Coloring composition
FIELD OF THE INVENTION 
     The present invention relates to a coloring composition suitable for a writing utensil, a print, a record, a stamp and a coloring of a paper. 
     BACKGROUND OF THE INVENTION 
     An aqueous ink contains various kinds of water soluble dyes. These aqueous inks have excellent solution stability, but have bad water resistance when used in a written trace or in a printed image. Especially, it is more difficult to provide the excellent water resistance to the aqueous ink right after writing down. 
     Various improvements have been proposed to overcome the above undesirable water resistance, for example, Japanese Pat. Publn. (unexamined) Nos. 31526/1976, 115306/1978, 116762/1981, 131678/1981, 10658/1982, 30772/1982, 102972/1982, 198768/1982, 202359/1982 and 1764/1983 and Japanese Pat. Publn. (examined) No. 6581/1965. Among them, the use of a direct ink was proposed, but this ink does not have sufficient water resistance and does not have good solubility at a low pH solution. A solution of a high pH hydrolyzes an acetate fiber used in a storage material of a felt tip pen container to lower physical properties of the ink or dye. Also the dye does not have a good color tone other than a black one. However the black dye may increase the viscosity or gelation of the ink. 
     An ink containing a water insoluble dye dissolved in an organic solvent provides sufficient water resistance. It, however, spreads easily and also has an irritating smell because of using an organic solvent. 
     Also, an emulsion or dispersion ink using the water insoluble dye or a water insoluble pigment was proposed. It, however, has an insufficient stability with time and may have a plugging of a capillary passageway of the storage material. 
     There exists an ink by which a written trace is made water insoluble with time because of a reaction of the written trace with light or oxygen in the air. It, however, takes a long time to appear the water resistance, and this ink has a possibility to change a color. 
     Furthermore, it was also proposed that an ink was prepared by adding an additive (including a polymer) increasing the water resistance to the water soluble dye. This ink is not expected to have the excellent resistance right after writing down. The ink is not stable to a pH change so that it has to be kept in a small range of pH. The additive ink having higher water resistant has a bad storage stability. 
     SUMMARY OF THE INVENTION 
     The present invention provides a coloring composition comprising a reaction mixture of 
     (a) a vinyl compound soluble in water or in a water soluble organic solvent, with 
     (b) a compound which contains more than two groups having an active hydrogen, at least one group of which is an amino group or imino group, 
     in the presence of a water soluble dye and optionally a solvent. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The coloring composition of the present invention provides an excellent property in the water resistance and the stability with time. It is believed that a reaction among the water soluble dye, the vinyl compound and the active hydrogen containing compound, or a polymerization reaction of the vinyl compound (a part of the vinyl compound indicates an exothermic reaction) contributes to an increase of the stability and an affinity with a paper. 
     Examples of the water soluble dye are a direct dye, an acid dye, a basic dye, a metallized complex dye and the like. 
     The composition of the present invention may contain the water soluble dye in the amount of from 30 to 50 percent by weight. Amounts less than 30 percent by weight are undesirable because of insufficient coloring value of the obtained composition. Amounts greater than 50 percent by weight make the reaction ununiform so as not to proceed the reaction under control. 
     Examples of the vinyl compound soluble in water or in an water soluble organic solvent are acrylic acid, 2-hydroxyethyl acrylate, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methacrylic acid, 2-hydroxyethyl methacrylate, diethylaminoethyl methacrylate, 2-methoxypolyethylene glycol methacrylate, allylsulfonic acid, styrenesulfonic acid, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylsuccinimide, 5-vinylpyrazoline, N-vinylethyleneurea, N-vinyloxazolidone, 2-vinylthiazole, 2-vinylpyridine, 4-vinylpyridine, 1-methyl-2-vinylpiperidine, 4-vinylpiperidine, N-vinylpiperidone, 2-vinylpyrazine, N-vinylcaprolactam and a mixture thereof. Preferred examples are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-methoxypolyethylene glycol methacrylate, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylsuccinimide, N-vinylethyleneurea, N-vinyloxazolidone, 1-methyl-2-vinylpiperidine, N-vinylpiperidone and N-vinylcaprolactam. 
     Preferably, the amount of the vinyl compound is from 10 to 40 percent by weight in the reaction composition. Amounts less than 10 percent by weight are undesirable because of insufficient water resistance in a written trace. Amounts greater than 40 percent by weight are undesirable, because large amounts of the water soluble organic solvent are required for making an ink solution. 
     The active hydrogen containing compound according to the present invention has more than 2 groups (or 2 atoms) which contain active hydrogen respectively, at least one group of which is an amino group or imino group. Examples of these compounds are m-aminophenol, p-aminophenol, 2-aminophenol-4-sulfonamide, m-phenylenediamine, p-phenylenediamine, 2-chloro-m-phenylenediamine, 2,5-dichloro-m-phenylenediamine, tolylene-2,4-diamine, m-xylylenediamine, m-phenylenediamine-4-sulfonic acid, o-tolidine, 2-phenyl-4,5,-dihydroxymethylimidazol, 5,5-dimethylhydantoine, melamine, melamine resin, guanidine, diphenylguanidine, benzoguanamine, urea, thiourea and a mixture thereof. Preferred examples are m-aminophenol, m-phenylenediamine, p-phenylenediamine, 2-chloro-m-phenylenediamine, m-phenylenediamine-4-sulfonic acid, 5,5-dimethylhydantoine, diphenylguanidine, benzoguanamine, urea and thiourea. Also the active hydrogen containing compound may contain a back-bone of the water soluble dye mentioned above in a molecule. The active hydrogen containing compound is preferably contained in the amount of 2 to 10 percent by weight in the reaction composition. Amounts less than 2 percent by weight are undesirable because of insufficient solution stability and water resistance of the obtained composition. Amounts greater than 10 percent by weight are undesirable because the obtained product has poor quality. 
     A molar ratio of the vinyl compound to the active hydrogen containing compound is 100:5 to 30. 
     In the present invention, the reaction of the vinyl compound with the active hydrogen containing compound can be conducted without a solvent or in the presence of a solvent. The solvent can dissolve all reactants such as the dye, the vinyl compound and the active hydrogen containing compound. Especially, preferred solvents are those that the reaction mixture can be dissolved to a low viscosity. Examples of the solvent are lower molecule alcohols having 1 to 6 carbon atoms; glycols such as ethylene glycol, diethylene glycol and the like; triethyleneglycols; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether and the like; glycol monoacetate; glycerol; glycolic acids; ethylene carbonate; butyrolactone; 2-pyrrolidone; N-methylpyrrolidone; dimethyl formamide; tetrahydrofuran; dioxane; dimethylsulfoxide; and a mixture thereof. The amount of these organic solvent is generally less than 40 percent by weight in the reaction composition. 
     According to the invention, the reaction of the vinyl compound with the active hydrogen containing compound may be conducted under the presence of a catalyst. Preferred examples of the catalyst are an acid catalyst such as hydrogen chloride, sulfuric acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, a free acid of the above vinyl compound, an acid salt of the active hydrogen containing compound, a free acid of the dye and a coloring acid; an azo-initiator such as 2,2-azobisisobutyronitrile, a peroxide-catalyst such as benzoyl peroxide, butyl peroxide and the like. Preferred catalyst is the acid catalyst. The content of the catalyst is less than 5 percent by weight in the reaction mixture. 
     The above reaction is conducted at a temperature of 10° to 160° C., preferably 60° to 110° C. for 0.5 to 10 hours. 
     The composition obtained from the above reaction, i.e. the reaction production of the above water-soluble dye, the vinyl compound with the active hydrogen containing compound is optionally dissolved in water and/or a water soluble organic solvent to obtain the coloring composition. The concentration of the composition is from 15 to 25 percent by weight in terms of amount of the dye. 
     In case that the obtained coloring composition indicates acidic, the pH can be adjusted with ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide, or an alkanolamine. 
     The coloring composition of the present invention has excellent stability with time and within the extended pH range. The extension of ph range is 2 to 3 in pH in comparison with a conventional one using the same dye. A dye which could be used only in a strong acid range or a strong basic range in a conventional type composition is made usable in a neutral range. 
     A process for preparing an ink composition from the obtained coloring composition can comprise mixing distilled water with 15 to 60 parts of the coloring agent and 15 to 30 parts of the water soluble organic solvent to obtain 100 parts of a mixture, optionally followed by filtrating. The resultant mixture, i.e. the ink composition can be formulated with another conventional additive such as a surfactant, an anti-corrosive agent and a mildewcide. 
     The ink composition prevents effectively corrosion and a plugging of a capillary passageway and has an excellent water-resistance of a written trace or a printed image. 
     The present invention is illustrated by the following examples, which, however, are not construed as limiting the present invention. In the examples, all parts and percentages are by weight unless otherwise specified. 
    
    
     EXAMPLE 1 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
Free acid type   100                                                      
C.I. Acid Red 87                                                          
4-vinylpyridine  68                                                       
Thiourea          8                                                       
N--methylpyrrolidone                                                      
                 50                                                       
______________________________________                                    
 
    
     The above ingredients were charged in a four-necked 500 ml flask equipped with a stirrer, a thermometer and a condenser and mixed for 1 to 2 hours at room temperature. The mixture was heated gradually and then it was held at 90° to 100° C. for one hour. The mixture was, furthermore, held at 60° C. for 2 hours. 
     To the resultant reaction product was added warm water of 200 parts and then the pH was adjusted to 8 to 9 with sodium hydroxide, followed by filtrating. To the reaction product was added water to obtain the coloring composition containing 20 percent by weight of C.I. Acid Red 87. 
     EXAMPLE 2 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients        Parts by weight                                        
______________________________________                                    
C.I. Acid Yellow 11                                                       
                   100                                                    
N--vinylmonoethyleneurea                                                  
                   73                                                     
m-phenylenediamine 10                                                     
Ethylene glycol    50                                                     
______________________________________                                    
 
    
     The above ingredients were charged in the reaction vessel used in Example 1 and mixed for one hour at room temperature. After hydrochloric acid of 10 parts was added into the resultant mixture, it was mixed for one hour and then heated as described in Example 1. 
     To the resultant reaction product was added warm water and then the pH was adjusted to 8 to 9 with lithium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 3 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients        Parts by weight                                        
______________________________________                                    
C.I. Acid Black 2  100                                                    
2-hydroxyethyl methacrylate                                               
                   85                                                     
Benzoguanamine     10                                                     
2-pyrrolidone      50                                                     
______________________________________                                    
 
    
     The above ingredients were charged in the reaction vessel used in Example 1 and mixed for one hour at room temperature. After azobisisobutyronitrile of 3 parts was added to the mixture, the reaction was conducted at a temperature of 90° to 100° C. for 5 hours. 
     To the resultant reaction product was added warm water and then the pH was adjusted to 9 to 10 with sodium hydroxyde to obtain a coloring composition containing 25 percent by weight of the dye. 
     EXAMPLE 4 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
Free acid type   100                                                      
C.I. Direct Black 154                                                     
N--vinylpyrrolidone                                                       
                 72                                                       
p-aminophenol    10                                                       
diethylene glycol                                                         
                 60                                                       
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 1 and then the pH was adjusted to 10 to 10.5 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 5 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients       Parts by weight                                         
______________________________________                                    
Color acid type   100                                                     
C.I. Acid Black 52                                                        
4-vinylpyridine   34                                                      
Acrylamide        23                                                      
Guanidine hydrochloride                                                   
                  10                                                      
N--methylpyrrolidone                                                      
                  50                                                      
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 1 and then the pH was adjusted to 7 to 8 with sodium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 6 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients       Parts by weight                                         
______________________________________                                    
C.I. Basic Violet 3                                                       
                  100                                                     
2-hydroxyethyl acrylate                                                   
                  75                                                      
Melamine          10                                                      
Methylene glycol  50                                                      
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 1 and then the pH was adjusted to 3 to 4 with ammonia to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 7 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients        Parts by weight                                        
______________________________________                                    
Free acid type     100                                                    
C.I. Direct Blue 86                                                       
4-vinylpyridine    68                                                     
2-aminophenol-4-sulfonamide                                               
                   15                                                     
N--methylpyrrolidone                                                      
                   50                                                     
p-toluensulfonic acid                                                     
                    2                                                     
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 9 to 10 with sodium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 8 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients        Parts by weight                                        
______________________________________                                    
C.I. Acid Blue 90  100                                                    
2-hydroxyethyl methacrylate                                               
                   37                                                     
N--vinylpyrrolidone                                                       
                   36                                                     
Tolylene-2,4-diamine                                                      
                   10                                                     
Ethylene glycol    70                                                     
Sulfuric acid       1                                                     
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 6 to 7 with sodium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 9 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Blue 25                                                         
                 100                                                      
Styrenesulfonic acid                                                      
                 46                                                       
o-tolidine        5                                                       
Diethylene glycol                                                         
                 60                                                       
Azobisisobutyronitrile                                                    
                  2                                                       
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 3 and then the pH was adjusted to 8 to 9 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 10 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients       Parts by weight                                         
______________________________________                                    
Free acid type    100                                                     
C.I. Acid Red 37                                                          
2-hydroxyethyl acrylate                                                   
                  85                                                      
5,5&#39;-dimethylhydantoine                                                   
                  10                                                      
Diethylene glycol 60                                                      
Sulfuric acid      1                                                      
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 7 to 8 with lithium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 11 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
Free acid type   100                                                      
C.I. Acid Black 41                                                        
N--vinylpyrrolidone                                                       
                 72                                                       
m-phenylenediamine                                                        
                 10                                                       
2-pyrrolidone    50                                                       
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 1 and then the pH was adjusted to 8 to 9 with sodium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 12 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
Free acid type   100                                                      
C.I. Acid Yellow 42                                                       
N--vinylpyrrole  75                                                       
Tolylene-2,4-diamine                                                      
                 10                                                       
N--methylpyrrolidone                                                      
                 50                                                       
p-toluenesulfonic acid                                                    
                  2                                                       
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 9 to 10 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 13 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
Free acid type  100                                                       
C.I. Acid Blue 45                                                         
N--vinylsuccinimide                                                       
                85                                                        
Melamine        10                                                        
Ethylene glycol 50                                                        
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 1 and then the pH was adjusted to 8 to 9 with sodium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 14 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients        Parts by weight                                        
______________________________________                                    
C.I. Basic Green 4 100                                                    
N--vinylpyrrolidone                                                       
                   37                                                     
2-hydroxyethyl methacrylate                                               
                   36                                                     
Benzoguanamine     10                                                     
Propylene glycol   70                                                     
Sulfuric acid       1                                                     
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 3 to 4 with ammonia to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 15 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients        Parts by weight                                        
______________________________________                                    
C.I. Acid Violet 41                                                       
                   100                                                    
Acrylamide         30                                                     
N--vinylmonoethyleneurea                                                  
                   45                                                     
o-tolydine          8                                                     
N--methylpyrrolidone                                                      
                   60                                                     
Butyl/peroxide      3                                                     
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 3 and then the pH was adjusted to 9 to 10 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 16 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
Color acid type 100                                                       
C.I. Acid Red 180                                                         
N--vinylpyrrole 75                                                        
Diphenylguanidine                                                         
                 8                                                        
Ethylene glycol 60                                                        
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 1 and then the pH was adjusted to 7 to 8 with ammonia to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 17 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Blue 1                                                          
                100                                                       
Acrylic acid    85                                                        
p-phenylenediamine                                                        
                10                                                        
2-pyrrolidone   60                                                        
Hydrochloric acid                                                         
                 1                                                        
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 6 to 7 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 18 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
Free acid type   100                                                      
C.I. Acid Yellow 17                                                       
Methyl acrylate  85                                                       
p-aminophenol    10                                                       
N--methylpyrrolidone                                                      
                 50                                                       
Hydrochloric acid                                                         
                  3                                                       
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 9 to 10 with lithium hydroxide to obtain a coloring composition containing 20 percent by weight of the dye. 
     EXAMPLE 19 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients         Parts by weight                                       
______________________________________                                    
C.I. Acid Black 51  100                                                   
Acrylamide          35                                                    
N--vinylpyrrolidone 50                                                    
2-phenyl-4,5-dihydroxyimidazole                                           
                    10                                                    
2-pyrrolidone       50                                                    
Azobisisobutyronitrile                                                    
                     3                                                    
______________________________________                                    
 
    
     The above ingredients were reacted at a temperature of 60° to 70° C. for 10 hours and treated generally as described in Example 3 and the pH was adjusted to 7 to 8 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     EXAMPLE 20 
     A coloring composition was prepared from the following formulation: 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
Free acid type   100                                                      
C.I. Direct Black 17                                                      
2-vinylpyridine  85                                                       
Thiourea         10                                                       
Diethylene glycol                                                         
                 50                                                       
Benzenesulfonic acid                                                      
                  2                                                       
______________________________________                                    
 
    
     The above ingredients were reacted and treated generally as described in Example 2 and then the pH was adjusted to 9 to 10 with sodium hydroxide to obtain a coloring composition containing 15 percent by weight of the dye. 
     COMPARATIVE EXAMPLE 
     For the purpose of comparison, concentrated solutions of water-soluble dyes were prepared from the following formulations by mixing and optionally filtrating. 
     COMPARATIVE EXAMPLE 1 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Red 87 20                                                       
N--methylpyrrolidone                                                      
                 25                                                       
Distilled water  55                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 2 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Yellow 11                                                       
                15                                                        
Ethylene glycol 20                                                        
Distilled water 65                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 3 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Black 2                                                         
                25                                                        
2-pyrrolidone   13                                                        
Diethylene glycol                                                         
                23                                                        
Distilled water 39                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 4 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Direct Black 154                                                     
                 15                                                       
N--methylpyrrolidone                                                      
                 10                                                       
Diethylene glycol                                                         
                 11                                                       
Distilled water  64                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 5 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Black 52                                                        
                 20                                                       
N--methylpyrrolidone                                                      
                 17                                                       
Ethylene glycol   6                                                       
Distilled water  57                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 6 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Basic Violet 3                                                       
                20                                                        
Diethylene glycol                                                         
                15                                                        
Ethylene glycol 12                                                        
Distilled water 53                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 7 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Direct Blue 86                                                       
                20                                                        
2-methylpyrrolidone                                                       
                24                                                        
Distilled water 56                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 8 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Blue 90                                                         
                 20                                                       
N--methylpyrrolidone                                                      
                  7                                                       
Diethylene glycol                                                         
                  7                                                       
Ethylene glycol  16                                                       
Distilled water 50                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 9 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Blue 25                                                         
                15                                                        
Diethylene glycol                                                         
                10                                                        
Distilled water 75                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 10 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Red 37                                                          
                20                                                        
Diethylene glycol                                                         
                30                                                        
Distilled water 50                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 11 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Black 41                                                        
                20                                                        
2-pyrrolidone   25                                                        
Distilled water 55                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 12 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Yellow 42                                                       
                 15                                                       
N--methylpyrrolidone                                                      
                 20                                                       
Distilled water  55                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 13 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Blue 45                                                         
                20                                                        
Ethylene glycol 20                                                        
Distilled water 60                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 14 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Basic Green 4                                                        
                 20                                                       
N--methylpyrrolidone                                                      
                  8                                                       
Propylene glycol 20                                                       
Distilled water  52                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 15 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Violet 41                                                       
                 15                                                       
N--methylpyrrolidone                                                      
                 15                                                       
Diethylene glycol                                                         
                  5                                                       
Distilled water  65                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 16 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Red 180                                                         
                 15                                                       
N--methylpyrrolidone                                                      
                 11                                                       
Ethylene glycol   9                                                       
Distilled water  65                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 17 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Blue 1                                                          
                15                                                        
2-pyrrolidone   10                                                        
Diethylene glycol                                                         
                13                                                        
Distilled water 62                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 18 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Acid Yellow 17                                                       
                 20                                                       
N--methylpyrrolidone                                                      
                  8                                                       
Diethylene glycol                                                         
                 12                                                       
Distilled water  60                                                       
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 19 
     
         ______________________________________                                    
Ingredients     Parts by weight                                           
______________________________________                                    
C.I. Acid Black 51                                                        
                15                                                        
2-pyrrolidone   15                                                        
Diethylene glycol                                                         
                 5                                                        
Distilled water 65                                                        
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 20 
     
         ______________________________________                                    
Ingredients      Parts by weight                                          
______________________________________                                    
C.I. Direct Black 17                                                      
                 15                                                       
N--methylpyrrolidone                                                      
                 13                                                       
Diethylene glycol                                                         
                  7                                                       
Distilled water  65                                                       
______________________________________                                    
 
    
     EXAMPLE A 
     The resultant coloring compositions according to the above examples and the comparative examples were subjected to a hue test and a stability test. Solution stability was determined by a stability after test by leaving the solution to stand for 3 months at room temperature. pH stability was recorded by a stability range of pH of the solution formed from diluting the composition with distilled water to dissolve completely. The result of the tests is shown in Table 1. 
     
                                           TABLE 1                                 
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Example               Comparative Example                                 
          stability      stability                                        
No.                                                                       
   Hue    solution                                                        
               pH     No.                                                 
                         solution         pH                              
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 1 clear  good more than 4                                                
                       1 good             more than 6                     
 2 same   &#34;    more than 5                                                
                       2 not complete dissolution                         
                                      (3%)                                
                                          more than 8                     
 3 &#34;      &#34;    more than 4                                                
                       3 &#34;            (15%)                               
                                          more than 8                     
 4 &#34;      &#34;    more than 6                                                
                       4 precipitate after one month                      
                                          more than 8                     
 5 &#34;      &#34;    more than 3                                                
                       5 not complete dissolution                         
                                      (15%)                               
                                          more than 5                     
 6 slightly dull                                                          
          &#34;    less than 7                                                
                       6 &#34;            (10%)                               
                                          less than 2                     
 7 &#34;      &#34;    more than 4                                                
                       7 &#34;            (10%)                               
                                          more than 6                     
 8 &#34;      &#34;    less than 7                                                
                       8 &#34;            (15%)                               
                                          less than 5                     
 9 same   &#34;    more than 5                                                
                       9 &#34;            (3%)                                
                                          more than 5                     
10 clear  &#34;    more than 4                                                
                      10 &#34;            (15%)                               
                                          more than 7                     
11 slightly dull                                                          
          &#34;    more than 6                                                
                      11 &#34;            (15%)                               
                                          more than 8                     
12 clear  &#34;    more than 4                                                
                      12 &#34;            (10%)                               
                                          more than 8                     
13 &#34;      &#34;    more than 6                                                
                      13 &#34;            (8%)                                
                                          more than 8                     
14 slightly dull                                                          
          &#34;    less than 6                                                
                      14 complete dissolution                             
                                          less than 5                     
15 &#34;      &#34;    more than 6                                                
                      15 not complete dissolution                         
                                      (5%)                                
                                          more than 9                     
16 clear  &#34;    more than 5                                                
                      16 &#34;            (10%)                               
                                          more than 8                     
17 slightly dull                                                          
          &#34;    less than 8                                                
                      17 complete dissolution                             
                                          less than 7                     
18 clear  &#34;    more than 4                                                
                      18 &#34;                more than 8                     
19 &#34;      &#34;    more than 6                                                
                      19 not complete dissolution                         
                                      (10%)                               
                                          more than 8                     
20 &#34;      &#34;    more than 6                                                
                      20 &#34;            (10%)                               
                                          more than 9                     
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     EXAMPLE B [Water resistance test] 
     An aqueous ink was prepared by the following formulation using the above coloring composition of the present invention or the concentrated solution of the comparative examples. 
     
         ______________________________________                                    
Ingredients         Parts by weight                                       
______________________________________                                    
The coloring composition                                                  
                    15 to 60                                              
(or the concentrated solution)                                            
Ethylene glycol     10                                                    
Diethylene glycol   10                                                    
Distilled water     All the rest                                          
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     The obtained aqueous ink was charged in a felt tip pen container to write down continuously with a writing machine. The written trace was dipped in distilled water for one minute after 30 minutes from writing down at the start and pulled up and dried up to evaluate the written trace. The result is shown in Table 2. 
     
                       TABLE 2                                                     
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Coloring         Evaluation                                               
       composition            Comparative                                 
No.    (parts)       Example  Example                                     
______________________________________                                    
 1     40            4        1                                           
 2     25            2        0                                           
 3     40            2        0                                           
 4     60            5        1                                           
 5     50            3        0                                           
 6     15            4        2                                           
 7     30            2        0                                           
 8     30            5        2                                           
 9     40            4        2                                           
10     40            2        0                                           
11     50            4        1                                           
12     40            3        1                                           
13     30            3        0                                           
14     20            3        0                                           
15     40            4        1                                           
16     50            3        1                                           
17     40            2        0                                           
18     25            2        0                                           
19     60            3        0                                           
20     60            4        2                                           
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 [Evaluation                                                              
 5: The written trace remains within the range of 100 to 90%.             
 4: The written trace remains within the range of 90 to 70%.              
 3: The written trace remains within the range of 70 to 50%.              
 2: The written trace remains within the range of 50 to 30%.              
 1: The written trace remains within the range of 30 to 10%.              
 0: The written trace remains within the range of 10 to 0%.