United States Patent [191 [11] Patent Number: 4,758,639 Koyanagi et al. [45] Date of Patent: Jul. 19, 1988

[54] PROCESS FOR PRODUCTION OF VINYL [56] References Cited POLYMER . U.S. PATENT DOCUMENTS [75] Inventors: Shunichi Koyanagi, Yokohama; 3,923,765 12/1975 Goetze et al...... 526/62 Hajime Kutamura, Ichihara; 4,049,895 9/1977 McOnie et al...... 526/62 Toshihide Shimizu; Ichiro Kaneko, 4,539,230 9/ 1985 Shimizu et al...... 526/62 X both of Ibaraki, all of Japan Primary Examiner-Joseph L. Schofer Assistant Examiner-F. M. Teskin [73] Assignee: Shin-Etsu Chemical Co., Ltd., Tokyo, Attorney, Agent, or Firm—0blon, Fisher, Spivak, Japan McClelland & Maier [21] Appl. No.: 94,020 [57] ABSTRACT [22] Filed: Sep. 3, 1987 A process for production of a vinyl polymer by suspen sion polymerization or emulsion polymerization of at Related US. Application Data least one kind of vinyl monomer in an aqueous medium is disclosed. [63] Continuation of Ser. No. 765,803, Aug. 15, 1985, aban In this process, the polymerization is carried out in a cloned. polymerizer, the inner wall surface and portions of the [30] Foreign Application Priority Data auxiliary equipment thereof which may come into contact with the monomer during polymerization hav Aug. 17, 1984 [JP] Japan ...... 59471045 ing a surface roughness of not greater than 5 pm and Aug. 17, 1984 [JP] Japan ...... 59-171046 being previously coated with a scaling preventive com [51] Int. Cl.‘ ...... C08F 2/18; C08F 2/22; prising at least one selected from dyes, pigments and CO8F 2/44 aromatic or heterocyclic compounds having at least 5 [52] US. Cl...... 526/62; 526/74; conjugated 7r bonds. According to this process, scaling 526/191; 526/201; 526/204; 526/2l8.1; on the inner wall surface of a polymerizer, etc. during 526/344.2; 427/239; 427/327 polymerization can be prevented effectively and surely. [58] Field of Search ...... 526/62, 74, 191, 201, 526/204, 218.1, 344.2; 427/239, 327 11 Claims, No Drawings 4,758,639 1 2 According to the process of the present invention, the PROCESS FOR PRODUCI'ION OF VINYL scaling preventive action possessed by the above scaling POLYIVIER preventive can be induced surely and potently, whereby scaling can effectively be prevented. Accord This application is a continuation of applicatidn Ser. 5 ingly, no labor or time is required for scale removal, No. 765,803, ?led on Aug. 15, 1985, now abandoned. enabling continuous use of the polymerizer and im This invention relates to a process for producing a proved running ef?ciency. Also, the cooling capacity of vinyl polymer, particularly to improvement of scaling the polymerizer can be maintained constantly, without prevention on the inner wall surfaces of a polymerizer, any fear of entrainment of scales into the product, etc. in the course of polymerization of vinyl chloride, thereby improving the quality of the product polymer. etc. The term “surface roughness” used herein means the In processes for suspension polymerization or emul Rmax (maximum height) as de?ned in Japanese Indus sion polymerization of vinyl monomer such as vinyl trial Standard (J IS) B 0601. The surface roughness chloride monomer in the presence of a polymerization Rmax can be measured by a probe method (I IS B 0651) catalyst, there is involved the problem that polymer or an optical method (115 B 9652), or the like. scales stick to the inner wall surface of the polymerizer It is difficult to elucidate the reason why scaling can or the portions of the auxiliary equipment of the poly be prevented effectively when the surface roughness of the surface to be coated with the scaling preventive is merizer which may come into contact with the mono mer, such as stirrer, during polymerization. Scales stick previously controlled to 5 pm or below, preferably 3 ing to the irmer wall of the polymerizer, etc. will result pm or below, in accordance with the present invention. However, where the surface roughness is in excess of 5 in a lower polymer yield and cooling capacity of the pm, the effect of the abovementioned scaling preven polymerizer, and may also cause so-called ?sh eyes tive is not fully displayed; namely, the scaling cannot be formed by the adhering scales peeling off the inner wall prevented effectively, even if the scaling preventive is of the polymerizer and mixing in with the product, 25 applied to the inner wall surfaces of the polymerizer, thereby lowering the quality of the product. Further, etc. the removal of the adhering scales requires enormous an The process of the present invention can be applied amount of labor and time; in addition, unreacted mono irrespective of the materials constituting the inner wall mers (vinyl chloride, etc.) are absorbed into the scales surface of the polymerizer and the portions of the auxil which may involve disadvantageously the danger of 30 iary equipment thereof which may come into contact bringing about hazards to the human body. with the monomer. The polymerizer and its auxiliary As the method for preventing scaling of polymer, it is equipment are generally formed of such materials as known in the art to apply a coating of a chemical rea stainless steel, carbon steel, Monel metal, titanium, etc., gent (hereinafter referred to as “scaling preventive”) on and in some cases the inner wall surface of the polymer the inner wall surface of the polymerizer; various such 35 izer is lined with glass. In the case of any such materials, scale preventives have been proposed. Among the vari scaling can be prevented effectively by controlling the ous known methods, there is known a particularly good surface roughness to 5 pm or below prior to coating the method in which a dye and/or a pigment is used as the surface with the scaling preventive. scaling preventive (Japanese Patent Publication No. Where the original surface roughness of the inner 30835/1970). However, this method is not always effec wall surfaces of the polymerizer, etc. is in‘ excess of 5 tive and sure in preventing scaling, and thus is not al pm, the surface roughness should be controlled to 5 pm ways satisfactory. or below by an appropriate polishing method, prior to Accordingly, an object of the present invention is to coating the surface with the scaling preventive. The provide a process for production of a vinyl polymer polishing methods which can be employed are not par which can surely prevent scaling in the course of poly 45 ticularly limited; examples of such methods include merization of one or more kinds of vinyl monomers. buffing, electrolytic polishing, and polishing with The present inventors in attempting to improve on emery paper. the method disclosed in Japanese Patent Publication According to the present invention, one or more No. 30835/1970 have consequently found that scaling compounds selected from dyes, pigments and aromatic can be prevented effectively and surely by use of a dye, or heterocyclic compounds having at least 5 conjugated a pigment or a speci?c compound having at least 5 1r bonds (hereinafter referred to simply as “conjugated conjugated 7T bonds as a scaling preventive, and also by 1:" bond compounds”) may be used singly or in combina controlling the surface roughness of the inner wall sur tion. However, it is preferable to use a dye or pigment, faces of the polymerizer, etc. to be coated with the and more preferably an azine dye. scaling preventive to a predetermined value or below. 55 The dyes and pigments which can be used as the According to the present invention, there is provided scaling preventive in the process'of the present inven a process for production of a vinyl polymer by suspen tion may be exempli?ed by: sion polymerization or emulsion polymerization of at azo dyes such as monoazo and polyazo dyes and pig least one kind of vinyl monomer in an aqueous medium, ments, metal complex azo dyes and pigments, stilbene characterized in that the polymerization is carried out in 60 azo pigments, thiazole azo dyes and the like; a polymerizer, the inner wall surface and portions of the anthraquinone dyes and pigments such as anthraqui auxiliary equipment thereof which may come into none derivatives, anthrone derivatives and the like; contact with the monomer during polymerization hav indigoid dyes and pigments such as indigo derivatives, ing a surface roughness of not greater than 5 pm and thioindigo derivatives and the like; being previously coated with a scaling preventive com 65 phthalocyanine dyes and pigments; prising at least one selected from dyes, pigments and carbonium dyes and pigments such as diphenylmethane aromatic or heterocyclic compounds having at least 5 dyes, triphenylmethane dyes and pigments, xanthene conjugated 11 bonds. dyes, macridine dyes and the like; 4,758,639 3 4 quinoneimine dyes such as azine dyes, oxazine dyes, 268, 276, 277, 282, 289, 301 and 302; Acid Black 1, 7, 24, thiazine dyes and the like; 26, 29, 31, 44, 76, 77, 94, 109 and 110; Mordant Yellow methine dyes such as polymethine or cyanine dyes and 1, 3, 5, 23, 26, 30, 38 and 59; Mordant Orange 1, 4, 5, 6, the like; ' 8, 29 and 37; Mordant Red 7, 9, 17, 19, 21, 26, 30, 63 and quinoline dyes; 89; Mordant Violet 5 and 44; Mordant Blue 7, 13, 44, 75 nitro dyes; and 76; Mordant Green 11, 15, 17 and 47; Mordant benzoquinone and naphthoquinone dyes; Brown 1, 14, 15, 19, 21, 33, 38, 40, 52 and 87; Mordant naphthalimide dyes and pigments; Black 1, 3, 7, 9, 11, 17, 26, 32, 38, 43, 44, 51, 54, 65, 75, perinone dyes; 77, 84, 85, 86 and 87; Food Yellow 3 and 4; Food Red 7 and 9; ?uorescent dyes; exemplary metal complex azo dyes are Solvent Yel azoic dyes; and low 61 and 80; Solvent Orange 37, 40 and 44; Solvent reactive dyes. Red 8, 21, 83, 84, 100, 109 and 121; Solvent Brown 37; These can be used either singly or in any desired combi Solvent Black 23; Acid Black 51, 52, 58, 60, 62, 63, 64, nation of two or more compounds. Of these dyes and 15 67, 72, 107, 108, 112, 115, 118, 119, 121, 122, 123, 131, pigments as exempli?ed above, particularly preferred 132, 139, 140, 155, 156, 157, 158, 159 and 191; Acid are azine dyes, as mentioned above. More speci?cally, Yellow 59, 98, 99, 111, 112, 114, 116, 118, 119, 128, 161, typical examples of these dyes and pigments are enu 162 and 163; Acid Orange 74, 80, 82, 85, 86, 87, 88, 122, merated below. 123 and 124; Acid Red 180, 183, 184, 186, 194, 198, 199, Azo dyes and pigments include the following com 20 209, 211, 215, 216, 217, 219, 256, 317, 318, 320, 321 and pounds. Exemplary monoazo and polyazo dyes are 322; Acid Violet 75 and 78; Acid Blue 151, 154, 158, Basic Yellow 32, 34 and 36; Basic Orange 2, 32, 33 and 161, 166, 167, 168, 170, 171, 175, 184, 187, 192, 199, 229, 34; Basic Red 17, 18, 22, 23, 24, 32, 34, 38, 39 and 40; 234 and 236; Acid Green 7, 12, 35, 43, 56, 57, 60, 61, 65, Basic Violet 26 and 28; Basic Blue 58, 59, 64, 65, 66, 67 73, 75, 76, 78 and 79; Acid Brown 19, 28, 30, 31, 39, 44, and 68; Basic Brown 1, 4, 11 and 12; Basic Black 8; 25 45, 46, 48, 224, 225, 226, 231, 256, 257, 294, 295, 296, Azoic Diazo Component 4, 21, 27 and 38; Disperse 297, 299 and 300; Direct Yellow 39; Direct Violet 47 Yellow 3, 4, 5, 7, 8, 23, 50, 60, 64, 66, 71, 72, 76, 78 and and 48; Direct Blue 90, 98, 200, 201, 202 and 226; Direct 79; Disperse Orange 1, 3, 5, 13, 20, 21, 30, 32, 41, 43, 45, Brown 95, 100, 112 and 170; 46, 49, 50 and 51; Disperse Red 1, 5, 7, 12, 13, 17, 43, 52, an exemplary stilbene azo dye is Direct Black 62, and 54, 56, 58, 60, 72, 73, 74, 75, 76, 80, 82, 84, 88, 90, 97, 99, 30 exemplary thiazole azo dyes are Direct Red 9 and 11. 101, 103, 113, 117, 122, 125, 126, 128 and 129; Disperse Anthraquinone dyes and pigments include the fol Violet 10, 24, 33, 38, 41, 43 and 96; Disperse Blue 85, 92, lowing compounds. 94 and 106; Disperse Brown 3 and 5; Disperse Black 1, Exemplary anthraquinone derivatives are Basic Vio '2, 10, 26, 27, 28, 29, 30 and 31; Solvent Yellow 2, 6, 14, let 25; Basic Blue 21, 22, 44, 45, 47, 54 and 60; Azoic 15, 16, 19, 21 and 56; Solvent Orange 1, 2, 5, 6, l4 and 35 Diazo Component 36; Vat Yellow 2, 3, 10, 20, 22 and 45; Solvent Red 1, 3, 23, 24, 25, 27 and 30; Solvent 33; Vat Orange 13 and 15; Vat Red 10, 13, 16, 31, 35 and Brown 3, 5 and 20; Solvent Black 3; Pigment Yellow 1, 52; Vat Violet l3 and 21; Vat Blue 4, 6, 8, 12, 14, 64, 66, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73 and 67 and 72; Vat Green 8, 13', 43, 44 and 45; Vat Brown 1, 83; Pigment Orange 1, 2, 5, 13, 14, 15, 16, 17, 24 and 31; 3, 22, 25, 39, 41, 44, 46, 57, 68, 72 and 73; Vat Black 8, Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 40 14, 20, 25, 27, 36, 56, 59 and 60; Disperse Orange 11; 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, Disperse Red 4, 9, 11, 15, 53, 55, 65, 91, 92, 100, 104, 116 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 112, 114 and 127; Disperse Violet 1, 4, 8, 23, 26, 28, 30 and 37; and 163; Pigment Blue 25; Pigment Green 10; Pigment Disperse Blue 1, 3, 5, 6, 7, 20, 26, 27, 54, 55, 56, 60, 61, Brown 1 and 2; Pigment Black 1; Direct Yellow 1, 8, 11, 62, 64, 72, 73, 75, 79, 81, 87, 90, 91, 97, 98, 99, 103, 104 12, 24, 26, 27, 28, 33, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100 45 and 105; Disperse Yellow 51; Solvent Violet l3 and 14; and 110; Direct Orange 1, 6, 8, 10, 26, 29, 39, 41, 49, 51, Solvent Blue 11, 12, 35 and 36; Solvent Green 3; Pig 57, 102 and 107; Direct Red 1, 2, 4, l3, 17, 20, 23, 24, 28, ment Red 83 and 89; Pigment Blue 22; Acid Violet 31, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 34, 35, 41, 43, 47, 48, 51, 54, 66 and 68; Acid Blue 23, 25, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 27, 40, 41, 43, 45, 54, 62, 72, 78, 80, 82, 112, 126, 127, 129, 230 and 231; Direct Violet 1, 7, 9, 12, 22, 35, 51, 63, 90, 50 130, 131, 138, 140, 142, 143, 182, 183, 203, 204 and 205; 94 and 98; Direct Blue 1, 2, 6, 8, 15, 22, 25, 71, 76, 77, 78, Acid Green 25, 27, 28, 36, 40, 41 and 44; Acid Brown 80, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 27; Acid Black 48 and 50; Mordant Red 3 and 11; Mor 196, 203, 207, 225, 236, 237, 246, 248 and 249; Direct dant Blue 8 and 48; Mordant Black 13; Pigment Violet Green 1, 6, 8, 28, 30, 31, 33, 37, 59, 63, 64 and 74; Direct 5; Brown 1A,. 2, 6, 25, 27, 44, 58, 59, 101, 106, 173, 194, exemplary anthrone derivatives are Vat Yellow 1 and 195, 209, 210 and 211; Direct Black 17, 19, 22, 32, 38, 51, 4; Vat Orange 1, 2, 3, 4 and 9; Vat Violet l, 9 and 10; 56, 71, 74, 75, 77, 94, 105, 106, 107, 108, 112, 113, 117, Vat Blue 18, 19 and 20; Vat Green 1, 2, 3 and 9; Vat 118, 132, 133 and 146; Acid Yellow 11, 17, 19, 23, 25, 29, Black 9, 13, 29 and 57; Vat Red 13; Acid Red 80, 82 and 36, 38, 40, 42, 44, 49, 61, 70, 72, 75, 76, 78, 79, 110, 127, 83. 131, 135, 141, 142, 164 and 165; Acid Orange 1, 7, 8, 10, Indigoid dyes and pigments include the following 19, 20, 24, 28, 33, 41, 43, 45, 51, 56, 63, 64, 65, 67 and 95; compounds. Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 57, Exemplary indigo derivatives are Vat Blue 1, 3, 5, 35 75, 77, 85, 88, 89, 97, 106, 111, 114, 115, 117, 118, 119, and 41; Reduced Vat Blue 1; Pigment Violet l9 and 122; 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, Acid Blue 74 and 102; Solubilized Vat Blue 5 and 41; 249, 252, 254, 257, 262, 265, 266, 274, 276, 282, 283 and Solubilized Vat Black 1; Food Blue 1; 303; Acid Violet 7, 11, 97 and 106; Acid Blue 29, 60, 92, exemplary thioindigo derivatives are Vat Orange 5; 113, 117 and 120; Acid Green 19, 20 and 48; Acid Vat Red 1, 2 and 61; Vat Violet 2 and 3; Pigment Red Brown 2, 4, 13, 14, 20, 53, 92, 100, 101, 236, 247, 266, 87 and 88; Vat Brown 3. 4,758,639 5 6 Phthalocyanine dyes and pigments may include, for Reactive dyes may include, for example Reactive example, Solvent Blue 55; Pigment Blue 15, 16 and 17; Yellow 1, 2, 3, 4, 6, 7, 11, l2, l3, l4, 15, 16, 17, 18, 22, Pigment Green 36, 37 and 38; Direct Blue 86 and 199; 23, 24, 25, 26, 27, 37 and 42; Reactive Orange 1, 2, 4, 5, Mordant Blue 58. 7, 13, 14, 15, 16, 18, 20, 23 and 24; Reactive Red 1, 2, 3, Carbonium dyes and pigments include the following 4, 5, 6, 7, 8, 11, 12, 13; 15, 16, 17, 19, 20, 21, 22, 23, 24, compounds. 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, An exemplary diphenylmethane dye is Basic Yellow 46, 49, 50, 58, 59, 63 and 64; Reactive Violet 1, 2, 4, 5, 2; 8, 9 and 10; Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, l3, l4, l5, exemplary triphenylmethane dyes are Basic Red 9; 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33, 34, 37, 38, Basic Violet l, 3 and 14; Basic Blue 1, 5, 7, 19, 26, 28, 29, 39, 40, 41, 43, 44 and 46; Reactive Green 5, 6, 7 and 8; 40 and 41; Basic Green 1 and 4; Solvent Violet 8; S01 Reactive Brown 1, 2, 5, 7, 8, 9, 10, 11, 14 and 16; Reac vent Blue 2 and 73; Pigment Violet 3; Pigment Blue 1, tive Black 1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14 and 18. 2 and 3; Pigment Green 1, 2 and 7; Direct Blue 41; Acid Further, pigments may be exempli?ed by inorganic Violet l5 and 49; Acid Blue 1, 7, 9, 15, 22, 83, 90, 93, pigments such as Chrome Yellow, Zinc Yellow, ZTO 15 type zinc chromate, red lead, iron oxide powder, zinc 100, 103 and 104; Acid Green 3, 9nd 16; Mordant white, aluminum powder and zinc powder. Violet l; Mordant Blue 1, 29 and 47; Food Violet 2; The “conjugated 1r bond” possessed by the conju Food Blue 2; Food Green 2; gated 1r bond compound which may be used as the exemplary xanthene dyes are Basic Red 1; Solvent scaling preventive in the process of the present inven Red 49; Pigment Red 81 and 90; Pigment Violet 1, 2 and V20 tion herein means two or more double bonds and/or 23; Acid Red 51, 52, 87, 92 and 94; Mordant Red 15 and triple bonds in conjugated relationship. And, the aro 27; Food Red 14; matic compounds having at least 5 conjugated 1r bonds exemplary acridine dyes are Basic Orange 14 and 15. which may be used in the present invention may include Quinoimine dyes include the following compounds. benzene derivatives, naphthalene derivatives, polynu Exemplary azine dyes are Basic Red 2; Basic Black 2; 25 clear aromatic compounds, quinones, non-benzene type Solvent Black 5 and 7; Acid Blue 59; Acid Black 2; aromatic compounds, etc., having at least ?ve conju exemplary oxiazine dyes are Basic Blue 3; Direct gated rr bonds. On the other hand, the heterocyclic Blue 106 and 108; compounds having at least 5 1r bonds may include, for exemplary thiazine dyes are Basic Yellow 1; Basic example, oxygen-containing heterocyclic compounds, Blue 9, 24 and 25. 30 nitrogen-containing heterocyclic compounds, sulfur Methine dyes include the following compounds. containing heterocyclic compounds, bicyclic com Exemplary polymethine (or cyam'ne) dyes are Basic pounds having a nitrogen atom in common, alkaroids, Yellow 11, 13, 14, 19, 21, 25, 28, 33 and 35; Basic Orange etc., having at least 5 conjugated 1r bonds. Speci?c 21 and 22; Basic Red 12, 13, 14, 15, 27, 29, 35, 36 and 37; examples of these compounds are enumerated below. Basic Violet 7, 15, 21 and 27. 35 The aromatic compounds having at least 5 bonds Quinoline dyes may be exempli?ed by Basic Green 6; include the following compounds. Disperse Yellow 54 and 56; Solvent Yellow 33; Acid First, as benzene derivatives, there may be included: Yellow 3. ‘ phenols and derivatives thereof, such as 2,6-ditert Nitro dyes may be exempli?ed by Disperse Yellow 1, butylphenylphenol, catecholphthalein, 2,2-diphenylo1 33, 39, 42, 49 and 54; Acid Yellow 1. propane, 3,7-dioxy-IO-methylxanthene, phenolphthal Benzoquinone and naphthoquinone dyes may be ex ein, 7-oxy-2,4-dimethylbenzopyrooxonium chloride, empli?ed by Disperse Blue 58 and 108; Acid Brown oxyanthraquinone, purpurogallin, Gallein, diphen 103, 104, 106, 160, 161, 165 and 188. ylether, a-methoxyphenazine, chloroglucide, 2,3-diox Naphthalimide dyes and pigments may be exempli yanthraquinone, 5,7-dioxy-4-methylcoumarine, dioxya ?ed by Pigment Red 123; Vat Violet 23 and 39; Acid 45 cridone, salicylic acid, a-hydrindone, B-phenyl Yellow 7. butyrophenyl, N-2,4-dinitrophenyl-N-phenylhydrox Perinone dyes may be exempli?ed by Vat Orange 7 ylamine, 1-(4-nitrophenyl)-3,S-dimethylpyrazole, 9,10 and 15. diphenylphenanthrene, acetophenone; Sul?de dyes may include, for example, Solubilized aromatic amines and derivatives thereof, such as N Sulfur Yellow 2; Sulfur Yellow 4; Sulfur Orange 3, 50 phenyl-p-benzoquinonediamine, quinoline, Safranine B, Sulfur Red 2, 3, 5 and 7; Solubilized Sulfur Blue 15; Rosaniline, Indiurine Spirit Soluble, Aniline Black, Sulfur Blue 2, 3, 4, 6, 7, 9 and 13; Sulfur Green 2, 3, 6, Para-Rosaniline, Methyl Violet, Methyl Orange, 14 and 27; Solubilized Sulfur Brown 1 and 51; Sulfur Methyl Red, Indigo, carbazole, Methylene Blue, 0 Brown 7, l2, l5 and 31; Sulfur Black 1, 2, 5, 6, 10, 11 and phenanthroline, p-phenanthroline, 3,6-diaminoacridine, 15; Vat Yellow 35, 42 and 43; Vat Blue 43 and 56. 55 Indanthrene Scarlet 2G, 4-aminodiphenylamine, Acri Fluorescent dyes may include, for example, ?uores dine Yellow, 3-aminophenothiazine, N’-diphenyl-p cent brightening agents 14, 22, 24, 30, 32, 37, 45, 52, 54, phenylenediamine, Rhodamine, 7-amino-4-methyl 55, 56, 84, 85, 86, 87, 90, 91, 104, 112, 121, 134, 135, 153, coumarine, 2-aminophenazine, phenothiazine, diphenyl ' 162, 163, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, amine, N-methylphenylamine, N-phenyltolylamine, 175, 176 and 177. ditolylamine, 2-oxy-4~methylquinoline, Hansa Yellow Azoic dyes may include, for example, Azoic Diazo G, N,N'—diphenylformamidine, phenanthrophenazine, Component 17, 20, 22, 24, 26, 31, 35, 41, 47, 48, 109 and Bismarck Brown G, 2,3-diaminophenazine, 2-aminodi 121; Azoic Coupling Component 2, 3, 4, 5, 7, 8, 10, ll, phenylamine, Chrysodine R, 2,3,7,8-tetraaminophena 12, 14, 15, 16, 17, 18, 19, 20, 23, 26, 28, 29, 35, 36, 37, 41 zine, aminophenoxazone, oxyphenoxazone, Tri and 108; Azoic Brown 2, 7, l1 and 15; Azoic Black 1 65 phenylenedioxazine, 2,4-dinitrophenoxazine, 2’,4’-dini and 5; Azoic Yellow 1 and 2; Azoic Orange 2, 3 and 7; tro-4-oxy-3-aminophenylamine; Azoic Red 1, 2, 6, 9, l6 and 24; Azoic Violet l, 2, 6, 7, nitro and nitroso derivatives, such as p-nitrosodi 9 and 10; Azoic Green 1. phenylhydroxylamine, phenazine, phenazine oxide, 1 4,758,639 7 8 phenylazo-Z-naphthol, 4-nitroxanthone, 4’-nitroso-2 yazobenzene, 2,2’-dioxy-5,5'-dimethylazobenzene, p nitrodiphenylamine; bromoazobenzene, p-nitroazobenzene, phenoazoxide; phenylhydroxylamine derivatives, such as 4,4'-dini aromatic unsaturated compounds, such as 2,3,4,5-tet trodiphenylamine, oxalic acid bis(,B-phenylhydrazine), raphenylcyclopentane-Z-ene-l-one, 1,2,3-tri malonic acid bis(B-phenylhydrazine), succinic acid phenyleneazulene, 2,2’-dimethyldiphenylacetylene, bis(B-phenylhydrazine), phthalic acid bis(B-phenylhy 4,4’-diethyldiphenylacetylene, 3,4,3’,4’-tetrarnethyl drazine); diphenylacetylene, 2,2’-dichlorodiphenylacetylene, aromatic halides, such as biphenyl chloride; 2,2’~dibromodiphenylacetylene, 2~nitrodiphenylacety aromatic aldehydes, such as Z-phenyl-l-benzyl-ben lene, 2,2’?dinitrodiphenylacetylene, 2,2’-diaminodiphe zimidazole, Leucomalachite Green, Malachite Green, nylacetylene, 2,2’-dimethoxydiphenylacetylene, stil tetrachlorohydroquinone monobenzoate, benzoflavin, bene, a-methylstilbene, a~ethylstilbene, a,B-dimethyl 2-phenylbenzthiazole, 4-benzhydrylbenzaldehyde, bis stilbene, a,B-diethylstilbene, a,B-dichlorostilbene, (1,5 phenylhydrazone, bis(4-nitrophenylhydrazone); debromostilbene, 2-chlorostilbene, 4,4’-diiodostilbene, aromatic ketones such as triphenylisooxazole, benzo a-nitrostilbene, a,B-dir1itrostilbene, 2,4,6-trinitrostil phenone potassium, 4-methylbenzophenone, p-toluyl 15 bene, 2-aminostilbene, 2,2'~diaminostilbene, 4,4'-di( acid anilide, benzoic acid toluidide, duryl phenyl ke dimethylamino)stilbene, 2,2’-dicyansti1bene, 2-oxysti1 tone, 2,4,2’,4'-tetramethylbenzophenone, calchon bene, Z-methoxystilbene, 2,2’-dioxystilbene, 2,2’-dime phenylhydrazone, 1,3,5-triphenylpyrazoline, dinitro thoxystilbene, 4,4’-dialkoxystilbene, 3,5,2’,4'-tetraoxys benzyl; tilbene; and benzoic acids, phthalic acids and derivatives thereof, 20 polyphenyls and derivatives thereof, such as biphe such as quinizaline, nitrodiphenylether; nyl, terphenyl, quaterphenyl, quinophenyl, sexiphenyl, benzene derivatives having further one substituent septiphenyl, octiphenyl, noviphenyl, deciphenyl, etc. other than aldehyde group, such as disalicylaldehyde, Next, as naphthalene derivatives, there may be in coumarine, 2-benzoylcoumarone, l-oxy-2,4-dimethyl cluded: alkyl, alkenyl and phenylnaphthalenes, such as l ?uorone, 3-phenylcoumarone, ethyl coumarine-3-car methylnaphthalene, Z-methylnaphthalene, l-ethylnaph boxylate, 3-acetylcoumarine, hydrovaniloin, 4-oxy-3 thalene, Z-ethylnaphthalene, 1,2-dimethylnaphthalene, methoxy-w-nitrostyrene, a-(nitrophenyD-B-benzoyle 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, 1,6 thyleneoxide, dinitrophenylindazole, 5-chloro-3-(4-oxy dirnethylnaphthalene, 1,7-dirnethylnaphthalene, 2,3 phenyl)anthranil, 3-nitroacridone, 6-nitro-3-phenylan 30 dimethylnaphthalene, 2,6-dimethylnaphthalene, 2,7 thranil, 2,8~dimethyl-l,9-anthrazoline, carbostyril, l,3~ dimethylnaphthalene, l-propylnaphthalene, l-iso dioxyacridine, oxyquinacdine, Phlorchinyl, Z-methyl propylnaphthalene, 2-isopropylnaphthalene, trimethyl quinazoline, 3-acetyl-2-methylquinoline, 2-oxy-3 naphthalene, diisopropylnaphthalene, l-vinylnaphtha phenylquinoline, 3~nitroquinoline, quinoline-2,3-dicar lene, 2-vinylnaphthalene, l-propenylnaphthalene, l boxylic acid ester; 35 allylnaphthalene, l-isopropenylnaphthalene, 2-iso benzene derivatives having further one substituent propenylnaphthalene, 1~phenylnaphthalene, Z-phenyl other than acyl group, such as 7-oxyflavanone, 7-oxy?a naphthalene, 1,4-diphenylnaphthalene, 1,2,4-triphenyl vone, 7,8-dioxy?avone, 7-acetoxy-4-methyl-3-phenyl naphthalene; coumarine, 7,8-diacetoxy-4-methyl-3-phenylcoumarine, dinaphthyls, such as l,l’-dinaphthyl, l,2'-dinaphthy1, o-oxybenzophenone, xanthone, Z-phenylbenzooxazole, 2,2'-dinaphthyl; m-oxybenzophenone, p-oxybenzophenone, 2-benzoylx naphthylarylmethanes, such as l-benzylnaphthalene, anthone, 2,4-dioxybenzophenone, 2,5-dioxybenzophe 2-benzylnaphthalene, l-(a-chlorobenzyl)naphthalene, none, 2,2'-dioxybenzophenone, xanthene, aurin, triox~ l=(a,a-dichlorobenzyDnaphthalene, diphenyl-a-naph ybenzophenone, 6,7-dimethoxy-3~phenylcoumarone, thylmethane, diphenyl-B-naphthylmethane, l,8-diben o-nitrobenzophenone, m-nitrobenzophenone, 4,4’» 45 zylnaphthalene, di-a-naphthylmethane, a~naphthyl-,B dibenzoylazoxybenzene, 2-(2-aminophenyl)-4-methylv naphthylmethane, di-B-naphthylmethane; quinone, 2-oxy-4~methylquinone, acridone, 2,4-dime» naphthylarylethanes, such as l-phenethylnaphtha thylquinazoline, 3-cyan-2-oxy-4»methylquinoline, fluo lene, l,2-di-a-naphthylethane, 1,2-di-B-naphthylethane, rene, anhydro(2-aminobenzophenone) dimer, 2-oxy-3 l, l-a-dinaphthylethane; phenylindazole, 3-phenylindazole, 2-phenylben hydronaphthalenes such as 1,2-dihydronaphthalenes, zimidazole, Z-methyl-8-benzoylquinoline, 2-methyl-4 1,4-dihydronaphthalene, l,2,3,4-tetrahydronaphthalene; phenylquinoline, 4-phenyl-2-quinazolone, aminobenzo nitronaphthalenes and derivatives thereof, such as phenone, chlorobenzophenone, 4-phenylbenzo-l,2,3 dinaphthylpyridazine, 7,8-benzoquinone, 5,6-benzoqui triazine-3-oxide, diaminobenzophenone, 7~methyl=3 none, naphthazarine, diperimidine, nitromethylnaph phenyl-4,5-benzo-1,2,6-oxydiazine, 4,4'-bisdime 55 thalene, nitromethylnaphthalene, nitrophenylnaphtha thylaminobenzophenone, 4,4’-bisdimethylaminobenzo lene, halo-nitronaphthalene, halo-dinitronaphthalene, phenoneimide, 2,4-dinitro-9-phenylacridine, 4,4'-diben~ nitrosonaphthalene, dinitrotetraline, dibenzophenazine, zoyldiphenyl; methylbenzoindole, 9-chloro=lazaanthracene, benzene,‘ toluene derivatives having three or more quinolinoquinoline, 1,2,3-triazaphenarene, perimidone, different substituents, such as tetramethoxyindigo, perimidine, dibenzoacridine, benzophenazine-l2-oxide, 5,6,5',6’-bismethylenedioxyindigo, 7-acetoxy-8 diaminonaphthalene, triaminonaphthalene, tet methoxy-3-(2-nitrophenyl)carbostyril, 2,2'—dinitr0di raaminonaphthalene, N-ethyl-a=naphthylamine, N phenyldisul?de-4,4’-dialdehyde, 6-chloro-3-benzoyl?a methylnaphthylamine, N,N-dimethylnaphthylamine, vone, 1,3,8-trinitrophenoxazine; N=rnethyl-=N-ethylnaphthylamine, N-methyl-N-ethyl aralkyl compounds, such as 9-benzylacridine; 65 naphthylamine, trimethylnaphthyl ammonium salt, N diazo compounds and azo compounds, such as azo phenylnaphthylamine, N-benzylnaphthylamine, N benzene, azotoluene, 2,2-dimethoxyazobenzene, 4,4’ naphthylethylenediamine, N-naphthylglycine, N-B dichloroazobenzene, l,1’-azonaphthalene, 2,2’-diox cyanomethylnaphthylamine, N-acetylnaphthylamine,

4,758,639 11 12 oxynaphthalene, l-acety1-Z-methoxynaphthalene, 1 4,5-biphenylfuran, 7-isopropyl-l-methylphenan acetyl-4-ethoxynaphthalene, Z-cinnamoyl-l-naphthol, threnequinone, 1-chlorophenanthrenequinone, 2 7,8-benzochromone, 3-acetyl-2-methyl-7,8-benzochro bromophenanthrenequinone, Z-iodophenanthrenequi mone, 3,4-dimethyl-7,8-benzocoumarin, 4-methyl-3 none, 2,7-dibromophenanthrenequinone, 2-nitro phenyl-7,8-benzocoumarin, l-benzoyl-2-oxynaphtha 5 phenanthrenequinone, 2,5-dinitrophenanthrenequinone, lene, 4-oxybenzanthrone, 4-benzoyl-1-naphthol, 3-oxy Z-aminophenanthrenequinone, 2,7-diaminophenan 1,2-benzo?uorenone, 2-acetyl-4-chloro-l-oxynaphtha threnequinone, 3,6=diaminophenanthrenequinone, 2,5 lene, a-naphthylglyoxal, B-naphthylglyoxal, 1,4~diben-= diaminophenanthrenequinone, 2-oxyphenanthrene~l,4~ zoylnaphthalene, phenyl-4-methyl-l-naphthyldiketone, quinone, 3-oxyphenanthrenequinone, 2-oxyretenequi and the like. none, 3-oxyretenequinone, 6-oxyretenequinone, 2-oxy-= Also, as the polynuclear aromatic compounds, there 3,4-dinitrophenanthrenequinone, 2-amino-3—oxyphenan may be included: threnequinone; and anthracenes and derivatives thereof, such as anthra polynuclear aromatic compounds and derivatives cene, 1,2-dihydroanthracene, l-chloroanthracene, 1,4 thereof, such as pentacene, hexacene, benzophenanth dichloroanthracene, 1,2,7-trichloroanthracene, 1,2,3,4 rene, benzo[a]anthracene, naptho[2,1,a]pyrene, diben tetrachloroanthracene, l-nitroanthracene, 9,10-dini zo[a,j]anthracene, pyrene, coronene, 1,12-benzopyrene, troanthracene, l-aminoanthracene, Z-dimethylaminoan ovalene, dibenzoanthracene, naphthacene, Terramycin, thracene, 2~anilinoanthracene, 9-methylaminoanthra Aureomycin, rubrene, o-toluoyl-l-naphthalene, ben-= cene, 1,4-diaminoanthracene, l~oxyanthracene, 9,10 zoanthraquinone, 5,6-dioxy-5,é-dihydrobenzoanthra dihydroanthrol, 10~methylanthranol, l0-phenylan= 20 cene, chrysene, triphenylene, dibenzonaphthacene, hex thranol, IO-nitroanthranol, Z-amino-l-anthranol, 1,2= ahydropyrene, perylene, 3,9-dichloroperylene, tetra dioxyanthracene, 9,10-dioxyanthracene diacetate, l chloroperylene, 3,9-dibromoperylene, 3,10-dinitropery methylanthracene, 4-chloro-l-methylanthracene, 1,5 lene, 4,6-dibenzoyl-1,3-dimethylbenzene, 6,13-dihy dichloro-Z-methylanthracene, 9-ethylanthracene, 9 dropentacene, naphtho[2,3-a]anthracene, dispirane, vinylanthracene, 9-propylanthracene, 9-isopropylan 25 dibenzo[a,h]anthracene, picene, picyleneketone, picene thracene, 9-butylanthracene, 9-isobutylanthracene, 9 5,6-quinone, dibenzo[c,g]phenanthrene, benzo[a]py isoamylanthracene, 1,3-dimethylanthracene, 9,10-die rene, benzo[a]pyrene-1,6-quinone, mesobenzoanthrone thylanthracene, l-phenylanthracene, 9-phenylanthra pericarboxylic acid anhydride, anthraceno[2,l-a]anthra cene, 1,5-dichloro-9-phenylanthracene, 10-nitro-9~ cene, dibenzo[a,l]naphthacene, phenanthrene[2,3-a]an phenylanthracene, 9-benzylanthracene, l-benzhy 30 thracene, naphtho[2,3-a]pyrene, dibenzo[a,h]pyrene, drylanthracene, 9,10-diphenylanthracene, 9,10-diben dibenzo[a,l]pyrene, zethrene, anthanthrene, ben zylanthracene, 9, l0-diphenyl-9, IO-dihydroanthracene, zo[l,l2]perylene, heptacene, tetrabenzo[a,c,h,j]anthra l-(B-naphthyDanthracene, 9-(a-naphthyl)-lo-phenylan cene, tribenzo[a,i,1]pyrene, tetrahydrodimethyldinapht thracene, 9,10-di(a-naphthyl)anthracene, l,1'-bianthryl, hyl, mesonaphthodianthrene, mesoanthrodianthrene, 2,2'-bianthryl, 9,9'-bianthryl, anthracene-9-aldehyde, 35 2,3;8,9-dibenzocoronene, pyranthrene, and the like. l-acetylanthracene, 9-benzoylanthracene, l0-nitroan As quinones and derivatives thereof, there may be thraphenone, 9,10-dibenzoylanthracene, anthrone, 9 included: mercaptoanthracene, 9, 10-disodium-9, IO-dihydroan benzoquinones and derivatives thereof, such as diben~ thracene, lO-bromo-9-anthrylmagnesium bromide, zoquinoyl disul?de, 2,5-bis(phenylthio)-p-benzoqui Anthryl-mercury chloride; none, bibenzoquinone, bitoluquinone, phoenicin, 00s phenanthrenes and derivatives thereof, such as phe porein, indophenol, indoaniline, Hydron Blue, inda nanthrene, 9,10-dihydrophenanthrene, l,2,3,4-tetrahy mine, Meldola’s Blue, Wurster’s Blue, Wurster’s Red, drophenanthrene, l-chlorophenanthrene, phenanth 4,4'=diphenoquinone, 4,4’-stilbenequinone, 3,5,3',5'-tet rene-9,10-dichloride, l—bromophenanthrene, 1-iodo= ramethyl-4,4'-diphenoquinone, 3,5,3‘,5’-tetra-tert~=butyl phenanthrene, 9-(chloromethyl)phenanthrene, 1 45 4,4’-diphenoquinone, ' 3,5,3’,5'~tetramethyl-4,4’-stil (bromomethyhphenanthrene, 4,5-bis(bromomethyl) benequinone, 3,5,3’,5’-tetra-tert-butyl-4,4'-stilbenequi phenanthrene, l-nitrophenanthrene, 10-bromo-9-nitro none; phenanthrene, l-aminophenanthrene, 9,l0—diamino naphthoquinones and derivatives thereof, such as phenanthrene, 9,9’-azoxyphenanthrene, 9,9'-azo 1,2-naphthoquinone, 3-oxy-2,2’-binaphthyl-l,4;3',4’ phenanthrene, l-oxyphenanthrene, cholesterol, estrone, diquinone, 5,6-benzoquinoxaline, 1,2-benzophenazine, androsterone, 10-bromo-9~phenanthrol, 9-nitro-3 2-benzoazo-l-naphthol, 4-(2,4-dioxyphenyl)-1,2-diox phenanthrol, 4-amino-1-phenanthrol, 10-benzoazo-9 ynaphthalene, 4-(3,4,5-trioxyphenyl)-1,2-dioxynaphtha phenanthrol, 1,2-dioxyphenanthrene, retene-3,8-diol, lene, l,2-naphthoquinone-l-phenylimide, 1,2-benzo 2,3,5,6-tetraoxyphenanthrene, l-methylphenanthrene, phenoxazine, 1,2-naphthoquinone-2-chloroimide, 1,2 l-ethylphenanthrene, l-vinylphenanthrene, 1,2-dirne 55 naphthoquinone-bis-chloroimide, 2-anilino-1,4-naph thylphenanthrene, 9,10-diethylphenanthrene, 9,10 thoquinone-4-anil, 2-oxy- l,4-naphthoquinone-4-anil, dipropylphenanthrene, Z-ethyl-l-rnethylphenanthrene, 1,2-naphthoquinone-1-oxime benzoate, 1,2-naphthoqui 7-isopropyl-l-methylphenanthrene, 9,10-dihydroretene, none-l-oxime methyl ether, l-nitroso-Z-naphthol, 2 aminoretene, S-acetoarninoretene, 6-acylaminoretene, nitroso-l-naphthol, naphtho[1',2’:3,4]furazane, 1,2 9-phenylphenanthrene, 9-benzylphenanthrene, l-(a naphthoquinone-Z-oxime benzoate, 1,2maphthoqui naphthyl)phenanthrene, 1,l'-biphenanthryl, 9,9’ none-Z-oxime methyl ether, 3=anilino-l,2;8,9-dibenzo biphenanthryl, l-phenanthraldehyde, 2-phenanthralde phenazine, Naphthyl Blue, Naphthyl Violet, l,2;5,6 hyde, 9-phenanthraldehyde, l-acetylphenanthrene, 2 dibenzophenazine, naphtho[1’,2’23,4]furazane-2-0xide, propionylphenanthrene, 3-acetylretene, l-benzoyl triphthaloylbenzene, hexaoxynaphthalene anhydride, phenanthrene; 65 2,2’~binaphthyl- 1,4; l’,4’~diquinone, l’,4'-dioxynaph phenanthrenequinones, such as phenanthrene-1,2-qui tho(2',3':3,4)pyrazole, 4,7-dioxy-3,3-diphenyl—5,6-ben none, phenanthrene-l,4-quinone, phenanthrene-SA-qui zindiazene, 2-diphenylmethyl-1,4-naphthoquinone, me none, phenanthrene-9,lO-quinone, 2-phenyl-3-acetoxy thylnaphtho [2',3’:4, 5]triazole- l ’,4’-quinone, 1,2,4 4,758,639 13 14 triacetoxynaphthalene, 1,4maphthoquinonephenyli oxynitrosoanthraquinone, l,1’-dianthraquinolyl, azox mide, l,4-naphthoquinone-mono(p-dimethylaminoanil), yanthraquinone, 8-chloropyrazoleanthrone, 2,6-dihy 1,4-naphthoquinonealkylimide, 4-nitroso-l-naphthol, drazinoanthraquinone, anthraquinone diazonium salt, phenylcarbamate, 4-nitroso-l-naphthylamine, 4~benz B-anthraquinonehydrazine, azoxyanthraquinone, hydryl-l,2-naphthoquinone, 2-benzhydryl-1,4-naph 5 pyrazoleanthrone, 1-(anthraquin-2-yl)-S-methylpyrazo thoquinone, 3-benzhydryl-2-methyl-1,4-naphthoqui lone, l-hydroxylaminoanthraquinone, 1,5-dihydrox none, 3-geranyl-2-methyl-1,4-naphthoquinone, 3-farne ylaminoanthraquinone, l-nitrosoanthraquinone, l syl-2—methyl-1,4-naphthoquinone, 2-methyl-3-phytyl hydrazinoanthraquinone, 1,5-dihydrazinoanthraqui 1,4-naphthoquinone, Vitamin K1, Vitamin K2, 3-allyl none, l-azidoanthraquinone, 2-azidoanthraquinone, an 2,6-dimethyl-1,4-naphthoquinone, 2,6-dimethyl-3-phy thraquinonemethylsulfoxide, l,4-dirhodaneanthraqui tyl-l,4-naphthoquinone, 2,3-diallyl-6,7-dimethyl-1,4 none, B,B'-dianthraquinolyl sul?de, anthraquinonesul naphthoquinone, Z-phenyl-1,4-naphthoquinone, 2-meth phenyl chloride, 2,2'-dianthraquinonyl, l,l’-dian yl-l,4-naphthoquinone, 2,6-dimethyl-3-phenyl-l,4 thraquinonyl, helianthrone, mesobenzodianthrone, 2,2’ naphthoquinone, 3-benzyl—2-methyl-1,4-naphthoqui diamino-l,l’-dianthraquinolyl, ?avanthrone, 2,2’ none, 2-methyl-3-(?-phenylethyl)-1,4-naphthoquinone, dianthryl, mesonaphthodianthrone, l,l'-dian 3-cinnamyl-2-methyl-1,4-naphthoquinone, Z-benzhyd thraquinolylamine, quinizarinquinone, hystazarinqui ryl-l,4-naphthoquinone, 4,7-diketo-8-diphenylmethyl none, alizarinquinone, 6-oxyquinizarinquinone, and the 4,7,8,9-tetrahydro-5,6-benzindiazene, 2-methyl-3 like. - diphenylmethyl-l,4-naphthoquinone, 2,3-diphenyl-l Further, as the non-benzene type aromatic com naphthol, naphtho[2',3’:3,4]-pyrazole-l',4‘-quinone, 3,4 pounds, there may be included, for example, azulene, dichloro-l,2-benzophenazine, 2-iodo-l,4-naphthoqui cyclodecapentane, cyclotetradecaheptane, cyclooc none, l,4,5,8-tetraoxy-2,3;6,7-dibenzothianthrene, 5,8 tadecanonaene, cyclotetracosadodecaene, heptalene, dioxy-2,3;6,7-dibenzothianthrene-1,4»quione, 2,3 fulvalene, sesqui-?uvalene, hepta?uvalene, perinaph diphenoxy-1,4-naphthoquinone, dinaph~ thene, indeno[2,l-a]perinaphthene, dibenzo[bt]oxepine, tho[2',3':2,3][l"2":5,4]furan-l’,4'-quinone, 2,3,5,8-tetra 25 dibenzo[bt]thiepine, indolizine, cyclo[3,2,2]azine, 4,5 chloro-l,4-naphthoquinone, N,N'-bis-(l,4-naphthoqui benzotropolone, 3,4—benzotropolone, SH-benzocy none-2-yl)-benzidine, 2~anilino-l,4-naphthoquinone-4 cloheptane, 7H-benzocycloheptane, colchicine, col anil, 4-anilino-1,2-naphthoquinone-2-anil, phenylrosin chiceine, colchinol methyl ether, ditropyl ether, ditro darine, 2-anilino-1,4-naphthoquinone-4-(p-dime pyl sul?de, cyclopentadienyltropylidene, benzoazulene, thylaminoanil), Z-anilino-1,4-naphthoquinoneclianil, 2~ 30 carbinol, 4,5-benzotropone, 2-phenyltropone, naph anilino-3-phenyl-l,4-naphthoquinone, 2-anilino~3 thocycloheptadienone, naphtotropone, tribenzotro bromo-l,4-naphthoquinone, 2-anilino-4-chloro-l,4 pone, l-amino-l,3-dicyanoazulene, benzoylhydrazone, naphthoquinone, 2,3-dianilino-1,4-naphthoquinone, 2,3 3-pheny1-l-oxaazuranone-2,Z-benzyltropone, 3-methyl dianilino-1,4-naphthoquinonedianil, nitrosoaminonaph Z-phenyltropone, 2,7-diphenyltropone, 2-(a-naphthyl) thoquinone, 3-chloro-2-phenylnitrosoamino-1,4-naph 35 tropone, 2,7-tetramethylene-4,S-benzotropone, 2,7 thoquinone, phenyl-bis-(3-ani1ino-1,4-naphthoquinone diphenyl-4,5-benzotropone, naphtho[2',3’-4,5]tropone, 2-yl)amine, 3-chloro-2-(p—tolylnitrosoamino)-1,4-naph naphtho[2',l'-2,3]tropone, dibenzosuberane, naph thoquinone, 2,7-dioxy-l~nitrosonaphthalene, 4-ben tho[l’,2'-2,3]tropone, dibenzosuberol, 4-oxy-2-phenyl zeneazo-1,3-dioxynaphthalene, di-(3-oxy-l,4-naph tropone, 4,5,7-tribromo-Z-phenyltropone, 3,5’-ditropo thoquinonyl-2-yl)-methane, anhydroalkannin, diquinox lone, 3-(p~methoxyphenyDtropolone, 4-oxy-2-phenyl alino[2',3’:1,2:2",3":3,4]-naphthalene, 3,4-phthaloylfura tropone, 3-(a-naphthyl)tropolone, 3,4-diphenyltropo zene; and ron, 3,7-dibenzyltroplone, 4-(65 -phenylpropyl)tropo anthraquinones and derivatives thereof, such as 1,2 lone, 3,5’-bitropolonyl, 4-(p-nitrostyryl)tropolone anthraquinone, 2,3-anthraquinone, 1,4-anthraquinone, methyl ether, 2-amino-l,3-dicyanoazurene, benzo[b] 9,10-anthraquinone, 1,5-anthraquinone, 2,6-anthraqui 45 tropothiazine, 5-bromo-2-phenyltropone, 4-bromo-2,7 none, 1,10-anthraquinone, 9,9-bis(p-oxyphenyl)an diphenyltropone, diphenylbiphenylcarbinol, thiazino throne, anthraquinone bisdiphenylmethide, bisphenyl tropone, and the like. hydrazone, benzanthrone, anthrahydroquinone, B Next, typical examples of the heterocyclic com ethylanthraquinone, l,3,5,7-tetramethylanthraquinone, pounds having 5 or more conjugated 7r bonds include 2,2'-dianthraquinonylethane, 2,2'-dian 50 the following compounds. thraquinonylethylene, 1,2,3-trioxyanthraquinone, an First, as the oxygen-containing heterocyclic com» thrachrysone, erythrooxyanthraquinone, alizarin, qui pounds, there may be included: nizarin, anthrarufm, chrysazin, hystazarin, anthra?avin, furan and derivatives thereof, such as 2,5-diphenylfu isoanthra?avin, anthragallol, purpin, oxyanthraru?n, ran, 2-phenylfuran, S-methyl-diphenylfuran, lepidene, anthrapurprin, oxychrysazin, oxyflavopurpurin, Ru? 55 pyridoxine, 2,4-diphenylfuran; opin, quinazarin, alizarinpentacyanine, ru?gallol, An benzofuran, isobenzofuran, dibenzofuran and deriva thracene Blue WR, alizarinhexacyanine, 2-chloroquini tives thereof, such as dibenzofuran, furano[2’,3'-7,8]fla zarin, l-nitroanthraquinone, 2,4,6,8-tetrabromoan vone, egonol, Euparin, l,S-diphenylisobenzofuran, tet thrachrysone, S-aminoanthrapurpurin, 1,8-dinitroan raphenyl glycol, tetraphenylphthalan, 9-phenylanthra thraquinone, a-aminoanthraquinone, l,l’-dian cene, o-oxymethyltriphenylcarbinol, 3,3’-diphenylph thraquinonyl, diauthraquinoneimide, 1,4-dime thalide, l-phenylphthalan, 1,1-phenylphthalan, 3,3 thylaminoanthraquinone, 5-amino-l-nitro-6,8 diphenylphthalide, rubrene, a-sorinine, dibenzofuran, dibromoanthraquinone, l,5-tetramethyldiamino-4,8 2,2’-dioxybiphenyl, 2,2’-diaminobiphenyl, phenazone, dinitroanthraquinone, anthraquinoneacridone, bis-N-(Z dibenzoquinone, Z-hydroxybenzofuran, Z-methylben oXyanthraquinolyDp-phenylenediamine, leucoquinaza 65 zofuran, benzo[a]benzofuran, benzo[b]benzofuran, rin, Quinazarin Green, l-amino-2,4-dibromoanthraqui dibenzo[a,?dibenzofuran, dibenzo[c,d]dibenzofuran, none, l,4~diacylaminoanthraquinone, anthraquinone-B dibenzo[c,e]dibenzofuran, bis(2-dibenzofuryl), bis(3 aldehyde, o-diazine, 6,7-phthaloyl-l,9-benzanthrone, dibenzofuryl);

4,758,639 17 18 pyridylazoresorcin, 4-pyridyl-m-phenylenediamine, thiazine and related compounds, such as o-ben 3-pyridyl-m-phenylenediamine; zaminophenyl-B-phenoxycarbonylethyl sul?de, pheno quinoline and related compounds, such as quinoline, thiazine, nitrophenothiazine, 3-chloro-l0-ethylpheno quinaldine, quinaldine-N-oxide, ethylquinoline, 2 thiazine, 4-amino-4'-anilinodiphenyl disul?de, 2-chloro phenylquinoline, 3-methylquinoline, 3-phenylquinoline, 5 l0-(3-dimethylaminopropyl)phenothiazine, chloro 4-methylquinoline, 4-phenylquinoline, é-methylquino promazine, l0-(2-dimethylamino-l-propyl)phenothia line, Gethylquinoline, 6-phenylquinoline, 2,4-dimethyl~ zine hydrochloride, l0-[2-(l-pyrrolidyl)ethyl]pheno quinoline, 2,4-diphenylquinoline, quinoline-4-methanol, thiazine hydrochloride, lO-[1-methyl-3-piperidylme quinoline[6,5-fjquinoline, quinophthalone, ?avaaniline, thyl]phenothiazine, 2-acetyl-IO-(S-dirnethylamino Quinoline Blue, Ethyl Red, pinacyanol, naphthocyanol, 10 propyl)phenothiazine, Methylene Blue; cryptocyanine, xenocyanine, azacyanine, 6,6’-octahy pyridazine and related compounds, such as cinnoline, droquinone, Besthorn’s red, 2,3'-biquinoline, 2,5’ 3-methylcinnoline, 4-chlorocinnoline, 3-bromocinno biquinoline, 2,6’-biquinoline, 2,7’—biquinoline, 3,3’ line, 4-cinnolinol, 4-aminocinnoline, phthalazine, 4 biquinoline, 4,5'-biquinoline, 4,6’-biquinoline, 5,5’ ethyl-Z-phenylphthalazinone, phthalazine thiol, 1(2H) biquinoline, 6,6'-biquinoline, 6,7'-biquinoline, 6,8’ 15 phthalazinone, 3-phenylpseudophthalazine, 4-methy1-3 biquinoline, 7,7’-biquinoline, 8,8’-biquinoline, 2 phenylpseudophthalazine, 2,3-dihydro-1,4-phthala ?uoroquinoline, 3-?uoroquinoline, 4-iluoroquinoline, zinedione; S-?uoroquinoline, 6-?uoroquinoline, 7-?uoroquinoline, pyrimidine and related compounds, such as 2-cin 8-?uoroquinoline, 3-bromoquinoline, 4-chloroquino namethylpyrimidine, 4,é-dimethyl-Z-phenylpyrimidine, line, 2,4-dichloroquinoline, 3-nitroquinoline, 4» 2,4,6-triphenylpyrimidine, alloxantin, 2,6-dioxy-4 nitroquinoline, 2,3-quinolinediol, quinoline-Z-thiol, 2 phenylpyrimidine, 4,6-dioxy-2-phenylpyrimidine, 5 oxyquinoline-3-thiol, 2-aminoquinoline, 8-aminoquino chloro-4,6-dioxy-2-phenylpyrimidine, sulfadiazine, sul line, 2-hydraziquinoline, pyroloquinoline, ?somidine, thonzylamine hydrochloride, Vitamin B1, thiazoloquinoline, pyrimido[4,5-b]quinoline, benzo[f thiochrome, co-carboxylase, allomycin, 6-(2-furfuryl ]quinoline; 25 )aminopurine, pteridine, 2,4-pterine diol, 2-amino-6 isoquinoline and related compounds, such as l methyl-4~pteridinol, xanthopterine, leucopterine, isox methylisoquinoline, 3-bromomethylisoquinoline, l anthopterine, quinazoline, 4-chloroquinazoline, 2,4 phenylisoquinoline, 4-phenylisoquinoline, 1,1’ dichloroquinazoline, 4-quinazoline, 2,3-diphenyl-4 biisoquinoline, 5,5'-biisoquinoline, l-chloroisoquinoline, quinazoline; S-iodoisoquinoline, 5-bromoisoquinoline, 5 30 pyrazine related compounds, such as 3,4-diphenyl nitroisoquinoline, isoquinoline-1,3-diol, 6,7 pyrazinol, quinoxaline, 2-methylquinoxaline, 2,3-dime methylenedioxyisoquinoline, l-aminoisoquinoline, l thylquinoxaline, 2-chloroquinoxaline, 2,3 cyanoisoquinoline, l-phenylbenzo [g]3,4-dihy dichloroquinoxaline, 2-(o-aminoaniline)quinoxaline, droisoquinoline, 3-(p-aminophenyl)-5,6-dihydro-8,9 N,N’-diphenyl-2,3-piperazione, 2-quinoxalinol, 2,3 dimethoxyimidazo[5, 1-a]isoquinoline; 35 quinoxaline diol, Z-aminoquinoxaline, 2,3 acridine and related compounds, such as acridine, diaminoquinoxaline, rnethylquinoxaline-2-carboxylic l-methylacridine, 9-phenylacridine, 9-(3-pyridinyl)acri acid ester, 2-(d-arabotetraoxybutyl)quinoxaline, ?ava dine, 2-chloroacridine, 2-bromoacridine, 2-acridinol, zole, glucazidone, phenazine, phenazine-S-oxide, phena acridine-3,6-diol, 4-methoxyacridine, 9-phenoxyacri 40 zine-5,l0-dioxide, 5-methylphenazinium-methylsulfate, dine, l-nitroacridine, 4-aminoacridine, l-aminoacridine, IO-methyl-S,l0-dihydro-2-phenazinecarbonitrile, 2 9-phenylaminoacn'dine, 9-oxyacridine, chrysaniline, phenazinecarbonitrile, l-phenazinol, l-methoxyphena acri?avine, 3,6-diamino-4,S-dimethylacridine, acrynol; zine, 2-phenazinol, 1,6-dioxyphenazine-5,IO-dioxide, phenanthridines, such as 3,4-benzoquinoline, 6 l-aminophenazine, 2-aminophenazine, 2,3-diamino methylphenanthridine, é-aminornethylphenanthridine, 45 phenazine, Neutral Red, 5,10-dihydrophenazine, 5 6-phenylphenanthridine, ?-chlorophenanthridine, 6 methyl-S, IO-dihydrophenazine, l,2,3,4-tetrahydro bromophenanthridine, é-nitrophenanthridine, l-amino phenazine; phenanthridine, 3-oxyphenanthridinone; tri- and tetra-hetero six-membered cyclic compounds, anthrazolines, such as pyrido[2,3-g]quinoline, 2,7 such as 2,4,6-triphenyl-s-triazine, 2,4-dichloro-6-o diphenyl[2,3-g]quinoline, 2,8-diphenylpyrido[3,2 chloroaniline-s-triazine, 5,6-diphenyl-as-triazine, 2,6 g]quinoline; diphenyl-2,3,4,S-tetrahydro-as-triazine, 5,6-diphenyl-as phenanthroline and related compounds, such as 1,7 triazine-3-ol, 1,2,4-benzotriazine, 1,2,4-benzotriazine-3 phenanthroline, 1,10-phenanthro1ine, 4,7-phenanthro o1, S-phenyl-1,2,3-benzotriazine-4-(3H)-one, 1,2,3-ben line, S-methyl-1,7-phenanthroline, 4,10-dioxy-l,7 zotriazine-4-ol, 1,2,3-benzotriazine-4-thiol, 3-amino phenanthroline, 3,5-dichloro-l,IO-phenanthroline, 2 55 1,2,3-benzotriazine, 2,3-diphenylosotetrazine, 5,6 amino-l,l0-phenanthroline, 5-oxy-4,7-phenanthroline, dimethyl-2,3-diphenylosotetrazine, 5-cyano-2,3 5-amino-4,7-phenanthroline; diphenylosotetrazine, 5,6-dibenzoyl-2,3-diphenylosotet pyridoindoles, such as 1,9-pyridoindole, 2,9-pyridoin razine, 2,3-dibenzoyl-S-methylosotetrazine, 2,3-dibenz dole, 4,9-pyn'doindole; oyl-5,6-dimethylosotetrazine, 2,3-dibenzoyl-5,6 naphthyridine and related compounds, such as 1,5 diphenylosotetrazine, 2,3-bis(2,4-dichlorophenyl)-5,6 naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine, diphenyl-l,2,3,4-tetrahydro-v-tetrazine, l,2,3,4-tetrae 1,6-naphthyridine, 2,6-naphthyridine, 2,7-naphthyri thoxycarbonyl-5,5-diphenyl-1,2,3,4,5,6-hexahydro-v dine, 1,5-naphthyridine-4-ol, 3-amino-l,5-naphthyri tetrazine, 7-rnethyl-2-(4-methylphenyl)-1,2-dihydroben dine, 2-amino-l,5-naphthyridine, 2-oxy-l.7-naphthyri zotetrazine, 3,6-diphenyl-1,2-dihydro-s-tetrazine, 1,3 dine; 65 diphenyl-l,4,5,6-tetrahydro-s-tetrazine, 3,3,6,6-tet oxazine and related compounds such as phenoxazi raphenyl-1,2,3,6-tetrahydro-s-tetrazine, and the like. none, resazurin, carocyanin, Nile Blue A, Meldora’s Further, the sulfur-containing heterocyclic com Blue, Brilliant Cresyl Blue; pounds may include: 4,758,639 19 20 sulfur-containing heterocyclic compounds, such as sine, papaverin, papaveraldine, laudanosine, laudanine, 2-phenylthiophene, 2,4-diphenylthiophene, 2,3,4,5-tet codamine, protopapaverine, almepavine, 4,4,5’-trime raphenylthiophene, metaphenylene hydrochloride, thoxy-2-vinylstilbene, coclaurine, d-isococlaurine, ne metapyrylene hydrochloride, chloroethene citrate, protin, corpaverine, phellodendrine, magnocurarine, thenyldiamine hydrochloride, a-quinquithienyl, a-sexi coclanoline, narcotin, narcotoline, aponarceine, cincho thienyl; nin, cinchotoxine, dihydrohydrastine, bicuculline, adlu fused thiophene type compounds, such as 3,3’ midine, corlumidine, cordrastine, magnolamine, berba diiminothioindigo, indigoron, dihydronaphtho[2,l mine, o-methylberbamine, etc. b]thianaphthene, 1,3~diphenylisothianaphthene, diben Among the conjugated n‘ bond compounds described zothiophene, 2=nitrodibenzothiophene, aminodibenzo l0 above, preferred are the ones having at least one amino thiophene, 2,8adiaminodibenzothiophene, dibenzothio group. Particularly preferred such compounds include, phene-S-dioxide, 4-oxydibenzothiophene, 2,8-diox for example, arninonaphthalenes such as diaminonaph ydibenzothiophene, 2-chlorodibenzothiophene, l thalenes, triaminonaphthalenes and tetraaminonaphtha bromodibenzothiophene, 2,8-dibromodibenzothio lenes, 1,4-diaminoanthracens, 9,lO-diaminophenanth phene, 2-iodo-dibenzothiophene, 2-acetyldibenzothio rene, 2,2’-diaminodiphenyl, 1,l’-diamino-2,2'-dinapht phene, 2,S-diacetyldibenzothiophene, naphthothio hyl, 2-amino-5-phenyl oxazole, l~aminophenanthridine, phene, 3-oxythiophanthrene, 2,3-thiophanthrene, naph 2-amino-4‘phenylthiazole, 2—amino-5-phenylthiazole, tho[2,3-c]thiophene, naphtho[l,2°b]thiophene, naph 3-amino-1,5-naphtyridine, l-aminophenanthridine, tho[2,1-b]thiophene, naphtho[l,2-c]thiophene, 1,2 aminoacridines such as 4-aminoacridine, 2~aminoacri naphtho[2, l-b]thiophenequinone, l-oxy-2-naphth0[2, l 20 dine, l-aminoacridine and 3,6-diaminoacridine, and b]thiophenealdehyde, naphtho[l,2-c]thiophene, 2H_ aminophenazines such as 1-aminophenazine, 2-amino naphtho[l,8]thiophene, benzo[b]thiophanthrene, 6,11 phenazine and 2,3-diaminophenazine. benzo[b]thiophanthraquinone, benzo[g]thiophanthrene, In a preferred embodiment of the present invention, 4,5-benzothiophanthrene, 8,9-benzothiophanthrene; the scaling preventive to be used in the present inven ?ve-membered monocyclic compounds containing 2 25 tion further contains, in addition to at least one of dyes, hetero atoms, such as 5-phenyl-l,2-dithiol=3=thione, pigments and conjugated 1r bond compounds, at least 3,4-dihydronaphtho-2,l-trithione, thiaflavone, one inorganic compounds. Although an inorganic com thiacoumarin, thiaxanthene, thiaxanthohydrol, thiaxan pound alone has no scaling preventive action, the seal thone, Milacil D, bisthiaxanthylene; ing preventive action possessed by dyes, pigments or six-membered cyclic compound having two or more 30 conjugated 1r bond compounds has unexpectedly been hetero atoms, such as 2,5-diphenyl-1,4-dithiadiene, thic found to be further enhanced when combined with the phenealdehyde, thianthrene, 2,7-dimethylthianthrene, inorganic compound. It has also been found that this l=thianthrenyl lithium, l-chlorothianthrene, phenox effect can further be exhibited, if the surface roughness thine, 2-vinylphenoxthine, Z-aminophenoxthine, 2 of the surfaces to be coated with the scaling preventive nitrophenoxthine, 3,7-dinitrophenoxthine, 10,10 35 is controlled by 5 pm or below. With a surface rough diphenylphenoxthine, 2,5-diphenylthiophene, and the ness in excess of 5 pm, the scaling preventive effect is like. not enough to prevent effectively scaling. Further, other useful compounds may include: When a mixture of a dye, a pigment or a conjugated dicyclic compounds having commonly a nitrogen or bond compound with an inorganic compound is to be atom, such as cinchonine, 2-phenylpyrrocoline, 3-ethyl 40 applied by coating on the inner wall surface of a poly Z-phenylpyrrocoline, 3-benzyl-2-phenylpyrrocoline, merizer, etc., the proportion of the both components 3-nitroso-2-phenylpyrrocoline, 2:3-benzopyrrocoline, may preferably be 0.1 to 2000 parts by weight of the 1,5,8-trimethyl=2:3-benzopyrrocoline, l-ethyl-5,8 inorganic compound, more preferably 1 to 1000 parts dimethyl-Z:B-benzopyrrocoline, l,8-dimethyl-2:3-ben~ by weight, per 100 parts by weight of the dye, pigment zopyrrocoline, 3=phenyl-7:8-benzopyrrocoline, cy 45 or conjugated 1? bond compound° clo[3.3.3]azine, cyclo[3.2.2]azine, 2-phenylcyclo[3.2.‘= Such inorganic compounds may include silicic acids 2]azine, 2,3-diphenylcyclo[3.2.2]azine, tricycladine, 7 or silicates, such as orthosilicic acid, metasilicic acid, methylbenzo[a]quinolinium bromide, 7-phenylbenzo[a] mesodisilicic acid, mesotrisilicic acid, mesotetrasilicic quinolidinium bromide, benzo[b]quino1idinium salt, tet acid, sodium metasilicate, sodium orthosilicate, sodium rahydro~=\ll-berberine, tetrahydroberberine, laudanoso 50 disilicate, sodium tetrasilicate, potassium metasilicate, line, tetrahydro-2,3,9,10-tetraoxy-7-methyldibenzopyr potassium hydrogen disilicate, lithium orthosilicate, rocolium chloride, homolaudanosoline, octadehy hexalithium orthodisilicate, water glass, 12-silicotung dromatrine, canadinemethoiodide, tetrahydropal stic acid, iso-12-silicotungstic acid, lo-silicotungstic matinemethoiodide; acid, potassium l2-silicotungstate, potassium iso-12 alkaloids, such as nicotyrine, 3',2-dipyridyl, cuspa 55 silicotungstate, potassium lO-silicotungstate, sodium rine, galipoline, 1-methyl-2-quinolone, casimiroin, 2~ l2-silicotungstate, sodium iso-l2-silicotungstate, pentylquinoline, 4-oxy-2-pentylquinoline, 4-methoxy-2 silicomolybdic acid, potassium silicomolybdate, sodium pentylquinoline, l-methyl-2-pentyl-4-quinoline, 4 silicomolybdate, and the like; methoxy~2~phenylquinoline, 7~methoxy-l-methyl-2 metal salts such as oxyacid salts, acetates, nitrates, phenyl-4-quinoline, cuspareine, dictamnine, skimmia= hydroxides or halides of metals selected from alkaline nine, evolitrine, maclurin, kokusagine, kokusaginine, earth metals such as magnesium, calcium, barium, etc., maculosidine, flindersiamine, evoxoidine, evoxine, aluminum family metals such as aluminum, etc., tin evolatine, acronycidine, medicosmine, acronidine, 'y family metals such as titanium, tin, etc., iron family fagarine, cinchonin, quininone, quinotoxin, N metals such as iron, nickel, etc., chromium family met bromoquinotoxin, dihydrocinchonicine, heteroquinine, 65 als such as chromium, molybdenum, etc., manganese evoxantidine, xanthoquinoline, l,3-dimethoxy-10~ family metals such as manganese, etc., copper family methylacridone, evoxanthine, xanthevodine, melico metals such as copper, silver, etc., platinum family met pine, melicopidine, melicopicine, acronycine, ?inder als such as platinum, etc.; 4,758,639 21 22 inorganic colloids prepared by mechanical crushing, tive, whereby the coating solution can be improved in irradiation of ultrasonic wave, electrical dispersion or economy and safety during transportation and storage. chemical methods, such as gold colloid, silver colloid, Such solvents includes: sulfur colloid, colloid of ferric hydroxide, colloid of alcohols such as methyl alcohol, ethyl alcohol, allyl stannic acid, colloid of silicic acid, colloid of manganese alcohol, n~propyl alcohol, isopropyl alcohol, and the dioxide, colloid of molybdenum oxide, colloid of bar like; ium sulfate, colloid of vanadium pentoxide, colloid of ketones such as acetone, acetonylacetone, diacetone aluminum hydroxide, colloid of lithium silicate and so alcohol and the like; on. esters such as ethyleneglycol monomethyl ether ace Among the above inorganic compounds, silicates, tate, diethyleneglycol methyl ether acetate, monoethyl silicic acid colloid and ferric hydroxide colloid are par ether acetate and the like; ticularly preferred. ethers such as dioxane, ethyleneglycol monomethyl For coating of the scaling preventive on the inner ether, ethyleneglycol monoethyl ether and the like; wall of a polymerizer, etc., it can be applied as such or furans such as tetrahydrofuran, furfuryl alcohol and as a coating solution prepared by dissolving or dispers the like; ing in an appropriate solvent. The concentration of the aprotic solvents such as acetonitrile, N,N-dimethyl scaling preventive in the coating solution is generally formamide, N,N-dimethylacetamide and the like. preferred to be 0.01% by weight or higher. When the scaling preventive to be used is a water-sol The solvent which may be used in preparation of the uble sulfonic acid type or carboxylic acid type dye coating solution may be water or various organic sol 20 having sulfonic acid groups or carboxylic acid groups in vents, including, for example: the form of an alkali metal salt or ammonium salt, water aliphatic hydrocarbons such as gasoline, petroleum, can be used as the solvent in which the preventive is to benzine, mineral spirit, petroleum naphtha, V.M. & P. be dissolved, as disclosed in Japanese Patent Publication naphtha, decalin, tetralin, p-cy'mene, and the like; No. 5442/ 1981, whereby there is the advantage in safety aromatic hydrocarbons such as benzene, toluene, 25 and hygiene that the solvent is non-toxic and harmless. xylene, and the like; If water is used as the solvent as described above, wetta halogenated hydrocarbons such as trichloroethylene, bility of the coating solution for the inner wall of a perchloroethylene, chloroform, carbon tetrachloride, polymerizer, etc. can be enhanced by addition of alco ethylene trichloride, benzene monobromide, benzene hols, preferably C3-C6 monohydric alcohols, such as monochloride, benzene dichloride and the like; n-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, alcohols such as amyl alcohol, ethyl alcohol, isopro sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, t pyl alcohol, Z-ethylbutyl alcohol, 2-ethylhexyl alcohol, amyl alcohol, iso-amyl alcohol, sec-amyl alcohol, sec cyclohexanol, methyl alcohol, methylamyl alcohol, hexyl alcohol, etc., as disclosed in Japanese Patent Pub benzyl alcohol, butyl alcohol and the like; lication No. 5444/1981. Also, as disclosed in Japanese ketones such as acetone, acetonylacetone, diisobutyl Patent Publication No. 5442/1981, for the purpose of ketone, diethyl ketone, dipropyl ketone, methyl amyl making drying of the coating solution after coating ketone, methyl butyl ketone, methylcyclohexanone, easier, an organic solvent compatible with water such as methyldipropyl ketone, methyl ethyl ketone, methyl alcoholic solvents, ester solvents, ketone solvents, may n-hexyl ketone, methyl isobutyl ketone, methyl propyl be added to the coating solution. In carrying out coat ketone, mesityl oxide, and the like; ing of the coating solution containing the scaling pre esters such as acetates, butyrates, propionates, for ventive on the inner wall of a polymerizer, etc. accord mates and the like; ing to the process of the present invention, various alcohol esters such as butyl lactate, isopropyl lactate, ?xing agents can be used for enhancement of the ?xing ethyl lactate, ethyl oxypropionate, diethyl maleate and characteristic, if desired. The ?xing agent may be used the like; 45 according to various methods, for example, the method ketone esters such as ethyl acetoacetate, ethyl pyru in which it is incorporated in the coating solution con vate and the like; taining the scaling preventive, the method in which the ethers such as isopropyl ether, ethyl ether, diethyl ?xing agent or a solution thereof is previously applied carbitol, diethyl cellosolve, butyl ether, and the like; on the wall surface prior to coating of the scaling pre ketone alcohols such as acetonylmethanol, diacetone ventive, followed by overlaying of the scaling preven alcohol, dihydroxyl acetone, pyruvyl alcohol and the tive thereon, and the suitable method may be selected like; depending on the kind of the scaling preventive and the ether alcohols such as isopropyl cellosolve, carbitol, kind of the ?xing agent. glycidol, cellosolve, glycol ether, benzyl cellosolve, Such ?xing agents may include the polymeric com butyl carbitol, butyl cellosolve, methyl carbitol, methyl 55 pounds as shown below: cellosolve, triethyleneglycol monoethyl ether and the olef'm polymers, such as polyethylene, polyethylene like; sulfonic acid, polypropylene, poly(l-butene), ketone ethers such as acetal ethyl ether, acetonylme polyisobutene, polycyclopentene, polycyclopen thanol ethyl ether, methyl ethoxyethyl ether, and the tylethylene, polycyclohexylethylene, poly(3-cyclohex like; yl-l-propene), poly(4-cyclohexyl-l-butene), poly(5 ester ethers such as butylcarbitol acetate, butyl cello cyclohexyl-l-pentene), poly(cyclotri?uoroethylene), solve acetate, carbitol acetate, cellosolve acetate, 3 poly(tetra?uoroethylene); methoxybutyl acetate, methylcarbitol acetate, methyl diene polymers, such as polyallene, polybutadiene, cellosolve acetate, and the like. polyisoprene, polychloroprene, poly(l-methoxybutadi When organic solvents highly compatible with water 65 ene), poly(2-tert-butyl-1,3-butadiene), poly(cyclopen are employed, water may be added to the coating solu tadiene), poly(1,3-cyclohexadiene), poly(dimethylful tion in an amount within the range which does not vene), poly(4-vinyl-1-cyclohexane), poly(l,5-hexadi impair solubility or dispersibility of the scaling preven ene), poly(1,5-cyclooctadiene), poly(bicyclo-[2,2,l] 4,758,639 23 24 hepta-2,5-diene), poly(5,7-dimethyl-l,6-octadiene), yaldehyde), poly(glutardialdehyde), poly(B-methyl poly(diallylphthalate), poly(diallylmethylsilane), poly( glutardialdehyde), po1y(B-phenylglutardialdehyde), diallylphenylphosphineoxide); poly(dimethylketene), polyacetone, poly(monobrom acetylene polymers, such as polyacetylene, poly(cy oacetone), poly(7-oxa-bicyclo[2,2,1]heptane), poly(3 anoacetylene), poly(hydroxymethyl)acetylene), poly( phenoxylene), poly(2,6-xylen0l), poly(ethylene oxide), butoxyacetylene), poly(phenylacetylene), poly(di poly(propylene oxide), poly(cyclopentene oxide), phenyldiacetylene), poly(pyridylacetylene); poly(cyclohexene oxide), poly(phenylglycidyl ether), aliphatic vinyl polymers and vinylidene polymers, poly(l,2-di(epoxyethyl)benzene), po1y(3,3-bis( such as polyvinyl alcohol, polyallyl alcohol, poly(vinyl chloromethyl)oxetane), poly(tetrahydrofuran); formal), poly(vinylacetal), poly(vinylbutyral), poly( polysul?des, polysulfones, such as poly(thiocarboxyl vinylisobutyral), poly(vinylcyclohexanoneketal), po1y(~ ?uoride), poly(ethylenedichloride-sodium tetrasul?de), vinyl acetate), poly(vinylchloroacetate), poly(vinyl poly(dichlorodiethyl ether-sodium disul?de), poly(di isobutyrate), poly(vinyl pivalate), poly(vinyl n-capro chlorodiethyl ether-sodium tetrasul?de), poly(pheny-= ate), poly(vinyl caprylate), poly(vinyl laurate), poly(vi lenesul?de), poly(ethylenesulfone), poly(propylenesul nyl palmitate), poly(vinyl benzoate), poly(vinyl sulfate), fone), poly(l-butenesulfone), poly(S-norbornenesul poly(vinyl chloride), poly(vinylidene chloride), poly( fone), poly(styrenesulfone), poly(l-pentylsulfone), po vinyl bromide), poly(vinyl methyl ether), poly(vinyl ly(l-hexylsulfone), poly(l-heptylsulfone), poly(butadi ethyl ether), poly(vinyl n-propyl ether), poly(vinyl iso enesulfone), poly(isoprenesulfone), poly(dimethyl propyl ether), poly(vinyl n-butyl ether), poly(vinyl iso butadienesulfone), poly(1,5-hexadienesulfone), poly( butyl ether), poly(vinyl tert-butyl ether), poly(vinyl 20 cis,cis-cyclooctadienesulfone), poly(norbornadienesul neopentyl ether), poly(vinyl carbomethoxymethyl fone); ether), poly(vinyl-2-methoxyethyl ether), poly(vinyl-2 various addition polymers, such as poly(methylene chloroethyl ether), poly(vinyl 2,2,2-tri?uoroethyl diisocyanate), poly(ethylene diisocyanate), poly( ether), poly(vinyl benzyl ether), poly(vinyl methyl ke trimethylene diisocyanate), poly(tetramethylene diiso tone), poly(methyl isopropenyl ketone), poly(l-nitro 25 propylene), poly(vinylsulfotluoride), poly(vinylsulfonic cyanate), poly(5-iminohydantoin, poly(per?uoro acid), poly(vinyl diphenylphosphineoxide), poly(vinyl glutarodinitrile), poly(l~(per?uorobutyryl)aziridine); diphenylphosphinesul?de), poly(dimethyl-2-cyano-2~ formaldehyde resins, such as phenol-formaldehyde propene-l-phosphonate), poly(diethyl-2-cyano-2-pro resin, melamine-formaldehyde resin, urea-formalde pene-l-phosphonate), poly(maleic anhydride); 30 hyde resin, aniline-formaldehyde resin, p-toluenesul aromatic vinyl polymers, such as polystyrene, poly fonamide-formaldehyde resin; (a-methylstyrene), poly(4»chlorostyrene), poly(4 polyesters, such as poly(l l-oxyundecanoate), poly( bromostyrene), poly(dichlorostyrene), poly(4-methoxy hexamethylene succinate), poly(hexamethylene seba styrene), poly(2,5=dimethoxystyrene), poly(vinyl-bis(l cate), poly(hexadecamethylene sebacate), poly(hex ethoxyethyl)hydroquinone), poly(4-vinyl-phthalic 35 amethylene-a,a'»dibutylsebacate), poly(octamethylene acid), poly(4-vinylphenylboric acid), poly(diphenyl-4 cis-hexahydroterephthalate), poly(octamethylene tran~ styrylphosphine oxide), poly(diphenyl-4-styrylphos shexahydroterephthalate), poly(hexamethylene male phine sul?de), poly(9-vinylanthracene), poly(4-vinyl ate), poly(hexamethylene fumarate), poly(hexamethy biphenyl), poly(acenaphthylene), polyindene; lene acetylenedicarboxylate), poly(ethylene terephthal heterocyclic vinyl polymers, such as poly(N-vinyl ate), poly(p-phenylene isophthalate), poly(4,4'-bipheny carbazole), poly(9-A5-pentenylcarbazole), poly(9-A5 lene isophthalate), poly(hexamethylene carbonate), po hexenylcarbazole), poly(N-vinylpyrrolidone), poly(2 ly(p-phenylene carbonate), poly(m~phenylene carbon vinylpyridine), poly(4-vinylpyridine), poly(2-methyl-2-= ate), poly(4,4'-isopropy1idenediphenylene carbonate), vinylpyridine), poly(2,4-dimethyl-6-vinyl-S-triazine), poly(4,4'-(2-pentylene)diphenylene carbonate), po poly(N-vinyl-l,2,4-triazine), poly(N-vinylbenztriazole), 45 ly(l,2-bis(hydroxymethyDcarborane-adipic acid), poly poly(N-morpholinone-(3)), polycournarone; (allylsulfonate), poly(hydroquinone-aryloxyphosphoryl acrylic and methacrylic polymers, such as poly dichloride), poly(hydroquinone-(chloromethyDphos acrylic acid, polymethacrylic acid, poly(methyl acry phoryl dichloride), poly(hydroquinone-(N-dimethyl) late), poly(ethyl acrylate), poly(butyl acrylate), poly(5 phosphoramidic acid)dichloride; cyano-3-thia-phenylacrylate), poly(methyl methacry polyamides, such as poly(isocyanate), poly( late), poly(ethyl methacrylate), poly(n-propyl methac vinylisocyanate), poly(butylisocyanate), poly(3-amino rylate), poly(n-butyl methacrylate), poly(isobutylme propionic acid), poly(6-aminopropionic acid), poly(ll thacrylate), poly(n-hexyl methacrylate), poly(2-ethyl aminoundecanoic acid), poly(hexamethylene adipa butyl methacrylate), poly(n-octyl methacrylate), po mide), poly(decamethylene adipamide), poly(3,3'-=(rne ly(n-lauryl methacrylate), poly(4-(tert-butyl)phenyl 55 thylimino)bistrimethylene adipamide), poly(benzidine methacrylate), poly(bornyl methacrylate), poly(B-(N isophthalic acid), poly(pyrromelliticdianhydride carbazyl)ethyl methacrylate), poly(tert-butyl cronton aromatic diamine), poly(l,6-hexamethylene-bis(carbox ate), polyacrylonitrile, polymethacrylonitrile, poly yethyDsuJ?de), poly(l,6-hexamethylenediamine-ben acrylamide, poly(N,N-dimethy1acrylamide), poly(N zene-l,3-bis-sulfonic acid chloride), poly(trans-2,5 (1,l-dimethyl-3=oxobutyl)acrylamide, poly(a» dimethyl—piperazine-4,4'~sulfony1-dibenzoyl chloride), crylopiperidine), poly(acrylomorpholide), poly(9 poly(bis(3-aminopropyl)phenylphosphine-adipic acid), acryloylcarbazole), polymethacrylamide, polyacrolein, poly(bis(3-aminopropyl)phenylphosphine-terephthalic poly(a-methylacrolein), poly(diacryloylmethane), acid), poly(bis(3-aminopropyl)rnethylphosphine oxide poly(acrylic anhydride), poly(methacrylic anhydride); adipic acid), po1y(bis(3-aminopropyl)n-octylphosphine polyethers, such as polyformaldehyde, polyacetalde 65 adipic acid), poly(bis(3-aminopropyl)phenylphosphine hyde, poly(mono-chloroacetaldehyde), polychloral, oxide-adipic acid), p0ly(hexamethylenediamine-bis(2 polypropionaldehyde, polyacrolein, poly(2-formyl-A5 carboxyethy1ene)pheny1phosphine oxide), poly(hex dihydropyrane), poly(trans-1,2-cyclohexanedicarbox amethylenediamine-bis(p-carboxyphenyl)phenylphos 4,758,639 25 26 phine oxide), poly(piperazine-bis(2-carboxyethyl) ing portions which monomers can possibly contact), for phenylphosphine oxide); example, stirring blades, stirring shaft, condenser, polyureas, polyurethanes, such as polyureas, po header, baf?es, search coil, bolts, nuts, etc. Preferably, ly(l , IO-decamethylenediamine- l , 6-hexamethylene-bis the scaling preventive is further applied on the portions ethylurethane), poly(diphenylmethane-4,4’-diisocya of recovery system of unreacted monomers where nate-4,4'-diphenylmethane), poly(toluene-2,4-diisocya scales may be sticked, for example, the inner surfaces of nate-N,N’-bis(trimethysilyl)-p,p'-diaminodiphenyl monomer distillation columns, condensers, monomer ether, polyurethane, polyurethane poly(propyleneox storage tanks, valves, etc. ide) basis; The method for applying the scaling preventive on various linear condensed polymers, such as poly(die l0 the inner surface of a polymerizer, etc. as mentioned thylcarbodiimide), poly(diallylcarbodiimide), poly(di~ above is not particularly limited, and may be inclusive n-butylcarbodiimide), poly(methylisopropylcarbodii typically of the brush coating, spray coating, the mide), poly(di-n-hexylcarbodiimide), poly(diphenylcar method of ?lling the polymerizer with a coating solu bodiimide), poly(4,4’-diphenylenemethanecarbodii tion followed by withdrawal thereof, and otherwise the mide), poly(hexamethylenecarbodiimide), poly(1,3 15 automatic coating methods as disclosed in Japanese xylylenecarbodiimide), poly(3-methyl-l,4 Laid-open Patent Publication (Kokai) Nos. 61001/ 1982, phenylenecarbodiimide), poly(2,2'-dimethyl~ 36288/1980, Japanese Laid-open Patent Publication biphenylenecarbodiimide), poly(2,2’-dimethoxy (Kohyo) Nos. 501116/1981, 501117/1981 and Japanese biphenylenecarbodiimidc), poly(l,5-naphthylenecar Laid-open Patent Publication (Kokai) No. 11303/1984. bodiimide), poly(adipyldihydrazide-succinoyl chlo 20 The process of the present invention can be applied to ride), poly(adipyldihydrazide-isophthaloyl chloride), various polymerizations of vinyl monomers in aqueous poly(isophthalicdihydrazide-terephthaloyl chloride), media. Typical examples of such polymerizations in poly(2,S-dimethylbenzylene), poly(-xyly1ene), poly(2,5 clude the production of polymers by suspension poly dimethylxylylene), poly(2,S-dimethoxy-p-xylylene), merization or emulsion polymerization of a vinyl halide poly(p-xylylidene), poly(a-cyano-m-xylylidine), poly 25 such as vinyl chloride or a monomeric mixture contain (a-cyano-p-xylylidine), poly(nitrophenylene), poly(tet ing the vinyl halide as a main constituent, such as a ramethyl-p-phenylenedimethylene), poly(2,5-dihydr mixture of vinyl chloride and vinyl acetate; the produc doxy-p-phenylenedimethylene), poly(4,4'-oxydi tion of beads or latex of polymers such as polystyrene, phenylenedimethylene), poly(2,5-dimethoxy-p polymethacrylate, polyacrylonitrile and the like; the phenylenedimethylene); 30 production of synthetic rubbers such as SBR, NBR, heterocyclic condensed polymers, such as poly(ben CR, IR, HR and the like (such synthetic rubbers are zoimidazole), poly(alkylene-S,5'-dibenzoimidazole), po generally produced by emulsion polymerization); the ly(allylene-S,5’-dibenzoimidazole), poly(pyromelliti production of ABS resins, etc. The system of polymeri mide), poly(benzooxazole), poly(oxadiazole), poly(ox zation may be either suspension polymerization or adiazolidine), poly(dithiazole), poly(benzothiazole), emulsion polymerization. Vinyl monomers which can poly(l,4-xylenyl)-2-methylpiperazine), poly(quinoxa be provided for polymerization may be exempli?ed by line), poly(S-triazinyleneimide); vinyl halides such as vinyl chloride, vinyl esters such as natural polymers, modi?ed natural polymers, such as vinyl acetate, vinyl propionate, acrylic acid, meth natural rubber, cyclized rubber, hydrochloric acid rub acrylic acid or their esters or salts, maleic acid or fu ber, chlorinated rubber, guttapercha, cellulose, methyl 40. maric acid, and their esters or anhydrides, diene mono cellulose, ethyl cellulose, propyl cellulose, butyl cellu mers such as butadiene, chloroprene or isoprene, fur lose, allyl cellulose, benzyl cellulose, hydroxyethyl cel ther styrene, acrylonitrile, vinylidene halide, vinyl lulose, carboxylmethyl cellulose, cyanoethyl cellulose, ether, etc. In carrying out the polymerization of one or cellulose triformate, cellulose acetate, cellulose triace more of such monomers, the object of scaling preven tate, cellulose tripropionate, cellulose tributyrate, cellu 45 tion can be effectively attained irrespective of the sys lose tricaproate, cellulose tricarbanilate, cellulose ni tem or formulation for the polymerization. trate, cellulose trinitrate, starch, amylose, amylose ace In the suspension or emulsion polymerizations, the tate, amylose carbanilate, amylopectin, alginic acid, polymerization catalysts generally employed are, for chitin, glycogen, gum arabic, gum tragacanth, heparine, example, organic peroxides such as t-butylperox pectin, rosin, kopal, shellac, casein, collagen(calf-skin), yneodecanate, di-2-ethylhexylperoxydicarbonate, 3,5,5 collagen(ichthyocol), gelatin, peanut-protein, soybean trimethylhexanoylperoxide, a-cumylperoxyneodecano protein, nucleic protein (calf thymus), nucleic protein ate, cmnene hydroperoxide, cyclohexanoneperoxide, (sperm of sea urchin), poly(sarcosine), sericin, silk, t-butylperoxypivalate, di-Z-ethoxyethylperoxydicar wool, zein, polyadenylic acid, deoxyribonucleic acid, bonate, benzoyl peroxide, lauroyl peroxide, 2,4 ribonucleic acid; 55 dichlorobenzoyl peroxide, diisopropylperoxydicarbon polysiloxanes, such as polysiloxane, polydimethylsi ate and acetylcyclohexylperoxide, etc., azo catalysts loxane; such as a,a’-azobisisobutyronitrile, a,a'-azobis-2,4 organic metal polymers, such as poly(bis dimethylvaleronitrile, water soluble persulfates such as (imidazolate)-metal(II)), poly(aluminumtriiso potassium persulfate, ammonium persulfate, etc. Also, propylateethylenediamine); and as a dispersant, there may be employed, for example, inorganic polymers such as polymetaphosphate, and suspending agents such as natural or synethtic poly so on. meric compounds, e.g., partially saponi?ed product of In the process of the present invention, the above polyvinyl acetate, polyacrylic acid, copolymer of vinyl mentioned scaling preventive is applied on the inner acetate and maleic anhydride, cellulose derivative such wall surface of a polymerizer and the portions of the 65 as hydroxypropylmethyl cellulose and gelatin; emulsi? auxiliary polymerizer equipment where scales may be ers as exempli?ed by nonionic emulsi?ers such as sorbi sticked, namely the portions which monomers may tane monolaurate, sorbitane trioleate, anionic emulsi? come into contact with during polymerization (includ ers such as sodium laurylsulfonate, sodium alkylben 4,758,639 27 28 zenesulfonate. As other additives, fillers such as calcium Next, the thus coated polymerizer was charged with carbonate, titanium oxide, etc., stabilizers such as triba 100 parts of vinyl chloride monomer, 200 parts of deion sic lead sulfate, calcium stearate, dibutyltin laurate, ized water, 0.022 part of partially saponi?ed polyvinyl dioctyltin mercaptide, etc., lubricants such as lice wax, alcohol, 0.028 part of hydroxymethyl cellulose and 0.03 stearic acid, cetyl alcohol, etc., plasticizers such as part of t-butyl peroxyneodecanate, and polymerization DOP, DBP, etc., chain transfer agents such as trichloro was carried out at 52“ C. for 7 hours. After completion ethylene, mercaptans, etc. and pH controllers may be of polymerization, the polymer was taken out and the added into the polymerization system. According to the polymerizer was washed with water at a flow rate of 0.1 process of the present invention, irrespeotively of m3/m2hr for the period of time shown in Table l. The which catalysts, dispersants or additives may be em 10 above operations from coating and charging to washing ployed, scaling can effectively be prevented in any with water were conducted for each batch and this was polymerization system. repeated for a maximum of 200 batches. The present invention is described in more detail Also, scaling after completion of each of the 10th, below with reference to the following Examples, by 30th, 50th, 100th, 150th and 200th batches was evalu which the scope of the present invention is not limited. ated visually according to the standards shown below, In the following, all parts are by weight unless other and the amount of scales adhering (g/m2) was also mea wise noted. sured after completion of the ?nal batch. The results are (Note: In the following Examples, Experiment Nos. also shown in Table 1. 277 to 300 are skipped.) A: no sticking of scale B: several percent sticking of sandy scales EXAMPLE 1 C: scales sticking thinly over part of the surface (about As shown in Table 1, for each experiment, a 100-l, 10% of surface) 1000.1, 2000-1, 40-m3 or 130-m3 stainless steel polymer D: scales sticking thickly over part of the surface (about izer was selected, and the inner wall surface of the poly 10% of surface) merizer and the portions of the auxiliary equipment 25 E: scales sticking thinly over part of the surface (about such as stirrers which may come into contact with mon 50% of surface) omer were treated to have the surface roughness F: scales sticking thickly over part of the surface (about (Rmax) shown in the Table. For each experiment, as 50% of surface) shown in Table l, a dye or a pigment was dissolved or G: scales sticking thinly over the entire surface dispersed in a solvent, optionally with the addition of an 30 H: scales sticking thickly over the entire surface inorganic compound or a polymeric compound as In Table l, the Experiment numbers marked with an shown in the Table to prepare a coating solution. The asterisk (*) indicate Comparative examples. In particu formulation ratio of the inorganic compound or the lar, Experiment Nos. 1 to 6 are examples in which the polymeric compound and the concentration of the dye inner wall surface of the polymerizer was subjected to or pigment in the coating solution are also shown in 35 no treatment with any compound. Also, the coating Table l. The coating solution was applied on the inner solution employed in Experiment Nos. 23 and 57 was wall surface of the polymerizer, etc. treated as men~ prepared by dissolving one part of sodium sulfide in 100 tioned above, dried at 80° C. for 10 minutes and then parts of water and adding 0.5 part of a dye to the resul thoroughly washed with water. tant solution, followed by heating at 80° C. for 30 min 40 utes. TABLE 1 Coating Solution (1) Inorganic (a)/(b) Polymeric (a)/(c) (2) Exp. Dye or pigment (a) compound weight compound weight conc. Solvent No. (Mixing ratio) (b) ratio (c) ratio % (Mixing ratio)

1: ______

2" — - -- -

3“ - - — —

4"‘ — — - -

5‘ — — — —

6” - - - — 7" Solvent Black 5 - - 0.5 Methanol 8° " Colloidal silica 100/100 — 0.5 " 9‘ — " 0/100 — 0.4 " l0‘ Solvent Black 5 - Atactic polypropylene 100/70 0.7 Acetone ll‘ — —- " 0/100 0.5 " l2 Solvent Black 5 — — 0.5 Methanol l3 Solvent Black 5 Colloidal silica 100/100 — 0.6 " l4 " Fe(OH)3 sol 100/5 - 0.6 " l5 Acid Blue 82 - -- 0.5 Water/Methanol (90/10) 16 " Water glass 100/100 — 0.7 Water/Methanol (90/10) 17 ” Colloid of sulfur 100/5 — 0.6 Water/Methanol (90/10) 18 " CuClz 100/2 —- 0.5 Water/Methanol (90/ i0) 19 Acid Violet 47 - - 0.8 Water 20 Acid Red 83 -- — 0.5 " 2l Acid Blue 102 — —~ 0.7 " 22 Direct Blue 199 - — 0.7 " 23 Food Blue 2 — — 2.0 " 24 Food Green 2/Acid Red 52 Colloidal silica 100/50 -— 0.8 Water/Isobutyl 4,758,639 29 30 TABLE l-continued (90/10) alcohol (90/10) 25 Direct Blue 108 — — 0.9 Water 26 Acid Brown 165 ~ — —- 1.0 " 27 Acid Yellow 7 Zn(CH3COO)2 100/5 — 0.5 ” 28 Sulfur Blue 2 — — 0.9 " 29 Fluorescent Brightening — - 0.8 " Agent 56 30 Reactive Yellow 2 —- — 0.9 " 31 Reactive Green 7 — — 017 " 32 Basic Red 2 Metasilicic acid — 0.8 " (100/ 80) 33 Reactive Blue 7 — — 0.5 " 34 Reactive Black 8 — - 0.8 " 35 Azoic Brown 2 — Polystyrene 100/30 0.7 Toluene 36 Azoic Orange 7 — — 0.9 Water 37 Basic Yellow 34 — — 0.5 " 38 Basic Orange 2 — — 0.8 " 39 Basic Red 17 - — 1.0 " 40 Basic Violet 26 - - 0.5 " 41 Basic Orange l4/Disperse Blue Colloid of lithium 100/ 150 — 1.0 Water/Acetone 66 (50/50) silicate (50/50) 42 Disperse Brown 3 — —— 0.7 Acetone 43 Pigment Blue 25/So1vent Black 5 — Polystyrene 100/20 0.7 Toluene (20/80) 44 Solvent Red 21 Sodium metasilicate 100/60 — 0.9 Methanol 45 Basic Blue 21 — ' — 0.6 Water 46 Vat Yellow 10 -— — 0.4 Xylene 47 Vat Red 16/Vat Brown 44 - - — 0.5 " 48 Solvent Black 7 Colloidal silica 100/100 - 0.4 Water/Methanol (30/70) 49 Dispetse Blue 104 -— Polyindene 100/50 0.7 Trichloroethylene 50 Vat Yellow 4 - - 0.9 Xylene 51 Vat Orange 4 — — 0.5 Methanol 52 Pigment Violet 122 -— Poly(4-chlorostyrene) 100/100 1.0 MEK 53 Vat Red 1 — — 0.8 Xylene 54 Pigment Green 38 -— Poly(4-methoxystyrene) 100/ 10 0.9 MEK 55 Acid Black Z/Basic Red 9 -— — 0.5 Water/n-Amyl alcohol (80/20) 56 Basic Green 1 — — 0.6 Water 57 Pigment Blue 1 — Poly(vinyl methyl 100/40 0.9 Acetone ketone) 58 Pigment Violet 23 - Atactic polypropylene 100/70 0.7 Toluene v59 Solvent Black 3/Basic Blue 24 -— — 0.6 Methanol 60 Basic Orange 22 Water glass — 0.8 Water (100/ 50) 61 Disperse Yellow 33 —- — 1.5 Xylene 62 Vat Orange 7 —- - 0.7 Pyridine 63 Sulfur Blue 4 Fe(OI-I)3 sol 100/5 -_— 0.6 Water 64 Fluorescent Brightening — — 0.7 Pyridine Agent 174 (3) (4) Surface roughness of Time for washing Scaling (l) inner wall surface, etc. with water after Visual evaluation (Amount attached g/m2) Exp. Capacity of (Rmax) completion Batch No. No. Polymerizer um min. 10 30 50 100 150 200 1' 1001 10-13 60 H (1200) 2' 40 1113 7-8 " H (1100) 3*’ 1001 0.8-1 30 H (900) 4' 130 m3 0.4-0.7 " E H (900) s“ 1 1113 0.2-0.3 " E H (800) 6' 2 m3 o.os-o.1 " B E H (700) 7' 40 m3 7-8 " B E H (400) 8' " " " B C F H (300) 9' 1 m3 0.2-0.3 " H (800) 10' 40 m3 7-8 " B c F H (450) 11' 1 m3 0.2-0.3 60 H (1100) 12 130 m3 0.4-0.7 10 A A A A A B (3) 13 " (3.4-0.7 " A A A A A A (0.2) 14 " ” " A A A A A A (0.5) 15 2 m3 0.05-0.1 " A A A B C D (20) 16 " " " A A A A A A (0.9) 17 " " ” A A A A A A (0.7) 18 " " " A A A A A A (0. 19 " ” " A A A B C D (21) 20 " " " A A A B C D (18) 21 " " " A A A B C D (19) 22 " " ” A A A B C D (15) 23 " " ” A A A B C D (20) 24 " " " A A A A A A (0.5) 25 1 m3 0.2-0.3 ” A A A B C D (16) 26 " " ” A A A B C D (18) 4,758,639 31 32 TABLE l-continued 27 " " " A A A A A A(0.9) 2s " " " A A A B c 13(20) 29 " " " A A A B c ‘ 13(22) 30 " " " A A A B 0 0(19) 31 " " " - A A A A B C(10) 32 1301113 0.4-0.7 " A A A A A A(0.8) 33 1163 0.2-0.3 " A A A B c D(l8) s4 " " " A A A A B 0(8) 35 " " " A A A A A B(3) 36 " " " A A A A B cum :7 " " " A A A B c 13(20) as " " " A A A A B c(9) 39 " " " A A A B c D(l8) 40 1001 0.2-1 " A A A B c 13(17) 41 " " " A A A A A A(0.7) 42 " " " A A A A A 8(3) 43 " " " A A A A A B(2.5) 44 " " " A A A A A A(0.4) 4s " " " ,A A A B c 13(19) 46 " " " A A A A A 13(4) 47 " " " A A A A B c(9) 4s " " 1s A A A A A A(0.2) 49 21113 nos-0.1 " A A A A A B(2.5) so " " " A A A A B ca) 51 " " " A A A A B c(9) s2 " " " A A A A B C(10) s3 " " " A A A B 0 13(19) s4 " " " A A A A A B(2.3) 5s " " " A A A A A A(0.9) 56 " " " A A A A B can 57 " " " A A A B c D(18) 58 11113 0.2-0.3 " A A A A A B(2.1) s9 " " " A A A A A A(0.7) 60 " " " A A A A A B(1.8) 61 " " " A A A A B c(10) 62 " " " A A A A B co) 63 " " " A A A A A A(0.6) 64 " " " A A A B c 0(7) Notes: (I) acomparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner Wall surface of the polymerizer and the portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 m3/m2h

zation was carried out at 52° C. for 10 hours. After EXAMPLE 2 completion of polymerization, the polymer was taken As shown in Table 2, for each experiment, a 100-1, out and the polymerizer was washed with water at a 1000-1, 2000-1, 40-m3 or l30-m3 stainless steel polymer flow rate of 0.1 m3/m2hr for the period of time shown izer was selected, and the inner wall surface of the poly in Table 2. The above operations from coating and merizer and the portions of the auxiliary equipment charging to washing with water were conducted for such as stirrers which may come into contact with mon each batch and this was repeated for a maximum of 200 omer were treated to have the surface roughness batches. (Rmax) shown in the Table. For each experiment, as 45 In the same manner as in Example 1, scaling after shown in Table 2, a dye or a pigment was dissolved or completion of each of the 10th, 30th, 50th, 100th, 150th dispersed in a solvent, optionally with the addition of an and 200th batches was evaluated visually, and the inorganic compound or a polymeric compound as amount of scales adhering (g/m2) was also measured shown in the Table to prepare a coating solution. The 50 after completion of the ?nal batch. The results are also formulation ratio of the inorganic compound and the shown in Table 2. polymeric compound and the concentration of dye or In Table 2, the Experiment numbers marked with an pigment in the coating solution are also shown in Table asterisk (*) indicate Comparative examples. In particu 2. The coating solution was applied on the inner wall lar, Experiment Nos. 65 and 66 are examples in which surface of the polymerizer, etc. treated as mentioned 55 the inner wall surface of the polymerizer was subjected above, dried at 80° C. for 10 minutes and then thor- to no treatment with any compound. Also, the coating oughly Washed with water. solution employed in Experiment Nos. 105 and 133 was Next, the thus coated polymerizer was charged with prepared by dissolving one part of sodium sul?de in 100 100 parts of vinyl chloride monomer, 200 parts of deion- parts of water and adding 0.5 part of a. dye to the resul ized water, 0.12.5 part of hydroxypropylmethyl cellu- 60 tant solution, followed by heating at 80° C. for 30 min lose, 0125 part of sorbitan monolaurate and 0.025 part utes. of a,ct'-azobis-2,4-dimethylvaleronitrile, and polymeri= TABLE 2 1 Coating Solution (1) Inorganic (a)/(b) Polymeric (a)/(c) (2) Exp. Dye or pigment (a) compound weight compound weight cone. Solvent No. (Mixing ratio) (b) ratio (0) ratio % (Mixing ratio) 4,758,639 33 34 TABLE 2-continued

66' ______67' Basic Black 2 —— — 0.8 Water/n-Butyl _ alcohol (80/20) 68’ " Colloidal silica 100/80 — 0.8 Water/n-Butyl alcohol (80/20) 69' — ” 0/100 —- 0.8 Water 70' — — Polyindene 0/100 0.5 Dioxane 71' Basic Red 2 ZnClz 100/5 — 0.8 Water/n-Amyl alcohol (80/20) 72' Acid Blue 59 Water glass 100/80 -- 0.5 Water/lsobutyl alcohol (90/10) 73‘ Basic Orange 14 Mesotrisilicic acid 100/50 -— 0.7 Water 74’ Acid Black 2 Manganese dioxide 100/5 — Water/Butyl alcohol (85/ 15) 75 Basic Orange 14 — - 0.6 Water 76 " ZnClz — " " 77 Basic Orange 14 Colloidal silica — 0.6 " 78 " Colloid of sulfur — " " 79 Direct Brown 44 — — 0.9 " 80 Acid Orange 33 -- —- 0.8 " 81 Basic Red 2 ZnClz 100/5 — 0.8 Water/n-Amyl alcohol (80/20) 82 Mordant Red 21 — —- 0.5 Water 83 Solvent Red 30 —- - 0.7 Methanol 84 Acid Black 110 — — 0.4 Water 85 Direct Blue 108 Mesotetrasilicic acid 100/40 — 0.7 " 86 Acid Blue 59 Water glass 100/80 — 0.5 Water/Isobutyl alcohol (90/ 10) 87 Solvent Orange 44 -— -— 0.9 Methanol 88 Solvent Black 5 — —- 1.0 " 89 Basic Orange 14 Mesotrisilicic acid 100/50 — 0.7 Water 90 Solvent Red 100 —— — 0.6 Methanol 91 Basic Blue 22 Al(OH)3 sol 100/2 — 0.5 Water 92 Vat Yellow 20 — —- 0.8 " 93 Vat Orange 13 -— — 0.4 ” 94 Disperse Violet 23 —- —- 0.9 Acetone 95 Solvent Black 3 — —- 0.7 " 96 Pigment Red 35 -— Poly(vinyl n-butyl 100/80 1.0 Methylene ether) chloride 97 Vat Green 2 — -— . 0.5 - 98 Pigment Red 88 — Polyvinyl methyl 100/70 0.8 Dioxane ketone 99 Pigment Blue 16 — Polyvinyl sulfonic 100/100 0.7 Water acid 100 Basic Blue 19 Ce(NO3)3 100/l0 — 0.7 " 101 Solvent Blue 73/Pigment Blue 2 -- Polyindene 100/50 0.5 Dioxane (50/50) 102 Solvent Black 49 Ni(N03)2 100/20 —— 1.0 Water . 103 Basic Black 2 Colloidal silica 100/80 —- 1.0 Water/n-Butyl alcohol (80/20) 104 Disperse Violet 42 — — 0.7 Acetone 105 Sulfur Blue 6 - — 0.9 Water 106 Solubilized Sulfur Brown 1 — —- 0.6 ” 107 Fluorescent Brightening —— -— 0.4 " Agent 22 108 Disperse Red 113 — — 0.8 Acetone 109 Pigment Red Z/Pigment — Polyacenaphthylene 100/100 0.8 Toluene Green 10 110 Pigment Yellow 13 — Poly(4-vinylbiphenyl) 100/30 0.6 Benzene l l 1 Basic Orange 2 MgCl; 100/l5 -- 0.9 Water 112 Basic Orange 33 — — 0.6 " 113 Basic Yellow 36 — — 0.7 " 114 Direct Violet 90 — — 0.5 " 115 Direct Blue 168 -— — 0.6 " 116 Direct Black 22 Water glass 100/50 — 0.6 Water/lsobutyl alcohol (90/10) 117 Acid Yellow 42 — — 1.0 Water 118 Acid Red 77/Food Yellow 4 — — 0.5 " (40/60) 119 Pigment Brown 5 —- Polyacrylomorpholide 100/50 1.0 DMF 120 Acid Black 115 Colloid of sulfur 100/20 -— 0.9 Water 121 Direct Red 11 — — 0.6 " 122 Mordant Blue 8 — — 0.8 " 123 Pigment Violet 5 -— Polyacrolein 100/40 0.9 DMF 124 Food Blue l/Food Green 2 —- — 0.7 Water 125 Pigment Red 90 — Poly(.l,5-hexadiene- 100/80 0.8 Acetophenone sulfone) 126 Acid Black 2 Colloid of manganese 100/ 5 — 0.6 Water/n-Butyl dioxide alcohol (85/15) 127 Acid Brown 103 - — 0.5 Water 128 Acid Yellow 7/Solvent Back 7 COCl2 100/2 — 0.7 Water/Methanol (90/10) (30/70) 4,758,639 36 TABLE 2-continued 129 Sulfur Green 2 0.9 Water 130 Fluorescent Brightening 0.4 Agent 87 131 Reactive Orange 20 0.5 132 Reactive Brown 7 0.8 133 Reactive Black 12 Sodium metasilicate ' 100/30 1.0 Water/Amyl alcohol (80/ 20) 134 Azoic Component 17 0.6 Water 135 Azoic Green 1 0.8 (3) (4) Surface roughness of Time for washing Sealing (1) inner wall surface, etc. with water after Visual evaluation (Amount attached g/mz) Exp. Capacity Of (Rmax) completion Batch No. No. Polymerizer pm 30 50 100 150 200

33323 w,mmwm

mmzmm11 F(60) 13ml”mnlunnsmnn?musmnnnHnH11H”l?nn?amnunuuuqjmnnnlHuHuuuHlHunHuun3muHH3mHuHHu3m 1M10l iwzwzge?,M.1.,.M,M,M ,.., 3.JJ 31353 'IIOIIIII-ln'lIlIII'IOIIIIIOIIIII!fl)1!!!IlI!Ill! 1 CCCCAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA"(WC HHHHBAAACCACCCAACAACACCCCBCBBACAACCCCCBAACCCCACCBACCBCBACABCCH D(18) FFFFAAAABBABBBAABAABABBBBABAAABAABBBBBAAABBBBABBAABBABAABAABBF C(11) 13(3)

3) 13(21) wwwwwwwmwwnmwnwwnwemummnwwmwéw?wwwmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmm midunnnnnuuuwnwunu"nun"mu”munn?un"nun"wmnnuuunuuwuwnnnuunnunuuwwunnnu HWGBMHBBBBAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA CAAADDADDDAADBADADDDDCDCCADAADDDDDCBADDDDADDCADDCDCADACDD F(60) 4,758,639 37 38 TABLE 2-continued 132 " " " A A B C D F(62) 133 " " " A A A A A B(3) 134 " " ” A A B C D _ F(60) 135 " " " A A B C D F(59)

Notes: (1) ‘comparative examples (2) Dye or pigment concentration in coating solution. (3) Surface roughness of the inner wall surface of the polymerizer and the portions of the equipment thereof which may come into contact with the monomer. (4) Flow rate of water 0.1 ms/mzh peroxide, and polymerization was carried out at 70° C. EXAMPLE 3 for 6 hours. After completion of polymerization, the As shownin Table 3, for each experiment, a 100-1, polymer was taken out and the polymerizer was washed 1000-1, 2000-1, 40-m3 or 130-m3 stainless steel polymer with water at a flow rate of 0.1 m3/m2hr for the period izer was selected, and the inner wall surface of the poly- 15 of time shown in Table 3. The above operations from merizer and the portions of the auxiliary equipment coating and charging to washing with water were con such as the stirrers which may come into contact with ducted for each batch and this was repeated for a maxi monomer were treated to have the surface roughness mum of 200 batches. (Rrnax) shown in the Table. For each experiment, as In the same manner as in Example 1, scaling after shown in Table 3, a dye or a pigment was dissolved or 20 completion of each of the 10th,,30th, 50th, 100th, 150th dispersed in a solvent, optionally with the addition of an and 200th batches was evaluated visually, and the inorganic compound or a polymeric compound as amount of scales adhering (g/rn2) was also measured shown in the Table to prepare a coating solution. The after completion of the ?nal batch. The results are also formulation ratio of the inorganic compound and the shown in Table 3. polymeric compound and the concentration of dye or 25 In Table 3, the Experiment numbers marked with an pigment in the coating solution are also shown in Table asterisk (*) indicate Comparative examples. In particu 3. The coating solution was applied on the inner wall lar, Experiment Nos. 136 and 137 are examples in which surface of the polymerizer, etc. treated as mentioned the inner wall surface of the polymerizer was subjected above, dried at 80° C. for 10 minutes and then thor- to no treatment with any compound. Also, the coating oughly washed with water. 30 solution employed in Experiment Nos. 177 and 178 was Next, the thus coated polymerizer was charged with prepared by dissolving one part of sodium sul?de in 100 80 parts of vinyl chloride monomer, 20 parts of vinyl parts of water and adding 0.5 part of a dye to the resul acetate monomer, 200 parts of deionized water, 0.3 part tant solution, followed by heating at 80° C. for 30 min of gelatin, 1 part of trichlene and 0.175 part of lauroyl utes. TABLE 3 Coating Solution (1) Inorganic (a)/(b) Polymeric (a)/(c) (2) Exp. Dye or pigment (a) compound weight compound weight conc. Solvent No. (Mixing ratio) (b) ratio (c) ratio % (Mixing ratio)

136' - - - -

137* - __ _ _ 138‘ Solvent Black 5 — — 0.5 Methanol 139‘ " Colloidal silica 100/50 — 0.8 " 140* — " 0/100 - 1.0 Water 141' Solvent Black 5 -- Polystyrene 100/50 0.7 Toluene 142' Basic Black 2 Water glass 100/50 — 0.9 Water/Isobutyl alcohol (90/10) 143* Disperse Blue 98 BaClz 100/5 — 0.8 Water/Acetone (50/50) 144‘ Basic Blue 65/Basic Red 34 CuSO4 100/20 — 0.9 Water (70/30) 145 Acid Violet 41 — —- 0.5 Methanol 146 " Colloidal silica 100/150 — 0.8 " 147 " Al(OH)3 sol 100/2 -— 0.5 ” 148 Acid Violet 41 FeClg 100/5 —- 0.5 Methanol 149 Direct Red 13 - _ " Water 150 Direct Green 31 NiClz 100/3 — 0.8 " 151 Basic Black 2 Water glass 100/50 — 0.9 Water/Isobutyl alcohol (90/10) 152 Basic Red 18 — - 0.5 Water 153 Basic Red 22 — -— 0.4 " 154 Basic Red 24 t - — 0.7 " 155 Basic Blue 65/Basic Red 34 CuSO4 100/20 — 0.9 " (70/30) 156 Azoic Diazo Component 21 — — 0.6 Methanol 157 Azoic Diazo Component 27 — — 0.6 Ethanol 158 Disperse Yellow 8 — Polyglutardialdehyde 100/100 0.8 Ethyl ether 159 Disperse Orange 45 —— — 0.6 Acetone 160 Disperse Red 58 — - 0.4 Acetone 161 Disperse Violet 24 Colloidal silica 100/40 —— 1.0 Water/Acetone (50/50) 162 Disperse Yellow 23 — — 0.8 Acetone 163 Disperse Red 74 — —- 0.9 " 164 Solvent Orange 31 — — 0.7 Methanol