100/100 0.0 THF 39 Pigment Red 07 - <α1y <1> 3-cyclo hexadien - 100/30 0.8 acetone 40 Solvent blue 73 - - 0, 4 methanol 41 Solvent worm 49 - - 0.7 42 Rezppustad 1 evá t »rvefl 49 Sulfur colloid 100/5 0.7 43 Basic plowing 15 - - 1.3 Water 44 Diluent Cer A 5 CuCls 100/2 0.7 Water / Methanol 30/70 45 Alkaline CerA 2 FeCl _a 100/0 0.0 Water 46 Alkaline Blue 3 Methacrylic acid IOO / IOO 1.5 47 Alkaline blue 9 - - Ú, B 48 Basic CerveA 13 4. 4 Water / n— Butyla1kohol 50/50

Table t (4> <continued)

(1) Pr. no. (3) Cl ”horses, upperx middle range ma * t.-min. ppm (4) Water wash time after min. visually InkruatAria evaluation (ρτίΓηιιΙΓ Batch no. annfitl e / e? 1 10 30 They are 10C 150 200 37 9 11-7 15 A A A A A A4O.61 38 10 12-8 A A A A D C <9> 39 13 15-10 A A A B C D <17) 40 8 10-5 10 A A A A B C <10) 41 10 12-E A A A A B C <11) 42 15 17-13 A A A A A And (O, 8) 43 14 16-12 · · A A A A B L (0> 44 13 13-11 A A A A A A (0,2) 45 15 17-12 A A A A A A (0.3> 46 17 19-15 · A A A A A A (0,5) 47 15 17-12 H A A A A B C <6.4> 4B 16 1Θ-13 · * A A A B C B (18)

Table 1 (5)

(1) Ex. no. Coating solution Dye or pigment ()) Inorganic (a) / (b) by weight ratio Polymary compound (c) (a) / (c> weight ratio (2) horses. FROM solvent Species Ratio of 1-month period (b) type Mixing ratio 49 RozPĹtťadlová Serň 5 Colloidal 910a 100/50 - 0.6 Water / 20/80 Matano 30 Direct plowing 57 - - 0.7 Water 31 Direct plowing 57 Colloid c / destroyed 100/10 acid - 0.7 · · 52 Direct red 1 / direct blue i58 30/50 - 0, 4 - 53 Direct greenery Θ - - 0.6 54 Direct Now 25 - - 0.5 53 Direct Now 25 ZnCl ₂ í 00/20 - 0.5 56 Direct Live J i - - about, and 57 Sour Red 37 - - 0, 4 Water / n- 50/50 Butyl) whom} 58 Acid Blue 60 / Acid Black 7 FaOH salt 100/20 - 0, 7 Water 59 Horidlová červená 9 - - 0.9 60 Horidlová zeleň 15 - - 1.0 ·

Table 1 (5) <continued®)

<1> Pr, no. (3) Cl ”horses, upper; middle lower: max.-min. ppm (4} Water wash time after completion min. inlay Q1 m2 i Visual value <adhered _ Batch no. mnn! st «o 10 30 50 IOC 130 200 49 18 20-15 10 A A A A A A (0,6) 50 15 17-13 A A A B C D (19) 51 10 13-B · · A A A A A A (0,9) 52 7-3 A A A A B C í 7) 53 16 18-14 A A A A B C (9) 54 13 15-10 A A A B C D (15) 55 11 13-9 A A A A A A (0,9) 56 14 16-1 1 - A A A B C Child 1Θ1 57 10 12-7 15 A A A B C D (1Θ) 58 9 11-6 A A A A A A (0.2> 59 7 9-4 A A A A B C (9) 60 18 20-15 A A A B C Dl 19>

Table 1 (6)

(1) Ex. e. Coatings? solution Dye or pigment (a) Inorganic 2-Protein (b) (a) Z (b) Polymer WEIGHT? compound ratio 1c) (a) / (c) by weight ratio <2) kane. X solvent Type Mixing ratio species Pomer mixing 61 Cerrt 30 - polyacrylamide 100/60 1.6 Water / Methanol 70/30 62 Moridlova Cerrt 9 - - 0.6 Water 63 Sauerkraut 12 - - 0.4 64 Sauerkraut 12 Cm (CH 2 -C 00) _a 100/15 0.4 65 Acid violet 7Θ - - 0.6 66 Acid Blue 151 - Polycyclopentylets] 100/20 0.6 water / methanol 30/70 67 Solvent Cerveri 109 - - 0.3 methanol 6B Acidic black 159 Methacrylic acid 100/300 1.6 Water / 90/10 Izobuty1a 1 of whom 1 69 Moridlova Cmrri 13 - - 0.8 Water 70 Sour Red 60 / 40/60 food blue 1 ZnCl _a 100/2 0.5 · 71 Acid Blue 74 - - 0.6 72 Acid Blue 74 oloid Mo0? 100/20 0.6

Table 1 (6) Indication

(1) Pr. no. (3) Cl-Kane. upper: middle lower: max, -min. ppm <41 Water wash times after min. visually inlay Q / lliJ) rating ( Batch No.  direct quantity 10 30 50 1Ó0 150 200 61 17 19-14 15 A A A A A 6 (2.5) 62 9 11-6 A A A A WITH C (10>) 63 18 20-15 '· A A A B C D (18) 64 15 18-13 10 A A A A A A (0.6> 65 15 17-12 15 A A A B C D (13) 66 13 15-10 10 A A A A A AÍ0.2) 67 11 13-7 · ' A A A A A B <2.5) 68 14 16-11 A A A A A A <0.3) 69 12 14-9 A A A B C D (19) 70 18 20-15 A A A A A And (O, 5) 71 19 21-16 A A A B C D (20) 72 14 17-12 A A A A A A (0,4)

Table 1 (7)

<1 1 Ex. no. Coating solution Dye or pigment (a) Inorganic (a) / (b) weight ratio Polymer compound (C) (a) / (c) the weight ratio <2) horses. X solvent from lucenma Species Mieftania ratio (b) species Pomer mxeSania 73 Direct blue * 86 - - 0.8 Water 74 floridlová modra 58 - - 1.0 75 Ro2pú <tadlav4 redd 3 colloidal SiO 100/50 - 0, 6 Water / methanol 20 / BO 76 Sour zelefl 9 - - 0.5 Water 77 Moridlová violet 15 - - 0.7 · 7Q Horidlová fialová 15 Al (OH)} salt 100/2 - 0.7 · 7? Pigmented celery 2 - polyallene 100/100 2.0 Water / Metenol 50/50 Θ0 Pigment violet 1 - Cellulose acetate 10 * 5/30 1.3 20/80 BI Food worm 14 - 0.2 Water B2 Sour Red 2 colloidal 51¾ 1OO / 2OO - 0.7 Water / nAmylalkohol 90/10 Θ3 Acid Blue 59 - - 0.5 Water B4 Direct blue 106 - - 0, 5 '·

Table 1 (7) (continued)

1 (1) Pr. no. (3 J Ci ~ kon. upper: middle lower: max.-min. PPíh f) Water wash time after min. ... ALnc Dose rating (attributed- quantity η / ιτ.- 1 Nr. 10 30 50 100 150 200 73 17 19-14 10 A A A B C D (15) 74 20 22-18 A A A B C D (17) 75 14 16-11 A A A A A AC0.4) 76 15 17-12 n A A A B C D (19) 77 13 15-10 * A A A A B C (10) 78 13 16-11 A A A A A A (0,5) 79 14 16-11 15 A A A A B C (9) and 9 11-6 ^M A A A A B CÍ10) ai 7 9-4 A A A B C D (20) 92 5 7-3 ' A A A A A A (0,7) Θ3 12 14-9 A A A A A 0 (1.5) 94 16 1Θ-13 A A A B C D (19)

Table * ΐιβ)

Coating solution C1) Pr. Dye or pigment (a) Inorganic (A) / (b) polymer * (a> / (c> I2> Roz púáťadlo no. zlucenxra weight compound weight accounts. Species Miefiania ratio (b) ratio (C) ratio FROM species Ratio mxeftania 85 Direct * blue IO3 - - 0.8 Water 86 Acid blue 102 / 80/20 Or flux 100/200 - 0.5 Water / 93/5 basic orange 14 acid 1zobutylalkohol 87 Solvent Red 5 Colloidal SiQ? 100/150 shellac 100/50 1.0 methanol 88 Solvent Black 5 - 0.5 89 Alkaline Cervefl 2 Fc (DH) and salt 100/50 - 0.8 » 90 Solvent ČerA 7 FeCl _a 100/5 - 0.5

Table I (8> (continued)

<1 1 Pr. no. (3) Cl 'horses. top! medium lower max.-min. ppm (4> Ink.rustÁr la mhpnie (prifnntó mnatmtva q Batch no. For l = Water wash time after quenching min. 10 30 50 100 150 200 83 20 22-7 15 & A A B C D (20) B6 15 17-12 A A A A A A (0,2> B7 14 16-11 A A A A A A (C> »3) es 12 14-9 A A A A A A (0,5) 89 15 17-13 · · A A A A A A (0,9) 90 14 16-10 A A A A A And (O, 7)

Notes) (1) * Comparative * Examples <2> Dye or pigment concentration in coating solution <3)

Concentration of chloride ion in suspension after polymerization

14) Water flow rate 0 »1 AP / lh

Example 2

As shown in Table Π, in each assay, the dye or pigment is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or polymer compound, to prepare a coating solution. In table Π, the ratio of inorganic compound to polymer compound and the concentration of dye or pigment in the coating solution are also given. The coating solution is then applied to the polished inner walls of a 1000-liter stainless steel polymerization vessel and to parts of the apparatus that come into contact with monomeroin, such as a stirrer; after application, the coating is dried at 70 ° C for 20 minutes and then thoroughly rinsed with water.

The coated polymerization vessel is then charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 2.2 kg of sodium lauryl sulfate, 3.2 kg of ethyl alcohol and 300 g of α'-azobis-2,4-dimethylvalelonitrile and the polymerization is carried out for 10 hours at 50 ° C. After the polymerization is completed, the polymer is removed, the polymerization vessel is washed inside with water 5 at a flow rate of 0.1 m ³ / m ² h, as shown in Table Π. Said operation from coating and filling to washing the polymerization vessel with water is performed for each batch and the operation is repeated a maximum of 200 times.

The chloride ion concentration is controlled as in Example 1, and the extent of the incrustations is also evaluated.

In the Π table, the comparative examples are also marked with an asterisk. In the case of Examples 91 and 92, no compound was treated within that wall of the polymerization vessel. The coating used in Examples 104 and 149 is prepared by dissolving one part sodium sulfide in 100 parts water and adding 0.5 parts far22.

In this case, the coating is dried at 80 ° C for 30 minutes.

Table 1K1I

Coating coating (1) Ex. Dye or pigment (a> inorganic (a) / (b) Palyroérna (a) / (c) weight ratio (2) solvent no. Type Mixing ratio compound (B) mass ratio compound (c> horses. X type Mixing ratio * 91 - - - - * 92 - - - - 93 * Sour zelef 16 - 0, 5 Water / 90/10 Isobutylalkohcl * 94 * · 12-Si 1 owowolTramic 100/150 acid - 0.5 Water * 95 Acid greenery Colloidal SiOa 100/100 - 1.0 methanol] * 96 - 0/100 - 1.0 Water * 97 Sour Black 2 Silicomolybds 100/100 - l.o * 98 » Solvent solvent 5 - - 0.5 Hetan 99 » CuCls 100/10 - 0.5 · 100 * Basic Black 47 Water glass 100/200 - 0.8 Water 101 » Pigment Blue 25 / Solvent Black 3 50/50 Colloidal SiOo 100/400 - 2.0 Water / 10/90 methanol 102 * Dissolve red 6 - 0.5 methanol

Table 11 (1> (continued)

() Pr. no. (3) Cl 'horses. upper »medium lower» max.-min. ppm (4) Water wash time after completion min. Incrustation Visual assessment (rnnmíst-vq a / Φ ² >) Dose C. 10 30 50 100 150 200 * 91 300 260-320 60 H (1400) * 92 13 and 17 H (1200) 93 * 290 260-31O 0 H (L100) * 94 300 260-320 · 8 C F H (900 * 95 350 310-390 · · B C F H t 800 * 96 15 11-19 · ' HC1200) * 97 280 260-290 B C F H (700) 9B * 300 260-320 B F H (1000) 99 * 300 260-320 '' B C F H <950> 100 * 270 240-280 B C F H (750) 101 * 320 270-330 · B C F H (650) 102 * 300 270-320 P F Hi 1000>

Table 1 T 2 2>

Coating solution (X> Pr. Dye or pigment (A) inorganic (A) / (b) Pe1ymérna i (a) (21 RozpúŠťadId no. of 1 sausage weight compound Type Mixing ratio (B) ratio (C) ratio FROM type Mixing ratio 103 « Pigment Red 81 - polystyrene 100/40 1.2 toluene 104 * Sulfur now 7 (oloid SiOs 100/60 1.0 Water 105 Disperse Red 12 - - 0.5 acetone 106 Acid Red 8 - - 0.0 Water 107 Alkaline Blue 64 - - 0, 7 108 Pigment Blue 25 / 50/50 Colloidal SiOs 100/400 - 1> 8 Water / 10/90 Black 3 methanol 109 Greenery 15 - - 0.4 Water 110 Solvent Red 8 - - 0.5 methanol 111 ' Rozúíťadlová Červená 9 Colloidal V _and 0> 100/3 - 0.5 - 112 Acid yellow 99 - - 0.3 Water 113 Solvent Orenl 40 - Poly (4 (vinylpyridin) tOU / 100 1.0 methanol Alkaline Blue 47 Water glass 100/200 - 0.8 Water

Table 11 (2) (continued!

U) Pr. C. <3) chickens, upper t middle lower: max, -min. ppm (4) Water wash time after completion min. Inkrusticu ViZUÁlhfl review í Divided annmtvn a / trfi i Batch no. 10 30 50 100 150 200 103 * 250 220-280 60 8 F H (900) 104 * 300 270—320 B F H (950) 105 13 9-18 10 A A A R C D (20) 106 15 11-20 · A A A B C D <19) 107 14 9-18 · A A B C D F <58> 103 17 13-21 · A A A A A B <3> 109 10 6-14 A A A 8 C D <18) 110 15 11-19 A A A B C D (20) 111 10 8-13 A A A A A B (3) 1 12 5 3-7 '· A A B C D F (60) 1Í3 9 5-13 A A A A 8 C <10! 1 14 16 13-10 15 A A A A A B (3)

Table] I i 3>

(1 Ex. t. Solvent solution Dye or pigment Inorganic compound a (b) <a> / (b) Polymer Critical compound ratio (c> (A), (2) weight horse ratio X Ros desert1 o Species Ratio stirring species Pomer mixing 1 15 kypová Čerň 25 / 60/40 Pol y < N-vi-carb (iol) 100/70 0.7 htetanol disperse violet 3 0 116 Solvents 1 blue 35 Mezokremiči ta 100/20 0.5 acid 117 Direct red 9 - - 0.0 Water / n- 80/20 butanol 118 Acid greenery Colloidal Si Or 100/100 1 »o Water / 40/60 methanol 119 Acid Red 82 - - 1.0 · ' 50/50 120 Solvent black 5 CuCl 100/10 0.6 3Q / 70 121 Solvent black 5 - - 0.4 methanol 122 Blue 41 - - 0.4 X y yen 123 Soluble vat Mezodikremičitá 100/300 0.7 Water black 1 acid 124 Kypová fialová 3 - - 0.5 xylene 125 Pigment green 37 - F'oly viny leter meter 100/40 L. 0 Mety 1 érj- chloride 126 Horidlová zeleň 58 Water glass 100/200 1.2 Water

Table J 1 (3) (continued)

(1) Ex. no. (3) Cl ^- horses. upper: middle lower: max.-min. ppm (41 water wash time after min. Visual assessment Dose O / Λ · ² 1 <pl. quantity and TVN it 30 50 1 00 150 200 1 15 B 6-1 1 15 A A A B C D (20> 1 16 15 10- 1 B A A A A A B <1.5) 117 9 5-12 * A A A 0 C D (20) ΠΒ 16 13-19 * A A A A A 0 (2.5) 119 e 5-10 · · A A B C D F (59) 120 7 5-9 · ' A A A A A B (3) 121 20 13-23 · · A A A A B C (5) 122 11 8-14 10 A A D C D F (55) 123 7 6-8 · ' A A A A A B (1,5) 124 15 11-17 '· A A A B C D (18) 125 16 11-18 A A A B C D <19) 126 10 5-12 · A A A 0 C D (20)

Table 11 (4)

1) Ex. coating solution Dye or pigment (a) Inorganic (A) / <b) polymer (A) / <c) (2) solvent no. z locemna nmocnosrny Species Mixing ratio <b) ratio from healing (C) weight ratio horses. FROM species Pomer mixing 127 Solvent Black 7 Mesotetracosilicate * 100/100 acid - 1.0 Mety 1énch1orid 12Θ Basic orange z Hwtacosilicic acid 100/40 0.8 Water 129 Basic XI »2 - - O, A · · 130 Alkaline Blue 40 - - 0.6 · 131 Sauerkraut 16 12-Siikowoltramic acid 100/150 - 0, 3 '· 132 Basic plowing 14 - - 1.0 Water / isobutyl 133 Basic plowing 14 MgCl 100/10 - 1.0 90/10 134 Pigment Red 81 - polystyrene 100/50 1.2 toluene 135 Acid Red 87 - - 0.8 Water 136 Acid blue 59 / 30/70 solvent blue 73 - 0.8 Water / Iron 1 40/60 137 Acid Black 2 Silicaffiolyhdenic acid 100/100 - 1.0 Water 138 Alkaline Blue 3 - - 2.0

Table 11 (4) (continued)

<1) Pr. t. (3) Cl ~ horses, upper: medium max.-min. P at (4) Water wash time after completion min. VizuAlne hod laExas.lAci * nat.ni ^ Batch (ρι, Γτιιι. ^ .nnl.tvn c / n. I no. 10 30 50 100 150 200 127 14 10 s 10 A A A A A B (3> 128 18 15-21 15 A A A A A B <4> 129 11 9-14 A A A B C D (16) 130 17 15-19 '* A A A B C D (17) 131 10 B-13 · · A A A A A B (3> 132 14 11-16 · · A A 8 C D Fí60) 133 11 9-13 · · A A A A A B (2.5) 134 12 9-14 A A B C D F <59> 135 9 7-11 · · A A B C □ F <57> 136 12 10-14 '* A A A A B C <6) 137 í 1 9-14 · · A A A A A B <3) 138 19 15-23 A A B C D F <60)

Table TI (5)

Coating solution Ex. Dye or pigment <a) inorganic (A) / kg) polymer (A> / tc) (2) Rozpúftťad1 o f !. z iocenins weight zIúčenins weight r.onc Species Ratio mieftania (B) ratio (c 1 ratio FROM type Mixing ratio 139 Direct blue 106 - 0.4 Water 140 Acid yellow 3 Nátriumortosilikát 100/20 - 1.2 · 141 Alkaline blue 24 - - 0, Θ · · 142 Alkaline red 27 Water glass 100/200 - 0, ľ · - 143 Dispersive Ht 54 - polystyrene 100 / 3i 0.6 toluene 144 Acid yellow 1 - - 0.8 Water / 70/30 isoamylalcohol 14S Acid yellow 1 2n (CH, -CQO>? 100/5 - 0.8 science 146 Disperse Blue 58 - - 0.5 acetone 147 Pigment Red 123 - poly -ni tropropy ln J 100/50 1 0 DMF 148 Kypová orítn! 15 - - 0.8 xylene 149 Sulfur red 3 - - 1.0 Water 150 Soluble sulfur blue 15 - - 0.7 ·

Table 1J (b) is continued

i 1) Pr. No. (3) Cl 'horses. upper t middle lower: max-min, ppm C4) Water wash time after the end c? N irti n, Vnuální snake inlay quantity d / ma) lutaniit dose t adheres * No. 10 30 50 10 ' 150 200 139 13 10-15 15 A A B C D F (60) 1 40 10 8-12 '· A A A A A B (3> 141 9 6-1 1 · A A B C D F (56) 142 14 io-ie A A A A A Bt2,5) 143 17 15-19 A A A B C D (20) 144 12 9-14 A A B C D F (59> 145 12 9-14 10 A A A A A B (2,0) 146 1 0 Θ-12 15 A A B C D F (57) 147 13 10-15 A A A B C D (19) 14B 9 5-11 J 0 A A B C D F (57) 149 20 15-23 A A A B C ĽK 13) 150 17 15-19 A A B ¼ D F (53)

SK 277795-6

Coating solution

(1> Ex. e. Dye or pigment (a) Inorganic compound a (b) (a) / (b> weight ratio Polymer compound (C &gt; (a) / (c) (1) weight horse. X ratio solvent Type Mixing ratio type PD®er mixing 151 Sulfur now 7 Colloidal SiCh 100/60 - 2, o fashion 152 Fluorescent brightener 163 - - O, B 153 Fluorescent Fluorescent Reagent 90 - 0.8 154 Azo Cerri Metacosilicic acid 1O0 / 5O - i .0 ¹¹ 155 Reactive blue - - 0.6 · · 156 Reactive red A 1B - - O, b Water / 80/20 1zobutylalkohol 157 Reactive Black 13 Colloidal MnOg 1OO / 2 - 0.6 Water

well 11 (6) (continued)

<3> Water wash time after completion min. (4 » Vičuálnp 10 inlay etve a / ir. '· 1 (1) Pr. no. Cl ~ horses, upper and middle lower: max.-min. ppm kinrinr.tk.nip dose _i ρηΓιιιιΙέ quantity ¢. x 50 1 00 150 2OO 151 16 14-19 10 A A A A A B (2.5) 152 11 8-14 β A A B C D (15) 153 6 3-e A A B C D F 154) 154 13 10-15 A A A A A P <3) 155 10 9-1 1 A A A B C D (16) 156 15 12-17 A A A 8 C D <20) 157 14 11-17 ^M A R A A A B (3>

Notes i (1) * Comparative Examples (2) Concentration and dye or pigment in the coating solution (3) Concentration of chloride ion in suspension after polymerization (4) Water flow rate 0, i

Example 3

As shown in Table ΙΠ, in each assay, the dye or pigment is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or polymer compound, to prepare a coating solution. Table ΙΠ also always shows the weight ratio of the inorganic compound and the polymer compound and the concentration of dye or pigment in the coating solution. The coating solution is then applied to the polished inner walls of a 1000-liter stainless steel polymerization vessel and to parts of the apparatus that come into contact with monomeroin, such as a stirrer; after application, the coating is dried at 70 ° C for 20 minutes and then rinsed thoroughly.

Thereafter, the coated polymerization vessel is charged with 160 kg of vinyl monomer, 40 kg of vinyl acetate monomer, 400 kg of deionized water, 600 g of gelatin, 2 kg of triclene and 350 g of lauroyl peroxide and the polymerization is carried out for 6 hours at 1070 ° C. Upon completion of the polymerization, the polymer is removed and internally washed with water at a flow rate

0,1 m ³ / m ² h as shown in table ΙΠ. Said operation from coating and filling to washing the polymerization vessel with water is performed for each batch and the operation is repeated a maximum of 200 times.

The chloride ion concentration is controlled as in Example 1, and the extent of the injections is also evaluated. The test conditions and results are shown in Table ΠΙ.

Table 111 i 1 i

In the ΠΙ table, comparative examples are also marked with an asterisk. In the case of Examples 158 and 159, the inner walls of the polymerization vessel were not treated or coated with any compound. The coating used in Example 5 (5) is prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 parts of dye to the resulting solution, and then drying the coating at 80 ° C for 30 minutes.

Pov lakový ruatok

(1> Pr. no. Dye or pigment (A) Inorganic compound, ania (b) (a / / (b) weight ratio) polymer 21found (c> (a) f i. c: weight ratio (21 horses FROM fíoztááadad1 o Species Ratio mici species Pomer mixing 158 · - 159 « - - - - 160 * Razpufiťad 1 c a á red * 7 - - 0.5 meten 161 * - poly tetrahydrofuran 100/30 0.6 THF 162 « Basic plowing 2 Colloidal SiO2. 100/100 - 1. about Water 163 « Razpútťadlcvä sherf, 5 - He went if 100/50 0.9 methanol 164 « - Fe (OH) ₃ salt 100/10 - 1, o 165 * KysIA Čerf 2 Oddné sklo 100/100 - 1.5 Water / Methanol 50/50 166 « Basic plowing 14 Matakr etnič i. t A acid - 1.5 methanol 167 « - Colloidal SiOa 0/100 - 1.0 Water 168 « Wingspan 1 dvA blue 2 - - O, S methanol 169 * purple violet 2 - - 0.3 xylene

Table II I (1) (continued)

(1) Ex. ¢. S) Cl cone. upper: middle lower! Min.-Max. ppm (4> lnKcu-fly hfirlr.n.pr. ia t ρηΓιιιι, or .. rwistwi α / ιτ. ) Dose C. Water washing time after finishing f min. Vnuálne. 1 0 IC 50 100 150 200 158 * 350 390-320 60 H (I100 3 159 » 10 32-7 H í 1000) 160 * 300 350-280 ^M p F H (500> 161 « 280 330-260 * 8 F H 300300 J 162 » 290 350-270 B C F H 163 » 230 290-230 · · P F H t 400) 164 * 290 340-270 · Ï C F H <3001 165 * 260 300-240 B C F HI250) 166 * 250 300-220 B C F H (280) 167 * 280 340-260 H (900) 16Θ * 270 320-250 · ' P F H (400> 169 * 290 340-270 D F H í 500)

Table * III (2>

1) Pr. Straight r t »s t ok Dye or pigment (a) Inorganic (A) / <b> F-'qlymérna (a> / (c> (2> solvent Species Ratio compound compound (b) weight ratio compound <c I weight horse ratio X type Mixing ratio 170 Roxpastad hunts black 7 - Palytetrahydrcturan 100/30 0.6 THF 171 Solvent ČerA 7 - - 0.5 Metano1 172 Pigment Red 17 - Polyethylene acetylene poly »C, B 173 Direct blue 96 Ortho-silicic acid 1ÚÓ / 2Ú - 0.8 Water 174 Basic orange 2 Colloidal SiO- 100/100 - 1.0 Water / n- 90/10 Buty1 alcohol 175 Straight Black 74 - - 0, 5 Water 176 Solvent Red 121 - 0.6 methanol 177 '· Colloidal lithium silicate 100/100 - 0.6 Ι7Θ Rorpúôadad1 uvi Čerň 5 - went ak. 100/50 0.8 179 Čer - - 0 »6 acetone 180 Morid Black 13 Metasilicate kyaalina 100/200 - 0.7 Water 1B1 Solvent blue 36 - - 0.4 methanol

Table 111 (3)

Coating solution 1) Pr. Dye or Pigment (a) inorganic (A) / <b) After 1 yamma i) / (C> (2) solvent e. Type Factor Ratio donor compounds 1 b) weight ratio compound (c> mass ratio horses X type Mixing ratio 182 Acid red 80 / 00/20 basic plowing 2 - - 0.8 Water / 50/50 methanol í 83 Solvent 1 ovi Cerfi 5 Fe (DH) j salt 100/10 - 1.0 - 1Θ4 Reduced vat blue t - - 0, b Water 105 violet 2 - - 0.4 Ky 1 én 186 Moridlová zeleň 29 - - 0.3 Water 1Θ7 Solvent blue 2 - - 0, 7 methanol 1B9 · · CoCl ₃ 100/1 - 0.7 1B9 Food red 14 - - ú, 8 Water 190 - AlCl 100 / L - 0.8 · 191 Acid Black 2 Water glass 100/100 - 1 .5 Water/ I collected 1 alcohol 192 Solvent Yellow 33 - - α, θ Water

Table 11 1 (-> (continued>

(1> Ex. no. (3 3 Cl-kone. upper: middle lower: ma>: .- min. ppm í 4) Water wash time after completion min. lakrusLtácxa Visual value ten i e_ (original_quality Q / m ^J > Giving to a no. 10 30 50 1 00 150 200 182 13 15-10 10 A A A A A B (3) 183 11 1 3—6 A A A A A A (0.5 3 1B4 18 20— 1 5 A A A B C Dl 191 185 14 19-14 · · A A A & C D (19> 106 19 21-16 '· A A A & C Dl 18) 1B7 20 22-17 15 A A A B C Dl 17) 188 20 22-18 10 A A A A A A <0.5) 189 12 14-9 15 A A A B C Dl 16) 190 12 14-9 10 A A A A A A <0.5) 191 5 7-3 15 A A A A A A (0,7> 192 16 18-13 A A A B C D (15)

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Table IHifl)

Coating flow. 1> Pr. e. Dye or pigment <a) Inorganic from 1 sausage (B) mass ratio Polymary of 1 smoked (c> <2> weight horses. poner X Rozpúíťadlo species Ratio mieCania Type Mixing ratio 193 Basic plowing 14 Ple tal.rcmlč 1 that acid 100/500 - 1.5 Water / _s sec-buty 1 and 1kohal 194 Acid brown 161 - - 0.6 Water 195 Sulfur blue 9 - - O. 7 ' 196 Fluorescent C Brightener - - 0.4 197 Reactive greenery 8 - - 0.5 198 Azová llť 2 - - O, 5 methanol 199 · ' Cocle 100/5 - 0.5

Table 111 (4) <continued e)

<1) Pr. no. (3> ll-horses, upper r middle lower: max.-min. PPm (4> Water wash time after min. visually Inkrmt.cn No, n.kt \ .o q / m- y horinotenie Batch (nn¾nnté e. 10 30 50 1OC 150 200 193 1 1 13-8 15 A A A A A A <0.9) 194 17 19-14 A A A Ï C D (20) 195 14 16-11 A A A A B C (10 &gt;) 196 8 10-5 A A A B C D (19) 197 16 18-12 · ' A A A B C D (15) 198 9 11-6 A A A B C D <16> 199 13 16-11 10 A A A A A A (0.7)

Notes t (i) * Comparative examples (2) Dye or pigment concentration in Coatings solution (3> Concentration of chloride ion in suspension after pulymerization (4> Water flow rate 0,1 m ³ / m ² h

Example 4

As shown in Table IV, in each assay, the dye or pigment is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or polymer compound, to prepare a coating solution. Table IV also always shows the leaching ratio of the inorganic compound and the polymer compound and the concentration of the dye or pigment in the coating solution. The coating solution is then applied to the polished inner walls of a 1000-liter stainless steel polymerization vessel and to parts of the device that come into contact with a monotherm such as a stirrer; after application, the coating is dried at 80 ° C for 10 minutes and then thoroughly rinsed with water.

The coated polymerization vessel is then charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 40 g of partially saponified poly5 vinyl alcohol, 60 g of hydroxypropylmethylcellulose and the polymerization is carried out at 57 ° C for seven hours. After the polymerization is completed, the polymer is removed and the polymerization vessel is washed inside with water at a flow rate of 0.1 m ³ / m ² h as shown in Table 10 IV. Said operation from coating and filling to washing with water is performed for each batch and the operation is repeated a maximum of 200 times.

The chloride ion concentration is controlled as in Example I, and the extent of incubation is also evaluated. The number of fisheyes in the product obtained from the polymer in the 10th, 30th, 50th, 100th, 150th and 200th batches is also evaluated for each test. A mixture of 100 parts by weight of the polymer obtained by dehydration and drying of the suspension after polymerization, 50 parts by weight of DOP, 1 part by weight of dibutyl laurate, 1 part by weight of cetyl alcohol, 0.25 parts by weight of titanium dioxide and 0.05 parts by weight of carbon black are mixed between two rolls at 150 ° C for 7 minutes and then processed to a 0.2 mm thick film. The number of fish eyes per 100 cm ^{3 of} foil is determined by the light transmission method.

The conditions and results of this test are shown in Table IV.

In Table IV, the comparative examples are also indicated by an asterisk. In the case of Examples 200 and 201, the inner walls of the polymerization vessel are not treated or coated with any compound.

Table IV t (t)

4 1) Ex. no. Coating solution Dye or pigment <a) Inorganic compound (b) <a) / (b> by weight ratio Polymeric compound ic) (a) / (c) weight ratio (2 1 horse X RozpúCťadlc Type of Fomar mixing species Pomer mixing 200 * - - - - 201 * - - - - 202 « Solvent Black 7 - - O, 5 methanol 203 « * Feldham)? shot 10Q / 20 - 0.3 Water / phthethanol 10/90 204 * Basic orange 2 / solvent black 60/40 3 - - 0.8 · ' 50/50 205 * Dissolvable red 5 Colloidal S1O2 100/80 - 0.8 methanol 206 « Sour Cerfl 2 fletakremiči ta kyee-1 ina 100/50 - 0.0 Water 207 Solvent Black 7 FelOHJa 100/20 - 0, S Water / Methanol 10/90 208 Alkaline Orange 2 / CerA 60/40 3 - - 0.8 50/50 209 Soluble sulfur brown 1 - - 0.S Water 210 Roľppustadlová čerA 5 colloidal SiO? LOO / BO - 0.8 methanol as 211 Azová čerfl 3 - Š e- lak. 100/100 1.0 · 212 Pigment green 38 Etylceltilóza 1OO / 4O 1. 4 ethanol

Table 1V (i> (continued)

<1> Pr. no. Cl ^- horses, upper: middle lower: << ax.-min PP * ) Wash with water for. termination min. C 4> ah j * Visual · Incr is stable rating i ΡτίΓ-ηιιΙέ mi-.ciž fetvD Q Fish nets Batch no ípocetl 10 30 D4vka č 30 1 00 50 200 10 30 50 100 150 200 200 * 300 60 H 1000> 300 260-330 201 * 10 B-12 H <9S0> 230 202 * 290 B F H (700) 10 180 250 250-310 203 « 3'J'j · ' D C F H (500 13 50 60 100 260-350 204 « 200 B F H í 650) 1 1 1 20 190 240-300 20S * 250 · · 9 C F H i 500 IB 40 00 1 20 200-270 206 * 260 B C F H (560 > 15 50 100 150 210-290 207 14 10-16 1 5 A A A A A A (0,5) 0 0 0 0 2 10 208 1O 8-12 A A A A A A (O »7 1) t, · 0 0 0 3 15 209 12 9-14 ' A A A A R C (10> 0 0 0 ² 7 20 210 8 6-10 A A A A A A (0,2) 0 0 0 0 1 5 211 13 15-10 A A A A B C <9) 0 0 0 1 10 23 2) 7 18 20-15 A A A A A C <1) 0 0 0 4 1O 19

box IV <2>

Coating solution í 1) Pr. Dye or pigment <a> Inorganic (A) / (b> Polym ^ rna (al / lcl (2? RozpúHľactla c · compound weight compound weight ktmc Species Milking ratio (hl ratio X ratio species Ratio mleftania Solvent CerA 5 - - 0.5 hetanoi 214 Basic orange 14 - - about,? Water / 90/10 J captured J whom) 215 Scooter Ferrt 23 - - 0.0 methanol 216 Solvent blue 73 - - 0, 4 217 Acid red 2 metasilicic 100/50 0.0 Water k y se] i on

Notes i <11 * Comparative examples <21 Concentration of dye or pigment in solution (3) Concentration of chlorine in suspension after termination after polymerization e (4) Water flow rate 0.1 eP / m ² h

Example 5

As shown in Table V, in each assay, the conjugated compound is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or polymeric compound, to prepare a coating solution. Table V also always shows the weight ratio of inorganic compound to polymer compound and the concentration of compound with conjugated n bonds in the coating solution. The coating solution is then applied to the inner walls of a 1000 liter polymerization vessel and to parts of the devices that come into contact with the monoinier, such as a stirrer; after application, the coating is dried at 70 ° C for 20 minutes and then thoroughly rinsed with water.

The coated polymerization vessel is then charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 44 g of partially saponified polyvinyl alcohol, 56 g of hydroxypropylmethylcellulose and 60 g of tert-butyl peroxyneodecanate and the polymerization is carried out at 52 ° C for seven hours. Upon completion of the polymerization, the polymer is removed and the polymerization vessel is washed inside with water at a flow rate of 0.1 m ³ / m ² h as shown in Table V. Said operation 5 from coating and loading to water washing is performed for each batch and operation. repeats up to 200 times.

The chloride ion concentration is controlled as in Example 1 and the range of 10 incrustations is also evaluated. The conditions and results are shown in Table V.

In Table V, comparative examples are also marked with an asterisk. In Examples 301 and 302, the inner walls of the polymerization vessel were not treated and coated with no compound. The coating solutions of Examples 333 and 334 are prepared by dissolving one part of sodium sulfide in 100 parts of water and adding 0.5 parts of dye to the resulting solution, drying the coating at 80 ° C for 30 minutes.

clay) Pr. Coating solution Z 1.s conjugovanýl n ties (a) Inorganic (A) / (b) Polymŕrna (R) / Ic) <2) Rczppustad1 o e. Species Ratio mixing compound (b) weight ratio compound <C) weight memory horses X type Mixing ratio 301 * - - - 302 « - - - - 303 · Rozanl1in - - 0.5 Methane 1 304 * - - v, 5 303 * ' - - 0.5 · 306 * · Colloidal SiOa 100/100 - 1.0 · 307 * 100/200 shellac 100/20 1 5 3oe * - 0/100 - 1 Q Water 309 * Leucochinizarin / 90/10 Solvent black 7 FetOHJa fiQľ 100/30 - 0.7 Water / 20/80 methanol 310 * Flevonol - - 0, S Methane 1 311 * Indisoazín Niclas 100/5 0.4 · 312 * Akridún - - 0.5

'Table V (l) (continued)

(1) Ex. no. (3) Cl-horse, upper: medium lower: max.-min. ppm (4) Water wash time after completion f min. VimAInfe l.ndnc Batch no. 50 100 150 200 10 30 301 * 300 2ΘΟ-350 60 ti <1 000) 302 * 15 12-17 · · H (900 J 30.3 * 300 270-350 B F H <850) 304 » 210 190-250 B F H <60µ> 305 * 140 120-1 BO '· P F H (500) 306 « 290 270-310 8 C F H <400) 307 * 240 220-300 B C F H <35O> 308 * 11 9-13 H t 900) 309 * 280 260-330 B C F H (350) 310 * 270 250-320 · · G H (500> 311 * 290 270-350 G H <300) 312 « 250 230-290 G Hí600)

T í t »u). and V (2>

<1) Pr. Coatings? solution. Zl.fc k he jugovaných ir bonds (and> Inorganic (a) / <b> Polymer (a) / (c) (2) solvent no. Species Eating ratio compound (B) weight ratio < c) ratio horses X type Po <n * r mixing 313 * 2-0xyt iofantrene - 0, 3 n.t.nol 314 * F ta 1az1 n / acid blue 59 50/50 - - 0.5 315 * - - So lacquered 1.0 316 * Caratyan ín - - 0.7 · 317 2.2-Diphenylolpropane - - 0.7 318 Dxyantraquinone / solvent black 50/50 5 - 0.9 '· 319 Rezaní1ln Colloidal SiCfe 100/100 0.6 Water / 20/80 methanol 320 Rozanilín / quinoline - Shellac 100/20 0.7 methanol 321 4-Amťnodifenylamín - - 0.5 · · 322 x-aminophenazine - - 0.Θ · 323 2-Amino-di-enylamine - - 4. 4 324 7-Amino-4-methylsulfonyl O, 7

Table VI2) continuation)

C 1) Pr. no. (3) Cl ”horses, hprnái middle lower: max.-min. ppm (4> Water wash time after min. inlay ZSTV ‘Know Σ Visual hndnnfenig i PnTniilť tons no. 10 30 dose 50 i 0i> 150 200 313 * 790 270-340 60 G H 1700) 314 * 270 250-320 · · G H C 350> 315 * 240 220-290 H <950> 316 * 220 200-280 G H (550) 317 13 10-15 10 A A A B C n <20) 318 15 13-17 A A A A A A <0 »7> 319 7 5-9 " A A A A A B (1.5) 320 4 3-5 A A A A A B <3) 321 1 7 14-21 '· A A A B C D (17) 322 14 10-18 A A A A B C (9) 323 16 12-18 '· A A A B C D <20> 324 13 10-17 A A A B C D (22>

Table V <3)

Coating (i)

Pr. e. Zn conjugated with π π bonds (a) Inorganic (a) / (b> Polymer weight compound ratio <c> (a) r (c) weight ratio c 2) horses X solvent type Po «> er mixing Type Mixing ratio Compound (b) 325 Phenolate oxide / 40/60 Acid red 2 kc 1 oi bottom of essential oil and 100/200 0.5 Water f 40/60 methanol 326 bi s (G-phenyl1) n> matonic acid - - < '9 Metáne1 327 3, a-Benlochinolŕn - - 0.7 32B benzoflavin - - about. 3 ' 329 TrifenylizQQNazol - - 0.9 · · 330 N iodium + enyl ether - - 0.4 · ' 331 Picene-5,6-quinone - Polypyridýlacetylán 100/100 1, 0 332 Indoanllŕn - - 0.4 333 Hydron blue / S0 / 20 alkaline Cerrt 2 - - 0.8 · ' 334 BenzotaJbenzofurán - - 0.5 335 3,4-Ftaloylíurazén - - 0, 5 336 3-Cinramy1-2-methyl 1 - - - 0.9

1,4 ·· η »· to toquinone

Table V (3) continuation)

i 1> Pr. no. (Ti Cl-kone, upper: * third lower: max.-min. ppm (4 f) Survival time with water after completion min. llxLrxLaLLáu.xä Batch no. IZA-l 10 30 50 100 150 200 325 11 4-1 4 15 A A A A A A (0,2) 326 9 7 12 · A A A D C D (i Θ) 327 12 Θ-15 A A A 9 C D (20) 328 10 7-13 A A A B C D (15) 3-29 15 11-17 - A A A B C 0 (17) 330 20 16-22 A A A B C DÍ21) 33 14 10-16 - A A A A B C í 1 0) 332 7 5-9 A A A B C D (20> 333 10 9-12 1O A A A A A B (, 3) 334 8 6-10 A A A B C D (18) 335 16 13-1Θ A A A b C D í 20) 336 10 912 · · A A A B C D (24)

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Tables V <4)

Coating solution 1) Pr. Zl.s conjugovaných w bonds (a) Inorganic <A) / (b) Polymárna (O> / (c) i 2) kane Solvent io C. compound hmotnaitn ý compounds * wEIGHT « Type Pflflifr mixing (b) ratio (C) ratio FROM type Mixing ratio 337 alizarin - 0.4 Metaná 1 33Θ Leukochini zar ín / 90/10 FeíOHl? 100750 0.7 Water / 20 / Θ0 Solvent) Hunting * Black 7 methanol 339 2. 2 “Diantraquinols) - - 0.8 methanol 340 Anhydrorium base - - 0.2 341 Chromate) / Basic plowing 14 20/80 - O, 5 342 flavonol - - 0.3 · 343 dicoumarol - - 1.0 344 J joxantOn - - 1.2 345 1-feny1pyrrol - - 0.8 346 3-feny1indol - POLYVIA others lizobutýral 100/20 1.0 chloroform 347 lndigoazín NíC1 ₃ 100/5 - 0.4 methanol 348 ft-isoindigo - - 0.6

Table V (4)

(1> Ex. no. í 3> Cl “horses, upper and middle up to max. Min. ppm (4) Water wash time after min. ICLkĽuiitÄclA n = i Batch no. 150 10 30 50 LOU 200 337 13 10-15 10 A A A B C D (21) 33Θ 12 9-14 A A A A A A (0,5> 339 9 6-11 15 A A A B C D <20> 340 1 i-13 · A A A B C Cl 18 » 341 19 1 S — 22 · · A A A A A B (1.4) 342 14 10-16 · · A A A B C D <10) 343 12 9-14 · · A A A B C D (19) 344 6 4-0 · · A A A B C D (20) 345 10 7-13 ¹⁴ A A A F C D (16) 346 14 11-17 A A A A A £> <3) 347 12 9-14 A A A A A B (1.2> 34Θ 19 15-23 A A A Ï C tK 17 »

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Table Vl5>

Coating solution 1> Pr. 21. Conjugated (Kα) Inorganic (a) / (b) Polymer (a) / (e) (2) Confrontad1 o no. Type Mixing ratio nútafun * weight compound weight (b) ratio (cl ratio kone X type Mixing ratio 349 1,1-D / carbazol - - 0.5 methanol 350 Porfyn / 20/0 RvJAnder Black 2 - Po1 yadi kos in 100/50 0.8 351 4-fonyltiazo) - - 4. 4 · 352 4 — hair dryers of 1 - - 0.0 353 5-íenyIpyrazol - - 0.9 · 3Ξ4 Fény 1ururoxan - - 0.5 · 355 2-Pheny1-1,3,4-1 i ad i βϊο1 Metatetrakremic tA acid 100/100 0.7 Water / 30/70 Metaná1 356 2-fony1-1,2,3-triazole - - Delta 4 Metaná 1 357 1-Oxy-5-teny1tetrazDl - - 0.0 - 358 4 — Pyridol-phenylenediamine - Hydroxyethylcellulose 100/100 1.0 acetone 359 Quino ta ta - · - 0.3 Metaná 1 360 5-Iodoquinoline - - 0.6 '*

Table V (5) (continued)

(1) Pr. e. (3> Cl ^- kejne. Upper and middle lower i have .— min, Ppm <4> □ both washes with water after min. visually hodnot.ni. 1 Adhered «nnlst ^ n g / m? 1 Lot no. 10 30 50 100 150 200 349 7 5-10 15 A A A B C D <20) 350 8 6-1 l A A A A A A (C, 5) 351 14 10-16 A A A B C D (18) 352 12 9-14 · · A A A B C D (17) 353 10 7-13 · A A A □ C Dt 15) 354 12 9-14 · · A A B C D F f 55) 355 15 12-13 * · H A Λ A A B (2.1) 356 8 5-10 · · A A B C D F (53) 357 14 11-17 10 A A B C D F (56) 358 7 5-9 A A A A B C <10) 359 10 8-12 A A A et C D <1 7) 360 12 10-14 A A B C D F (56>

Table Vié>

Coating solution (1> -----

Pr. 21. with conjugated r bonds ta) inorganic a (a) / (b> Polymer) (A) / (c) (2) solvent No. Type Mixing ratio Compound (b) weight compound ratio (c) weight ratio kone Z type Mixing ratio 361 9-phenoxy) -cridine - 0, 5 methanol 362 3-0xyfenantridinón - - OJ C,, p. 4 363 2-Benzoyl coumarone - - 0.8 - 364 HydrevaníJloyl / 20/80 Solvent devils 5 Fe (QH > i salt) 100/5 0.5 '· 365 1.3-Dioxyakridín - - 0. 7 366 o-Dxybenzothenone Z 70/30 solvent blue 73 - - 0.8 · · 367 2.5-Dioxybenzofenón - - 0.7 368 acridone - - 0.5 · 369 2-Dxy-3-Ťenylirdazol - - 0.5 370 Kanten - - 0.6 371 2,4-Dinktro-9ferylacridine - - 0.8 · · 372 4,4'-Dibenzoyldi hair dryers 1 - - 0.4

Table V (6) (continued)

(1) Pr. No. (J) Cl-kone. upper: middle lower: max.-min. ppm (4) Water wash time after completion mm. Ink r.ustáciáa Batch no. "Tr.-st o / mil) 1O 3 < » 50 1ÚO 150 200 361 15 12-18 10 A A A B C D (15) 362 20 17-23 A A A B C D (17) 363 13 10-16 ¹¹ A A B C D F (54) 364 16 14-19 · · A A A A A A (0.5 J 365 12 9-15 A A A B C D t 18) 366 9 5-1 1 15 A A A A A Bt2.3> 367 17 14-20 A A A B C D (15) 368 11 B — 14 · · A A A B C D (13) 369 12 9-15 A A A B C D (16) 370 B 5-10 A A A B C D <17> 371 5 3-7 A A A B C D (20) j 372 12 9-14 · A A A B C D t 16)

Table V (7)

1) Coating solution Pr. Zl.e kanjugovaných n ties (·) Inorganic After) ymérna (a) / (c) (2) RoapúíťadJo no. compound hmotnoetný compound weight Xonca. Species Ratio mieftania (B) ratio Cc ratio FROM species Pomer mixing 373 Diaminobenzofanôn - ButyIcelulóz and 100/20 0.8 ethanol 374 Tetrametoxyindi go / 60/40 Colloidal SjO? 100/200 0.8 Water 4 tíí btj fenoazOKid methanol 375 Terfeny1 / 1,4di hair dryer Lnat talen 50/50 - - 0.6 methanol 376 Afliinothenetins and phenylene - - 0.8 377 1-Jodonaftalón - - 0.3 · · 37Θ 3,4-Benzocarbazole - - 0.5 379 α-Naf tol - - 0, 7 · 380 Methylan-di-O-naphtol - - 0.4 · · 381 2-methoxy-naphthalene - - 0, 7 · 3B2 «Β-Naftotenyxazín - - 0.8 '· 383 2.6 ~ Naphtoquinone / basic red 2 70/30 - 0.3 3Θ4 2-2'-Naftalan Colloidal SiOa 100/50 1.0 Water / 30/70 indolindigo Methanol

Table V <7) (continued>

(1> Pr. no. (3) C1 ~ horses, upper: middle lower: max.-min. ppm (4) Water wash time after completion min. visually hodnatenie dose i ΡτίΓιιιιΙΓ__mnn? .tvn no. aZa ^and l 10 30 50 100 150 200 373 8 5-10 15 A A A A A 8 (1.8) 374 1 4 11-17 A A A A A A (0) 375 17 14-20 10 A A A B C D (17) 376 11 7-15 A A B C D F (58) 377 16 14-18 · · A A B C D F (57) 378 10 7-13 · A A A B C D <15) 379 15 13-17 A A B C D F (53) 38 O 8 5-10 A A B C D F (52) 381 15 11-i · · A A A D C D (20) 382 17 13-20 A A A B C 0 (18) 383 1 1 9-14 '· A A A A A B (1.9) 384 12 10-15 A A A A A B (2.3)

SK 27779S B6

T * t r r V <8>

Povlakový rcztcrk Pr. no. )). con jugovariýuii ir bonds (a) Inorganic · of 1 apprentice irtd (B) (a) / (b) weight ratio Ymα1 ytmary compound (c (a) / (c · 2) weight lonr ratio Z Rozpúátíad10 Species Ratio mletaníe kind of F’omer mxaäania 385 Na1toani1id - - 0.3 methanol 386 [alpha] -Pyridone on tlone / Solvent black ύ 10/90 - - 0.3 * · 387 α-N i trzo-ft-naphtol Colloidal SiO2 1 <»Ô / 100 - 0.0 Water / Methanol 40/60 388 2 - Ar »x 1 £ noan t racene - - 1.0 methanol 389 2-Amino-1-Antrena - - 0.9 · 390 Antracin-9-α-dihyd - - 0.5 391 1-Am i to fonan training - - 0.6 · 392 Phenanthrene-1,2-quinone - - 0.8 393 2-Jodofenantrán - - 0, 7 394 2-Amino-3axyfenantrénchinón Colloidal SiO? 100/500 - 0.8 Science / Methanol 20/80 395 2,7-Diphenyl [2,3-9] quinoline - - 0.6 Metaná1 396 1. 10-Phenanthroline Fe (OH>> salt) 100/20 - 0.8 Water / Methanol 50/50

(1> Fr, no. (´> Cl “horses, upper: middle lower: max.-min, ppm (4) Water wash time after completion of min. Iot.ru »'' ic ic ic ic ic ic ic tv tv tv tv tv tv tv tv tv tv tv tv tv dose no. 10 SO 1Ó0 150 20G 385 1O 7-13 10 A A B C D F (53 » 396 14 11-1B · A A A A A B (2.5) 3B7 14 11-17 ¹¹ A A A A A A <0.4) 3ΒΘ 18 15-22 A A B B C D (1?) 389 5 3-7 A A B B C D (20) 390 11 9-14 A A A B C D C 22) 391 9 6-12 · · A A B B C Dt 18) 392 12 10-15 15 A A B B C D C 20) 393 and 5-11 · · A A A B C 8 (21) 394 11 8-14 A A A A A B <2.7) 39S 15 12-18 A A A C D F <52) 396 10 - A A A A A B (l 5>

Table V (9)

Pov1 and metal tcl · <1) ---

Pr. no. Zl.s conjugovaných Species Poaar π vMzkami (a) Inorganic (a) / (b) Polymer <a) / (c) weight compound weight ratio (c) ratio (2) horses X Solvent 10 type Mixing ratio mixing compound (B) 397 1 ·> 9-Pyrxdoindole - - 0.4 methanol 398 3-amino-5naftylidín - Poly (N-vinyl) 12-4-100 / 30 shaking 1.0 DMF 399 Caratyanín - - 0.7 methanol 400 phenothiazines Colloidal S1O2 100/40 0.9 Water / 30/70 methanol 401 F ta) axi n / Acid Blue 59 50/5 '? - 0.5 methanol 402 1 -Amlnophenazin n - - 0.4 403 2,4,6-Trifsny 1-Str - Pol y <9-100 / 50 vinylan tracén) 0.6 Metylénchlond 404 2-Feny1tiofén - - 0.9 methanol 405 3-Oxy thiophant wound - - 0.3 406 Tietlavún - - ij, 4 407 2-Aminophenoxin - - 0 5 408 Tetrahydroberberin - - 0.8 ·

Table V <9) (continued)

11) Ex. C. (3) C 1 - to or. c. upper: middle lower: max. min. ppm (4) Water wash time after completion min. inlay Vunálne rating dose (Direct amount q / m ») Nr. 10 30 50 100 150 200 397 13 10-16 15 A A A B C Dí 17) 398 20 15-25 A A A A A B (1.9) 399 12 11-13 A A B C D F (55) 400 10 8-14 A A A A A A (0.7> 401 7 5-9 ' A A A A A EU 1.8> 402 19 1 4-23 10 A A A B C D (ie> 403 16 13-19 A A A A A B (2.3> 404 14 11-18 A A A B C 0 (20) 405 16 13-19 · A A A B C D (J7) 406 20 16-24 A A A B C r> (J6>) 407 6 5-8 A A B C D F (53) 408 9 7-12 A A B C D F (55)

Table 9 (10)

Coating solution 1) Pr. 21. · conjugated k π binding (inorganic) (A) / (b) polymer (a) / (c> (1) RazpOŠťad1 o C. from 1 lesson to weight compound massive canoe Kind of ratio mixing (b) ratio (c X ratio type Mixing ratio 409 Niko / Leri - - 5 »5 methanol 410 And? fiefs - - ň, 7 411 Rasarín - - 0.5 · 412 Colloidal SiOa 100/200 Selak. 1.5

Table V (10)

<1> Pr. (3) Cl ^- horses, upper: medium lower: max.-min. ppm i4> Water wash time after min. visually Incrustation of valuations! iiikCL q / n J. 10 30 5U 1OO 150 200 40? 11 9-13 10 A A A B C D (18> 41U 1B 15-21 A A A B C D (1θ> 411 A A A B C D (20) 412 A A A A A A (0,5)

Notes with (1) * Comparative examples (2) Concentration of compound with conjugated π bonds (3) Concentration of chloride ion after polymerization (4) Water flow rate 0.1 nP / m2h

Example 6

As shown in Table VI, in each assay, the n-conjugated compound is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or polymer compound, to prepare a coating solution. Table VI also shows the weight ratio of the inorganic compound and the polymer compound and the concentration of the compound with conjugated n bonds in the coating solution. The coating solution is then applied to the polished inner walls of a 1000 liter polymerization vessel and to parts of the apparatus that come into contact with the monomer, such as a stirrer; after application, the coating is dried at 70 ° C for 20 minutes and then thoroughly rinsed with water.

Then the coated polymerization vessel is filled with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 0.25 kg of hydroxypropylmethylcellulose,

0.25 sorbitol monolaurate and 50 g, α'-azobis-2,4-dimethylvalelonitrile and polymerization is carried out at 57 ° C for ten hours. Upon completion of the polymerization, the polymer is removed and the polymerization vessel is rinsed with water at a flow rate of 0.1 m ³ / m ² h as shown in Table VI. Said operation from coating and filling to washing with water is performed for each batch and the operation is repeated a maximum of 200 times.

The chloride ion concentration is controlled as in Example 1, and the extent of the injections is also evaluated. The conditions and results are shown in Table VI.

In Table VI, the comparative examples are again marked with an asterisk. In the case of Examples 413 and 414, the inner walls of the polymerization vessel were not treated and coated with no compound.

T * burt * vi <i>

(1> Coating solution Pr. Z i with honjugated w bonds (a) Inorganic (A) / (b) polymer (A> / (c) <2) solvent compound weight tlucenina nmotnostny horses. Species Ratio ml.i.ni. (b> ratio (C) ratio X type Mixing ratio 413 * - 414 · - - - - 413 « 1 -Β »tHTtor.a f tal éi i - - 0.5 methanol 416 « t-na f talen — 2 '- F e (DH) j with G 1 i 00/30 0.6 Water / 20/80 indolindigo methanol 417 * 9.10-diamino-50/50 Colloidal SiO _s 100/100 1.2 · 30/50 phenanthrene / fenotiarín 418 * Di oxyacridone - - 0. 6 methanol 419 * - Colloidal oxide 0/100 1.0 Water kremititý 420 * 7-Oxy-3,4 - Poly tetrahydrofuran 100/50 0.7 benzene benzokurMrín 421 * - - 0/100 0.5 · 422 * indophenine - - 0.6 methanol 423 * Nltrofgnatiaiín - - 0.4 424 * Diantrachinónimid - - O 5 ·

Table Vl (l) (pukraCavaníe>

(J) Ex. 3) Cl ^- horses. upper t medium (4) Water wash time after Had had nat had Pr Pr Pr Pr Pr Pr jinaístvra q / ml no. lower: max.-min. ppm min. 10 30 50 100 1S0 200 413 » 300 260-300 60 H t 1400) 414 « 13 B-17 H (1200) 415 * 280 260-330 g h (i ooo) 416 * 270 250-320 C F H (900) 417 * 240 220-300 · · C F H (850) 410 * 280 260-320 G H (1000) 41 '? » 230 210-290 · ' H (1300) 420 * 290 270-350 · □ H (900) 421 * 220 200-280 H (1330 &gt;) 422 * 260 240-310 · ' G H t 800) 423 * 250 230-280 '· G H (800) 424 * 300 2Θ0-350 ⁴¹ G H 950)

Table Vl! 2>

(1> Pr. C. Pvokplak solution 21. with conjugated π bonds Type Mixing ratio (a) Anervanic compound (B) (a) / (b) a tin-saline ratio Po J y molar compound (C) (a) / (c) palliative ratio <2> horses FROM Solvent1 o species Pomer mixing 425 * 6-Phenykumarine / 20/80 Solvents lrt 5 Colloidal oxide to remittance 100/80 - 0.6 water / methanol 30/70 426 N-Naphthylethylenedia * t n - Polycyclic. lopentánox id 100/30 0.8 benzene 427 1-Throonaphthalene - - 0.5 methanol 428 1,1'-Diamino-2, 2'bxnafty 1 Colloidal silicon dioxide 100/50 - 1.0 Water / Methanol 30/70 429 Benzoindanún - - 0.6 curling 430 Oxybenzoakridín - - 0.7 431 l-hUftal6n-2'indolindigo F (IDH) _and salt 100/30 - 0.6 Water / Methanol 20/80 432 α-Naftaamzdoxim - - 0.5 methanol 433 ot-Our tylglyDxal - - 0.5 434 9-Merkap Sealing Racer » - - 0. 7 ¹¹ 435 9,10-Diamino-50/50 phenanthrene / phenothiazine in Colloidal silicon dioxide 100/100 - 1.2 Water / Methanol 50/50 4 36 2-Aminofonantrínchinón Polybutadlér 100/10 0.5 70/30

Table VI (2) (continued)

and 1 3) Cl-kone. upper and middle lower: ma: t. -mi n. ppm (4) Daba washing VOdDU after completion min. Vi routine. 1nnrrrrrrrrrrng (Adm 30 Batch no. 10 50 1 00 150 200 425 « 290 270-340 60 C F H (700) 426 14 11-18 15 A A A A 8 Cí 10) 427 9 6-12 · · A A B C D F C 60) 42Θ ii 7-13 A A A A A Bil, 5) 429 8 6-9 · · A A R C D F (57) 430 5 3-7 A A A B C D (19) 431 19 17-21 - A A A A A BI2 _f 7) 432 16 14-18 10 A A A & C DÍ1G) 433 20 18-23 A A 8 C Γ » F (5 <?) 434 e 5-11 A A B C D F (62) 435 9-14 A A A A A B (1.2) 436 14 1 1-17 A A A A 8 C (9)

Table VI (3)

1 Pr. no. Coating solution. 21 »* conjugated w links (a) Inorganic compound (B) (O / t weight ratio After 1 yeast compound (C) 1 · 1 / (C) weight ratio <2) horses X solvent Type Mixing ratio species Pomer mixing 437 Perylene / 2,2'- 90/10 diOKyazobenzén - - 0.0 methanol 438 1,2-Ďen2ofpniíťn - - 0.4 · · 439 2-Iodo ~ l, 4naftochinón - - 0.5 440 Dlantrachinónimíd - - 0.5 441 Chinizari nquinone FelOH) salt 100/10 - 0.5 Water / Metáne1 20/80 442 DloxyakrIdón - - 0.6 methanol 443 3, a-diaminoacridine Colloidal silica oxide 100/300 - 0.B Water / Metaná1 40/60 444 4'-Nitrozo-2-ni trodi feny 1λλϊn - 0, 7 methanol 445 4,4 Dinitradlfsnylamín - - 0.9 446 Dinitrofcny1indazol - - 0.5 - 447 Amphnobenzophenone Phonantran / Phenothlaz 1 n Colloidal oxide with silica or thio 100/100 - 1 ϋ Water Methanol 50/50 4 ^ 3 1,3, B-Triní li ufencx and ϊη - - 0.5 Metano1

Table 3> <Contact 11 *>

í 1) Pr. No. 13) L ”horse, upper: middle lower: max.-min. ppm Water wash time after min. Visual assessment (Batch Dose no. amount «a / mJ 1 10 30 50 100 150 200 437 17 14-19 1O A A A B C D (1Θ) 43 & 10 0-12 10 A A 8 C D F (57) 439 6 5-7 A A 8 C D F (61) 44O 11 9-13 '· A A B C D F (60) 441 19 16-22 A A A A A 8 (1.9) 442 8 5-i 1 · · A A & C D F (58 1 443 17 14-20 · · A A A A A B (3> 444 9 5-13 A A A B C DI9> 445 15 11-10 A A B C D F (59> 446 17 1 4-20 A A 8 C D F (55> 447 1 1 9-13 A A A A A B (2.5> 448 14 11-17 A A B C D F (57)

SK 277795-6

Table V] (4)

1> Pr. no. Coating solution Z1. * to Dn her cooking them n bonds (a) Inorganic (a) / (b) a weight ratio Polymer (a> / <c> compound weight (c) ratio (2) horses X solvent Species Ratio mixing Compound (b) species Pomer mixing 449 2.2'-Diokybi bitches 1 - - 0, 5 methanol 450 6-Fénylkumarln / 20/00 Colloidal oxide 100/60 - u, 6 Water / 30/70 Roxppustadlová čerA 5 silica methanol 451 7-0xy-3,4- - Aulytetrahydrofuran 100/50 0.7 Ben zén thiocoumarin 452 2-Feny1-3- Colloidal oxide 100/40 0, 9 Water / 50/50 fenylasoindol silicon i th methanol 453 Indofer (n - - 0.6 methanol 454 Polyfyraj in - - 0.7 455 4-Phenyl 1 oxaxo 1 - - 0, 6 ¹¹ 436 5-Benzoy1-3.4dl hairdryers> aziaz - - 0, 4 457 2-Amino-4- Colloidal oxide 100/150 - 0.0 Water / 30/70 fanyltiaxol silica methanol 45B 2-Fenyla2olmidazol - - 0.5 methanol 459 4-Pyridazorezorc in Colloidal oxide 100/200 - O, Θ Water / 40/60 silica methanol 460 2,3 — hi hi nd i ol - - 0.6 methanol

Table VI (41 (continued)

(1) Ex. no. (3) Cl “horses, upper and middle bottom have>: .- min. ppm <4) Water wash time after min. inlay Batch no. Zuà x 10 7.0 50 100 150 200 449 12 9-14 15 A B C D E F (59) 450 17 14-20 A A A A A B (1.5) 451 1B 14-71 A A A B C D <19) 452 12 10-14 A H A A A β (1, S>) 453 20 10-22 · · A A B C b VtbQ) 454 16 13-19 A B C D E F (65> 455 9 6-12 A A B C D F (39) 436 11 8-14 A A B C D F í 55) 457 19 17-21 10 A A A A A B (1,6) 45Θ 6 5-10 A A 3 C D F (60) 459 6 3-7 A A A A A 8 (1.51 460 1 1 9-13 A B C D E F C 57)

SK 277795-6

Table VI

Coating solution Pr. C. 21.with conjugated n bondsia) Inorganic (a) / (b) Polymary <a) / (c> C2>) weight horse ratio% solvent Species Ratio mixing Compound by weightChem (b) ratio (c>) type Mixing ratio 461 1-Aminoisoquinoline - Q »7 Methane 1 462 9-Axyacridine / basic orange 14 70/30 Polýchinaxŕ.l tn 100/60 l.O DMF 463 Ni trofenothiazťn - 0 »4 methanol 464 2-Fenadinol - O, β 465 2, β-Díaminodibenzotioíén - 0.6 · 466 CyklaC3,3,3Jsz ín F »(OH >> salt 100/30 0.6 Water / 10/90 methanol

Table VH5> (continued)

<1> Pr. no. <3> Cl ^- horses. upper: middle lower: max.-min. ppm (4> Water wash time after completion min. 10 inlay Batch no. lDŽStVD Q ΖΠΓλ 30 5ϋ 1OO 150 200 461 17 14-20 10 A A 9 C D F (56> 4T2 19 15-24 * A A A A A 1) 463 10 8-13 A B C D E F (60 5 464 7 5-9 - A A B C D F (62> 465 6 5-7 A B C D E F i 57 1 466 11 9-13 A A A A A Bil, 3)

Notes: (1) * Comparative examples (2) Concentration of the compound with conjugated π bonds in the coating solution (31 Concentration of chloride ion in suspension after ultonCent polymerization (4) Water flow rate 0.1 m * / ms h

Example 7

As shown in Table Vn, in each assay, a compound with conjugated n bonds is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or a polymeric compound, to prepare a coating solution. Table VII also shows the weight ratio of inorganic compound and polymer compound and the concentration of compound with conjugated n bonds in the coating solution. The coating solution is then applied to the polished internal walls of a 1000 liter polymerization vessel and to parts of the apparatus that come into contact with the monomer, such as a stirrer; after application, the coating is dried at 60 ° C for 20 minutes and then thoroughly rinsed with water.

Thereafter, the coated polytnerization vessel is charged with 160 kg of vinyl chloride monomer, 40 kg of vinyl acetate monomer, 400 kg of deionized water, 600 g of gelatin, 2 kg of triclene and 350 g of lauroyl peroxide and the polymerization is carried out at 70 ° C for six hours. After the polymerization is complete, the polymer 5 is removed and the polytnerization vessel is rinsed inside with water at a flow rate of 0.1 µm for ² hours, as shown in Table VR The above operation from coating and loading to water washing is performed for each batch and the operation is repeated up to 200 times.

The chloride ion concentration is controlled as in Example 1, and the extent of the incrustations is also evaluated. The test conditions and results are shown in Table VII.

In Table VII, the comparative tests are also marked with an asterisk (15). In the case of Examples 467 and 468, the inner walls of the polymerization vessel were not treated and coated with no compound.

Table VU (l)

(1) Pr. J Coating coating 1 · * with juggled e bonds (a) Inorganic (A) / (b) Polymŕrna <A) / (c) (2) solvent no. Type Mixing ratio (b) hmotnoetný ratio Compound (c) hmotnoetný ratio horses X type FOiwr mixing 467 * - - - - 468 « - - - - 469 « 2,2 ‘-Diaminodiphenyls1 - - 0.5 methanol 470 * colloidal silicon dioxide Íûõ / IOO - 1.0 471 * - 0/100 - 1.0 Water 472 « 1-Amínofenantridín - Polycyclopentadiene 50/50 1.2 Benzénl 473 * - - 0/100 1.0 474 * 2-Chl - - 0.5 methanol 475 * Pyrazoiantrôn - - 0.6 ethanol 476 « 4,10-Dioxy-1,7-enanroline FeCl _a 1OO / 2 - 0.5 methanol 477 * 1,2-Dihydronattalén Fe (OH> 3 salt) 100/10 - 0.5 47B * 3,3'-Azopyridín - - 0, Θ · ·

Table VII (i> (continued)

i 3 J (4) InkrusiAr i a (1) CI— horses. Wash time Viau: r.e hodnotateni. (Swipe many Ex. upper and middle water after Batch no. No. lower: max.-min. termination ppm min. 10 30 50 100 150 200

467 * 350 320-390 60 H <1100) 468 « 10 7-12 H <1000) 469 * 290 270-350 G H <700> 470 * 270 250-320 C F H (600) 471 « 250 230-310 H (900) 472 « 280 260-330 '· C F H (500 &gt;) 473 * 250 230-320 ^H H «1000) 474 * 240 220-300 ^M G H (950) 475 » 300 280-350 '· □ H (BOO) 476 * 310 290-360 C F H (700) 477 * 240 220-2Θ0 C F H (650) 478 * 260 240-310 G H (850)

Table VII (2)

<1) Ex. no. Tell you about the solution Z1 with conjugated n bonds Type Mixing ratio (a) Inorganic compound <b> (a) / (b) by weight ratio Polymer compound (c (a) / (c) weight ratio (?) horses FROM solvent type Mixing ratio 479 * 1-Amino-5-fény1tetrazo) - - 0.8 Etano1 480 * Phenazine / 70/30 Black & White 3 - - 481 2,2-Di »minDbifenyl - - 0.5 methanol 482 · ' Colloidal silicon dioxide 100/100 - 1.0 483 Roeeindol FeOH), salt 100/20 - 0.5 · · 484 Indofen i n - - 0, 5 · 485 Chlorophyll b - - 0.5 ethanol 486 Phthalotanamine / 2,4-50 / 50 Diaminophenazin Ortho-kremite and the acid 100/50 - 0, 7 methanol 487 3,3'-Azopyrídín - - 0.8 · 488 7, B-Dloxyflavôn - - 0, 5 ethanol 489 N-Nitroso-α-naphthylhydroxylamine - - 0, 3 Methane 1 490 2-Chloroquinoxzar tn - - 0.5 -

Table V1IC2) (continued)

(1> Ex. no. <3) Cl 'horses. upper: middle lower: max.-min. ppm <4> Water wash time after completion min. Batch no. Zjfll-2 10 30 50 100 150 200 479 * 280 260-330 60 □ H (000) 480 * B C F H (500> 481 9 6-11 Lô A A B C t * F <60) 4B2 10 8-12 '· A A A A A And (O, 5) 483 8 5-10 A A A A A E * (2.5) 484 15 12-17 A A B C D F (55) 485 20 16-22 A A B C D F (28) 486 15 12-17 · ' A A A A A A (0) 4) 487 13 10-15 A A B C D F (56) 488 14 1 1-16 A A A B C D (20) 489 11 8-13 A A A B C BC 18) 490 10 7-12 A A B C D F C 57)

Table VIl <3>

Coatings? solution 1> Pr. e. 21. with conjugated vaws (a) Inorganic (a) / <b> weight ratio Polymer compound <c> (a) / (c> weight ratio (2) horses X solvent Type Mixing ratio z lLKinina (B) type Mixing ratio 491 2- <o-Aminophenylloxazole Netatetracosilicate 100/200 acid - 1.5 HetanDl 492 2-Phenylazothiazole - After 1yutobutene 1.0 · ' 493 1-Amino * 5phenyls 11 · tr azo i - - 0.8 ethanol 494 3.2'-Diindoles 1 colloidal silicon dioxide 100/20 - 1 0 Meter, ol 495 1-Amínofenantoridin - Polycyclopentadiene 50/50 1.5 benzene 496 4, JO-dioxo-1,7- phenanthroline FeCl? 10072 - 0.5 Netanel 497 Fen.azin n / 70/30 Roappustad1 Black 3 - - 0.5 490 dibenzosuberol - - 0.3 499 «-Netcxytenazťn - - 0, 7 ethanol 500 2-Pheny1ben ot ot to az1 - - 0.5 Metand 501 3-phenylcoumarone - - 0.3 toluene 502 1,2-Dihydronaphthalene FeiOHh salt 100/10 - 0.5 Netanel

Table VII (3> <continued>

- v υ - Q. <3) Cl-kOGC. hprriäs «middle bottom: in ::, -min. PPm «4i Water wash time after min. VizuAlng L-.krĽstAF rating i Prihnite clay .fe.ivn _a Zí1l ² 1 10 30 50 100 150 200 491 9 6-1 1 15 A A A A A A 10,7) 492 1 2 9-14 A A A A A B (2,3> 493 14 11-16 A A & C b F (58) 494 15 13-17 A A A A A A (0,6> 495 14 11-16 A A A A A 8 (3) 496 15 12-17 '· A A A A A And (O, 4) 497 17 14-19 '· A A A A A And (o, 7) 498 1 1 8-13 · · A A B C D F (5FC> 499 18 16-20 '· A A A B C 0 (21) 501 14 11-16 A A & C D F (55 I 502 10 7-12 A A B C D F (54) 503 9 5-10 10 A Fiction A A A A <0.5>

Table Vil (4)

1) Pr. e. Coating solution 21. * conjugated π bonds (a) Inorganic (a) Z (b) compounds * weight (b) ratio polymer X 1 <C (a) / (c> weight ratio) (2) horses X solvent Species Ratio mixing type Mixing ratio 503 Perimidine / Phenylroindindarin 20/80 - - 4, 4 THF 304 benzoazol lO-phenanthroline-9 • HiCla 100/5 - 0.5 methanol 503 4-Nitroso-naphthyl-1 amine - - Q.7 M 506 Pyrazolantrón - - O.B ethanol

Table VI1 (4 t (continued)

(1) Ex. no. (3) Cl ”horses, upper: middle lower: max.-min. ppm í 4 i Water wash time after min. VižuAlnf hnrlr lotion (PriTnnté nno Batch no. ifitvo u / m-) 10 70 SO 1OO 130 200 503 12 9-14 10 A A A B ¼ D (20 Mar 504 9 6-11 · · A A A A A 8 (2.1) 505 10 7-12 ¹¹ A A A B C D (9) 506 15 12-17 A A D C D F160 J

Notes: (1) * Comparative examples (2) Concentration of compound with conjugated n bonds in solution (3) Concentration of chloride ion in the suspension after polymerization Γ4> Water flow rate 0.1 m ³ / m ² h

Example 8

As shown in Table VID, in each assay, a compound with conjugated n bonds is dissolved or dispersed in a solvent, optionally with the addition of an inorganic compound or polymer compound, to prepare a coating solution. In Table VI, the weight ratio of the inorganic compound and the polymeric compound and the concentration of the compound with conjugated n bonds in the coating solution are also given. The coating solution is then applied to the polished internal walls of a 1000 liter polymerization vessel and to parts of the apparatus that come into contact with the monomer, such as a stirrer; after application, the coating is dried at 80 ° C for 10 minutes and rinsed thoroughly with water.

The coated polyinerization vessel is then filled with 200 kg of vinyl chloride monomer, 400 kg of dionized water, 40 g of partially saponified polyvinyl chloride, 60 g of hydroxypropylmethylcellulose and 80 g of di-2-ethylhexylperoxycarbonate and the polymerization is carried out at 57 ° C for 7 hours. After the polymerization is complete, the polymer is removed and the polyinerization vessel is washed with water at a flow rate of 0.1 5 minutes, as shown in Table VI. Said operation, from coating and filling to washing with water, is performed for each batch and the operation is repeated a maximum of 200 times.

The chloride ion concentration is controlled in the same manner as in Example 1, and the extent of incrustation is also evaluated. The number of fisheyes in the products obtained from the polymers produced in the 10th, 30th, 50th, 100th, 150th and 200th batches is similarly determined as described in Example IV. Test conditions and results are shown in Table 15 of the VHI. In the VRI table, the comparative tests are also marked with an asterisk. In the case of Examples 507 and 508, the inner walls of the polyinerization vessel were not treated and coated with no compound.

Table VI1K1>

Coating solution (1) Pr. Conjugated w binding · í (a) Inorganic 4 a) / (b) Pniymárna (A) / (c) <2) Rospúfiťad1 o e. ' Species Ratio • ioáania 2lúCenina (B) weight ratio COMPOUND (c) weight ratio kone Z type Mixing ratio 507 * - - - - 509 * - - - - 509 * 2-Phenyl-3- fenylazoindol - - 0.3 - 510 « * Fluorremium acid 100/300 - 1.0 - 511 * - 0/100 - 0.9 - 512 * 9-Acridine / Acid Black 2 80/20 Colloidal silicon dioxide 100/100 - 1.5 - 513 * 2-Fony1tiofán - - 0.5 - 514 * Alizar ín - - 0.5 - 515 2-Feny1-3- 1eny1azoindol - - 0.5 ethanol 516 · · Orthocremic tA acid 100/300 - 1.0 517 2-aminophenazine - - 0, 7 methanol 51B Alizarŕn - - ú, 5

Table VI11 (1) C continued)

(1) Pr. e. C 3) Cl 'horses, upper) middle lower: eax.-ain. ppm (5> Inkrui Wash wash Visual assessment Anthracite a / m => C. Fish et al. D4vk. e tpoŕgt) after min. dose 10 30 50 100 150 200 10 30 50 100 150 200 507 * 280 260-300 60 H (1000) 300 SOB * 10 8-12 · · H <950> 200 509 « 290 240-300 '· G Hl900) 1 10 220 510 * 290 250-310 w B C F H1950) 20 40 90 130 511 * 15 13-18 H <1000) 290 512 * 270 230-290 B C F H C500) 18 35 80 10O 513 * 250 230-280 * □ H (950) 100 200 514 * 310 290-350 □ MÍ900I 90 210 515 13 10-15 10 A A A B C D <20) 0 0 2 9 23 37 516 12 9-15 A A A A A A <0.3) 0 0 0 0 2 6 517 15 13-18 A A A B C IK 101 0 0 6 11 20 35 316 17 15-20 A A A B C D (21) 0 0 3 10 30 41

Table VIII

tl Coated swarm flow .. Pr. e. 21. »KonjuQovanýffli ir bonds (a) Inorganic <a> / C b> polymer <a> / <c) (2) solvent zlúfeninA weight from compound weight horses. Type Ratio miH »ni * (B) ratio (c ratio % type Mixing ratio 519 1-Aminophenanthridine Fb <OH). AOL 100/10 0.5 methanol 520 1O benzoazol-9fenantrol - - 0.6 · ' 521 ? -Acridine / 80/20 Colloid oxxd 100/100 0.8 Sour Black 2 silica 522 Dinitrofeny1indazol - - 0. 5 benzene 523 4-Fyridy1-mfenyléndiamín - - 0 »7 ethanol 524 2-Fenyltiofán - Polycyclic 1-hexane oxide 1.5 toluene 525 «-Nitroso-fl-naphtha to L FeCl ₌ 100/5 - 0, 7 methanol

Notes with <1) * Comparative examples

12) Concentration of compound and cannulated ir bonds in coating solution (3) Concentration of chloride ion in suspension after polymerization (4) Water flow rate 0.1 m

Industrial usability

The solution can be used in the chemical industry in the production of vinyl chloride polymer.

Claims (9)

A process for the production of vinyl chloride polymer by suspension polymerization or emulsion polymerization of a vinyl chloride monomer with a vinyl monoinomer copolymerizable with a vinyl chloride monoinomer in an aqueous medium, characterized in that the polymerization is carried out in a polymerization vessel having internal walls and interfacing components. with a monoiner in the polymerization, they are pre-coated with an incrustation prevention agent comprising at least one substance selected from the group consisting of azo dyes and pigments, anthraquinone dyes and pigments, indigo dyes and pigments, flalocyanine dyes and pigments, carbon dyes and pigments, carbon dyes and pigments , nitro-dyes, benzoquinone and naphthoquinone dyes, naphlalimide dyes and pigments, perinone dyes, 10 fluoroscopic dyes, sulphide dyes, insoluble azo dyes and reactive dyes and, where appropriate, e, the concentration of chloride ion in the reaction mixture is not more than 100 ppm. The method of claim 1, wherein the incrustation prevention agent is an azo dye. 3. The method of claim 1, wherein the incrustation prevention agent comprises an inorganic compound as an additive. The method of claim 3, wherein the inorganic compound is selected from the group consisting of silicas and silicates, alkaline earth metal salts, zinc group metals, aluminum group metals, tin group metals, iron group metals, metals chromium groups, manganese group metals, copper group metals and platinum group metals and inorganic colloids. 5. The process of claim 4 wherein the inorganic compound is a silicate, colloidal silicic acid, or colloidal ferric hydroxide. Method according to claims 1 to 5, characterized in that the agent for preventing incrustations comprises a fixing agent for promoting its adhesion. 7. The method of claim 6, wherein the fixing agent is at least one compound selected from the group consisting of olefinic polymers, diene polymers, acetylene polymers, aliphatic vinyl or vinylidene polymers, aromatic vinyl polymers, heterocyclic vinyl polymers, acrylic or methacrylic. polymers, polyethers, polysulfides, polysulfones, addition polymers, polyesters, polyamides, polyurethanes, polyureas, linear condensed polymers, heterocyclic condensed polymers, natural polymers, modified natural polymers, polysiloxanes, organometallic polymers, and inorganic polymers. The process according to claims 1 to 7, wherein the parts of the system for recovering unreacted monomers where they can adhere to the incrustations are further pre-coated with an incrustation prevention agent. Method according to claims 1 to 8, characterized in that the inner surface of the walls and the parts of the auxiliary device of the polymerization vessel which can come into contact with the monomer have a surface roughness of at most 10 micrometers.