Patent Publication Number: US-4317682-A

Title: Pigment compositions and use thereof

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to pigment compositions which have excellent properties for various applications, particularly with regard to non-flocculation and non-crystallization, and to use of such pigment compositions. 
     2. The Prior Art 
     In general, useful pigments which exhibit clear colour tone and high tinting strength in various coating compositions consist of fine particles. However, when fine particles of pigment are dispersed in non-aqueous vehicles such as offset printing inks, gravure printing inks and paints, it is difficult to obtain stable dispersions and various problems arise which have a serious influence on the preparation, and also on the value, of the resulting product. For instance dispersions which contain pigments consisting of fine particles are often highly viscous and thus not only is it difficult to withdraw the dispersion product from a dispersing machine and transport it but also, in a worse case, it cannot be used due to gellation during storage. Further, when pigments of different types are mixed, undesirable phenomena such as colour separation by flocculation and precipitation can take place and may cause the dispersion system to be uneven in colour and may also considerably lower the tinting strength. There may also arise problems such as lowering of gloss, an inferiority of levelling and the like in films made from the dispersion system. 
     In addition to the problem of dispersion of the pigment, some organic pigments undergo a phenomenon involving a change in the crystal structure of the pigment. That is, crystal particles of a pigment which are unstable (from an energy viewpoint) change their sizes and form into a more stable state in a non-aqueous vehicle such as is used for offset printing ink, gravure printing ink and paint and may thus damage the commercial value of the dispersion system, due to a remarkable change in colour tone, reduction of tinting strength and formation of coarse particles. 
     In order to improve the anti-flocculation and crystal stability of pigments as mentioned above, heretofore there have been proposed a number of pigments including copper phthalocyanine pigments and quinacridone pigments. 
     The prior attempts may be broadly classified from a technical point of view into the following categories. One approach includes coating the surfaces of pigment particles with colourless compounds such as silicon oxide, aluminum oxide and tert-butyl benzoate as disclosed in U.S. Pat. Nos. 3,370,971 and 2,965,511. The second class includes, as typically described in Japanese Patent Publication No. 41-2466, U.S. Pat. Nos. 4,088,507 and 2,761,865, processes of admixing pigments with compounds which are obtained by introducing onto the organic pigment, as a matrix skeleton, substituents (on side chains) such as a sulphonyl group, a sulfonamide group, an aminomethyl group, a phthalimidemethyl group and the like. 
     The processes of the second class are better than those of the first class in that the second class of processes provide better non-flocculation and crystal stability and ensure easy preparation of pigment compositions. 
     However, the second class of processes have a disadvantage, in that, because the added compound is derived from a compound of the same chemical structure as an intended pigment and thus possesses an inherent intense colour, its application is severely restricted when such a compound is used in combination with a pigment whose tone colour is different from the compound. Accordingly, compounds corresponding to individual pigments must be provided, which is very disadvantageous in preparing pigment compositions. 
     In order to overcome the above disadvantage of the second class of processes, there has been proposed (in Japanese Laid-open Publication No. 54-17932) a pigment composition, as a third class, in which colourless or slightly coloured aromatic compounds, which are obtained by incorporating aliphatic hydrocarbon chains having more than 5 atoms into aromatic compounds having at least 9 atoms which constitute a ring, are added to pigments. However, investigations made by the present inventors have revealed that this pigment composition did not show a satisfactory effect when non-aqueous vehicles, and particularly aromatic solvents such as xylene, toluene and the like, are used. 
     The inventors of the present invention have made an intensive study of methodologies to inhibit flocculation and to improve the crystal stability of pigments. As a result, it has been found that substantially colourless aromatic compounds which have a substituent of a specific type are effective for the intended purpose when used in combination with pigments. 
     According to the present invention, there is provided a pigment composition comprising 100 parts by weight of a pigment and from 0.3 to 30 parts by weight of a colourless or slightly coloured aromatic compound having the following general formula (I) ##STR4## wherein Q represents a residue of an aromatic polycyclic compound which is joined directly or through A to --SO 2  --, A represents a member selected from the group consisting of --O--, ##STR5## --S--, --CO--, --SO 2  --, ##STR6## a divalent phenylene residue or a combination thereof, in which R 4  and R 5  represent, independently, a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, R 1  and R 2  represent, independently, a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, or together form a heterocyclic ring together with N* in the formula (I), R 3  represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, m is a integer of from 1 to 6 and n is an integer of from 1 to 3. 
     The residues of the aromatic polycyclic compounds represented by Q in the general formula (I) include, for example, those of naphthalene, anthracene, phenanthrene, pyrene, chrysene, indole, thiazole, benzimidazole, quinoline, acridone, anthraquinone, phenothiazine, quinazoline, carbazole, benzanthrone and perylene. Q may also include other substituents such as --R 6 , --OR 6 , ##STR7## --COOR 6 , --NHCOR 6 , ##STR8## --NR 6  --CO--R 7 , --NO 2 , --CN, --CF 3  and --SO 3  M, in which R 6  and R 7  represent, independently, a hydrogen atom, a saturated or unsaturated alkyl group containing from 1 to 20 carbon atoms or an aryl group and M represents one equivalent of a mono- to trivalent cation. 
     A of the general formula (I) represents such divalent groups as defined hereinabove or a combination thereof, but Q may be bonded to --SO 2  -- radical of the compound (I) directly, not through A. Combined divalent groups may be combinations of three or more groups such as ##STR9## 
     The preparation of the compounds represented by the general formula (I) is not specifically limited. For instance, some of the compounds may be easily obtained by reacting compounds of the following general formula (II) with compounds of the following general formula (III): ##STR10## (in which Q, A, R 1 , R 2 , R 3 , m and n have the same meanings as defined in the formula (I), and X represents a halogen atom). 
     The compounds of the general formula (I) have a basic group and thus show a strong affinity for the anionic moiety, for example a carboxyl group, of the resin component ordinarily contained in vehicles, which is a reason why the compound improves the dispersability of pigment in many applications. 
     Examples of pigment useful in the present invention include organic pigments, such as insoluble azo pigments, condensation azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolenone pigments, perylene pigments, perynone pigments, dioxazine pigments, lake pigments, vat dye pigments and basic dye pigments, and inorganic pigments such as carbon black, titanium oxide, chrome yellow, cadmium yellow, cadmium red, red iron oxide, iron black, zinc flower, Prussian blue and ultramarine. 
     The compounds of the general formula (I) used in the present invention are preferred to be used in an amount in the range of from 0.5 to 30 parts by weight per 100 parts by weight of the pigment. Amounts less than 0.5 parts by weight may not satisfactorily attain the aforementioned advantages, whereas amounts larger than 30  parts by weight may be usable but no increased effect can be expected. 
     Although the pigment composition according to the present invention may be prepared by merely mixing a powder of a pigment with a powder of the compound represented by the general formula (I), good results can also be obtained by mechanically mixing them in kneaders, rollers, attritor, super mills or various types of powdering or milling machines, by adding a solution containing the compound of the general formula (I) to a suspension system of a pigment in water or an organic solvent, thereby permitting the compound of the general formula (I) to deposit on the surface of the pigment, or by dissolving both an organic pigment and the compound of the general formula (I) in a solvent having strong dissolving power, such as sulphuric acid, and then co-precipitating them with use of a poor solvent, such as water. 
     When the thus-obtained pigment composition is used as a colourant for polyolefins, polyesters and various vinyl resins and as offset printing ink vehicles, such as for various resin-modified resins, and is used to prepare gravure printing inks, such as with lime rosin varnishes, polyamide resin varnishes and vinyl chloride resin varnishes, or is used to prepare nitrocellulose lacquers, room temperature drying or baking paints, urethane resin paints and the like, it serves to lower the viscosity of the dispersant and reduce the structural viscosity of the dispersion system and thus shows good fluidity as compared with a pigment used alone. In addition, the pigment composition according to the invention normally presents no problems such as colour separation or changes in crystalinity and imparts good colour tone and gloss to printed matter, mouldings or films. 
    
    
     In the following Preparatory Examples, there are described general procedures of preparing typical compounds represented by the general formula (I). 
     PREPARATORY EXAMPLE 1 
     β-hydroxynaphthoic acid was reacted with an equimolar amount of thionyl chloride in benzene by heating under reflux for 1 hour while agitating to give a chloride. After completion of the reaction, amines were each added to such a reaction system, followed by further heating under reflux and agitation for 1 hour to obtain compounds of the following formulae: ##STR11## 
     PREPARATORY EXAMPLE 2 
     2,6-naphthalenedicarboxylic acid was reacted with thionyl chloride in benzene in a molar ratio of 2:1 thionyl chloride to acid while heating and agitating the system under reflux for 1 hour to prepare a chloride. After completion of the reaction, amines were each added to the reaction system to obtain compounds of the following formulae: ##STR12## 
     PREPARATORY EXAMPLE 3 
     2&#39;-hydroxy-3&#39;-naphthoic acid-2,5-dimethoxy-4-chloroanilide was sulfonated in 98% 10 times its weight of sulfuric acid while agitating the system at below 20° C. for 1 hour. The resulting sulfonate was found to contain 1.2 sulfornate groups per molecule. 
     When the sulfornation reaction was conducted at 40° C. for 1 hour, there was obtained a compound containing 2.1 sulfonate groups per molecule. The thus obtained sulfonates were each reacted with thionyl chloride in the same manner as in Preparatory Example 1 for chlorination, followed by reacting with amines to obtain compounds of the following formulae: ##STR13## 
     PREPARATORY EXAMPLE 4 
     2,6-dimethyl-3-hydroxyquinoline-4-carboxylic acid was chlorinated with thionyl chloride in the same manner as in Preparatory Example 1 and then reacted with an amine to obtain a compound of the following formula: ##STR14## 
     PREPARATORY EXAMPLE 5 
     Phenothiazine was reacted with an equimolar amount of 98% sulfuric acid in 10 times its weight of dioxane to obtain phenothiazinesulfonic acid. This phenothiazinesulfonic acid was found to contain 0.9 sulfonic acid groups per molecule. The thus obtained sulfonic acid was chlorinated with thionyl chloride in the same manner as in Preparatory Example 1 and then reacted with amines to obtain compounds of the following formulae: ##STR15## 
     PREPARATORY EXAMPLE 6 
     2-Acetylamino-6-carboxybenzothiazole was treated in the same manner as in Preparatory Example 1 to obtain a chloride, followed by reacting with amines to obtain compounds of the following formulae: ##STR16## 
     PREPARATORY EXAMPLE 7 
     3-phenyl-5-nitroindole-2-carboxylic acid was chlorinated in the same manner as in Preparatory Example 1 and then reacted with amines to obtain compounds of the following formulae: ##STR17## 
     PREPARATORY EXAMPLE 8 
     1 mole of acridone was reacted with 1.5 mole of chlorosulfonic acid in concentrated sulfuric acid in an amount 10 times the weight of the acridone at 80°-90° C. for 1 hour to obtain acridonechlorosulfonic acid. This product was found to contain 1.2 chlorosulfone groups per molecule of acridone. Similarly, acridone was reacted with chlorosulfonic acid in a molar ratio of 1:2.5 to obtain a compound having 1.8 chlorosulfone groups per molecule of acridone. The thus obtained acridonechlorosulfonic acid was reacted with amines to obtain compounds of the following formulae: ##STR18## 
     PREPARATORY EXAMPLE 9 
     Anthraquinone-2-carboxylic acid was chlorinated in the same manner as in Preparatory Example 1 to give the carboxylic acid chloride and then reacted with amines to obtain compounds of the following formulae: ##STR19## 
     PREPARATORY EXAMPLE 10 
     Acenaphthene-5-sulfornic acid was chlorinated in the same manner as in Preparatory Example 1 and then reacted with an amine to obtain a compound of the following formula: ##STR20## 
     PREPARATORY EXAMPLE 11 
     10-hydroxy-3,5,8-pyrenetrisulfonic acid was chlorinated in the same manner as in Preparatory Example 1 and then reacted with an amine to obtain a compound of the following formula: ##STR21## 
     The following Examples and Comparative Examples further illustrate the present invention. Compound Numbers in the Tables refer to the Preparatory Examples. 
     COMPARATIVE EXAMPLES AND EXAMPLES 1 TO 10 
     Gravure Printing Ink Test 
     To a vinyl chloride resin varnish for gravure printing were added various types of pigments used singly (Comparative Example) and in admixture with the compounds obtained in Preparatory Examples 1 to 11 in such a way that the content of each pigment was 10% or 25% (when inorganic pigments were used), thereby producing gravure printing inks. The viscosity of these inks was measured. The results are shown in Table 1, from which it is apparent that the pigment composition of the present invention have excellent fluidity. 
     Further, it was found that the gravure printing inks using the pigment compositions of the invention were excellent as regards clearness of colour tone of printed matter, tinting strength and gloss. 
     
                       TABLE 1                                                     
______________________________________                                    
Viscosity of Gravure Printing Inks                                        
(B.M. type rotary viscometer)                                             
                              Viscosity                                   
                              Viscosity (CPS)                             
                              Number of                                   
Ex-             Com-          revolutions                                 
ample           pound   Mixing                                            
                              of rotor                                    
No.   Pigment   No.     ratio 6    12   30   60                           
______________________________________                                    
      C.I. pig  --      --    3720 1630 920  710                          
      Yellow 14                                                           
1     C.I. pig  XII-1   90:10 1060 720  650  590                          
      Yellow 14                                                           
2     C.I. pig  IX-1    95:5  1020 700  630  580                          
      Yellow 14                                                           
3     C.I. pig  III-1   &#34;     1100 750  670  590                          
      Yellow 14                                                           
4     C.I. pig  VI-1    85:15 1240 920  710  630                          
      Yellow 14                                                           
      C.I. pig  --      --    5400 2810 1780 1000                         
      Red 17                                                              
5     C.I. pig  IX-2    95:5  2870 1530 870  770                          
      Red 17                                                              
6     C.I. pig  VI-2    85:15 3180 1750 980  820                          
      Red 17                                                              
      *C.I. pig --      --    850  600  540  500                          
      Yellow 34                                                           
7     *C.I. pig III-2   95:5  610  470  390  370                          
      Yellow 34                                                           
8     *C.I. pig II-1    90:10 620  490  400  390                          
      Yellow 34                                                           
      *C.I. pig --      --    770  580  520  500                          
      White 6                                                             
9     *C.I. pig X-1     95:5  570  450  420  390                          
      White 6                                                             
10    *C.I. pig XI-1    90:10 580  460  420  390                          
      White 6                                                             
______________________________________                                    
 *Inorganic pigments. The content of pigment in gravure printing ink is   
 percent by weight.                                                       
 
    
     EXAMPLES 11 TO 29 
     To an aminoalkyd resin varnish for baking paint were added various pigments singly (Comparative Examples) and in admixture with the compounds obtained in Preparatory Examples 1 to 11 in such a way that the content of pigment was 6% or 25% (when an inorganic pigment was used), thereby preparing paints. The viscosities of the paints were measured. The results are shown in Table 2. 
     The aminoalkyd paints of Examples 11 to 21 in accordance with the invention were found to have excellent fluidity and stability of crystals and films obtained from such paints were also excellent in clearness of colour, tinting strength and gloss. As for storage stability, they did not show any tendency to increase in viscosity and were thus excellent in this respect. 
     
                       TABLE 2                                                     
______________________________________                                    
Viscosity of Aminoalkyd Resin Baking Paints                               
(B.M. Type Rotary Viscometer)                                             
                              Viscosity                                   
                              Viscosity (CPS)                             
                              Number of                                   
Ex-             Com-          revolutions                                 
ample           pound   Mixing                                            
                              of rotor                                    
No.   Pigment   No.     ratio 6     12   30   60                          
______________________________________                                    
      C.I. pig  --      --    8500  6000 3500 2540                        
      Blue 15                                                             
11    C.I. pig  IX-1    95:5  1910  1280 970  920                         
      Blue 15                                                             
12    C.I. pig  III-1   &#34;     2190  1400 1250 980                         
      Blue 15                                                             
13    C.I. pig  II-1    90:10 2050  1370 1110 1010                        
      Blue 15                                                             
14    C.I. pig  IV-1    &#34;     2120  1380 1190 1030                        
      Blue 15                                                             
      C.I. pig  --      --    7900  4520 2100 1200                        
      Violet 19                                                           
15    C.I. pig  IX-2    95:5  4750  2870 1410 960                         
      Violet 19                                                           
16    C.I. pig  III-2   &#34;     4830  2940 1510 1000                        
      Violet 19                                                           
17    C.I. pig  XIV-1   90:10 4580  2620 1320 950                         
      Violet 19                                                           
18    C.I. pig  IV-2    &#34;     4980  3010 1600 1080                        
      Violet 19                                                           
      C.I. pig  --      --    11500 6830 4520 3600                        
      Red 168                                                             
19    C.I. pig  VII-2   90:10 6570  4810 3130 2490                        
      Red 168                                                             
      C.I. pig  --      --    9280  6310 4100 2680                        
      Yellow 108                                                          
20    C.I. pig  X-1     90:10 5220  3760 3100 2750                        
      Yellow 108                                                          
21    C.I. pig  II-1    &#34;     5640  3910 3330 2880                        
      Yellow 108                                                          
22    C.I. pig  VII-1   85:15 5100  3690 2900 2650                        
      Yellow 108                                                          
23    C.I. pig  XI-1    &#34;     5290  3810 3210 2770                        
      Yellow 108                                                          
      C.I. pig  --      --    12600 7100 4320 3730                        
      Black 6                                                             
24    C.I. pig  X-2     90:10 8590  5610 3620 2760                        
      Black 6                                                             
25    C.I. pig  VIII-1  80:20 7930  5130 3560 2620                        
      Black 6                                                             
26    C.I. pig  VII-2   &#34;     8290  5240 3310 2560                        
      Black 6                                                             
      C.I. pig  --      --    780   630  590  570                         
      Red 101                                                             
27    C.I. pig  V-2     95:5  630   520  480  460                         
      Red 101                                                             
28    C.I. pig  VII-2   &#34;     680   570  520  490                         
      Red 101                                                             
29    C.I. pig  VI-2    90:10 690   590  560  540                         
      Red 101                                                             
______________________________________                                    
 
    
     To test the dispersion stability of the paints, several paints were subjected to a flocculation test, in order to judge their susceptibility to colour separation which must be below a certain level for practical applications. That is, the paints listed in Table 3 below were each made using a base paint of titanium oxide, which had been previously prepared using an aminoalkyd resin varnish, so that the mixing ratio of pigment to titanium oxide was 1/10, thereby providing light-coloured paints. 
     Each light-coloured paint was further diluted with xylene and adjusted to have a viscosity of 20 seconds (25° C.) when measured by the Ford Cup No. 4, followed by charging it along a test tube to observe the flowing state of the charged paint running along the wall surface of the glass tube. The results are shown in Table 3 below. 
     
                       TABLE 3                                                     
______________________________________                                    
                                Just 1 day 1 week                         
                                after                                     
                                     after after                          
Exam-            Com-           prep-                                     
                                     prep- prep-                          
ple              pound    Mixing                                          
                                ara- ara-  ara-                           
No.   Pigment    No.      Ratio tion tion  tion                           
______________________________________                                    
(Com- C.I. Pigment                                                        
                 --       --    Δ                                   
                                     x     x                              
para- Blue 15                                                             
tive                                                                      
Exam-                                                                     
ple)                                                                      
11    C.I. Pigment                                                        
                 IX-1     95:5  ⊚                          
                                     ⊚                     
                                           ⊚               
      Blue 15                                                             
(Com- C.I. Pigment                                                        
                 --       --    ○                                  
                                     Δ                              
                                           x                              
para- Violet 19                                                           
tive                                                                      
Exam-                                                                     
ple)                                                                      
17    C.I. Pigment                                                        
                 XII-1    90:10 ⊚                          
                                     ⊚                     
                                           ⊚               
      Violet 19                                                           
(Com- C.I. Pigment                                                        
                 --       --    ○                                  
                                     ○                             
                                           Δ                        
para- Red 168                                                             
tive-                                                                     
Exam-                                                                     
ple)                                                                      
19    C.I. Pigment                                                        
                 VII-2    90:10 ⊚                          
                                     ⊚                     
                                           ⊚               
      Red 168                                                             
______________________________________                                    
 Evaluation:                                                              
 ⊚ Completely uniform.                                     
  ○ White streaks appear in a slight degree.                       
 Δ A white stripepattern appears.                                   
 x White substance is completely separate.                                
 
    
     From the above, it will be seen that the pigment compositions according to the invention are excellent with respect to colour separation tendency. 
     EXAMPLES 30 TO 41 
     To a nitrocellulose lacquer were added pigments singly and as compositions of the present invention with the mixing ratios indicated in Table 4 so that the content of pigment or pigment composition was 5.5 wt%. The resulting paints had viscosities as indicated in Table 4. 
     Further, it was found that the paints using the pigment compositions of the present invention have excellent flowability and coloured films obtained from such paints were also excellent in gloss, clearness of tone colour and tinting strength. 
     
                       TABLE 4                                                     
______________________________________                                    
Viscosity of Paints Using Nitrocellulose Lacquer                          
(B.M. Type Viscometer)                                                    
                              Viscosity                                   
                              Viscosity (CPS)                             
Ex-                           Number of                                   
am-             Com-          revolutions                                 
ple             pound   Mixing                                            
                              of rotor                                    
No.  Pigment    No.     ratio 6     12   30   60                          
______________________________________                                    
     C.I. Pig   --      --    7500  4350 3100 2930                        
     Blue 15                                                              
30   C.I. Pig   IX-2    95:5  4320  2780 2050 1880                        
     Blue 15                                                              
31   C.I. Pig   III-2   &#34;     4440  2910 2370 2010                        
     Blue 15                                                              
32   C.I. Pig   II-1    90:10 4210  2620 1890 1780                        
     Blue 15                                                              
33   C.I. Pig   IV-2    &#34;     4390  2830 2160 1950                        
     Blue 15                                                              
     C.I. Pig   --      --    8900  6010 5430 4960                        
     Red 123                                                              
34   C.I. Pig   XIII-1  95:5  3520  1950 1380 1020                        
     Red 123                                                              
35   C.I. Pig   VII-2   90:10 3480  1610 1290 1010                        
     Red 123                                                              
     C.I. Pig   --      --    11000 7650 5420 4610                        
     Yellow 12                                                            
36   C.I. Pig   XI-1    95:5  6270  4490 3120 2920                        
     Yellow 12                                                            
37   C.I. Pig   III-1   90:10 5990  4120 2860 2610                        
     Yellow 12                                                            
38   C.I. Pig   II-2    &#34;     6180  4380 3010 2820                        
     Yellow 12                                                            
39   C.I. Pig   IV-1    85:15 5920  4080 2840 2590                        
     Yellow 12                                                            
     C.I. Pig   --      --    11350 7930 5860 5200                        
     Black 6                                                              
40   C.I. Pig   X-2     90:10 8870  6620 5490 5010                        
     Black 6                                                              
41   C.I. Pig   VIII-1  80:20 8790  6530 5380 4980                        
     Black 6                                                              
______________________________________                                    
 
    
     The paints of the Examples indicated in Table 4 were then kept stored for 3 months at 50° C. and then their viscosity was measured with results as shown in Table 5 below. 
     
                                           TABLE 5                                 
__________________________________________________________________________
Viscosity of Paints using Nitrocellulose                                  
Lacquer Immediately after their preparation                               
and 3 months after the preparation.                                       
                       Viscosity                                          
                       Viscosity (CPS)                                    
                       Number of                                          
        Com-                                                              
            Mix-       revolutions                                        
        pound                                                             
            ing Measuring                                                 
                       of rotor                                           
Pigment No. ratio                                                         
                time   6   12  30  60                                     
__________________________________________________________________________
  C.I. Pig                                                                
        --  --  Immediately                                               
                       7500                                               
                           4350                                           
                               3100                                       
                                   2930                                   
  Blue 15       after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        --  --  After  11200                                              
                           7420                                           
                               5150                                       
                                   3210                                   
  Blue 15       3 months                                                  
30                                                                        
  C.I. Pig                                                                
        IX-2                                                              
            95:5                                                          
                Immediately                                               
                       4320                                               
                           2780                                           
                               2050                                       
                                   1880                                   
  Blue 15       after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        &#34;   &#34;   After  4560                                               
                           2870                                           
                               2310                                       
                                   2010                                   
  Blue 15       3 months                                                  
  C.I. Pig                                                                
        --  --  Immediately                                               
                       8900                                               
                           6010                                           
                               5430                                       
                                   4960                                   
  Red 123       after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        --  --  After  12500                                              
                           8320                                           
                               5580                                       
                                   5110                                   
  Red 123       3 months                                                  
34                                                                        
  C.I. Pig                                                                
        XIII-1                                                            
            95:5                                                          
                Immediately                                               
                       3520                                               
                           1950                                           
                               1380                                       
                                   1020                                   
  Red 123       after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        &#34;   &#34;   After  3910                                               
                           2350                                           
                               1620                                       
                                   1270                                   
  Red 123       3 months                                                  
  C.I. Pig                                                                
        --  --  Immediately                                               
                       11000                                              
                           7650                                           
                               5420                                       
                                   4610                                   
  Yellow 12     after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        --  --  After  17100                                              
                           12300                                          
                               8870                                       
                                   7010                                   
  Yellow 12     3 months                                                  
36                                                                        
  C.I. Pig                                                                
        XI-1                                                              
            95:5                                                          
                Immediately                                               
                       6270                                               
                           4490                                           
                               3120                                       
                                   2920                                   
  Yellow 12     after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        &#34;   &#34;   After  6390                                               
                           4560                                           
                               3200                                       
                                   2870                                   
  Yellow 12     3 months                                                  
  C.I. Pig                                                                
        --  --  Immediately                                               
                       11350                                              
                           7930                                           
                               5860                                       
                                   5200                                   
  Black 6       after prepa-                                              
                ration                                                    
  C.I. Pig                                                                
        --  --  After  18130                                              
                           13210                                          
                               9850                                       
                                   7920                                   
  Black 6       3 months                                                  
40                                                                        
  C.I. Pig                                                                
        X-2  90:10                                                        
                Immediately                                               
                       8870                                               
                           6620                                           
                               5490                                       
                                   5010                                   
  Black 6       after pre-                                                
                paration                                                  
  C.I. Pig                                                                
        &#34;   &#34;   After 3                                                   
                       8960                                               
                           6830                                           
                               5590                                       
                                   5160                                   
  Black 6       months                                                    
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     As is clear from the results shown in Table 5, the paints using the pigment compositions of the invention all have excellent storage stability. 
     EXAMPLE 42 AMINOACRYL BAKING PAINT VARNISH 
     An aminoacryl baking paint varnish had incorporated therein C.I. Pigment Orange 36 alone (Comparative Example) and in admixture with Compound V-2 in a mixing ratio of 90:10 so that the pigment and composition were present in an amount of 6 wt%. The resulting paints were compared with respect to their fluidity and it was found that the paint using the pigment composition according to the present invention was much superior to the Comparative Example. 
     The thus-prepared paints were further mixed with an aluminium paint base, which has been previously prepared with an aminoacryl paint varnish, in a mixing ratio of pigment to alumina of 1/5. In this case, the paint according to the invention showed clearer colour tone and a more excellent gloss than the conventional paint. 
     EXAMPLE 43 URETHANE PAINT VARNISH 
     A urethane paint varnish was with C.I. Pigment Yellow 95 alone (Comparative Example) and in admixture with Compound XI-1 in a mixing ratio of 90:10 so that the pigment was contained in an amount of 10% in each case, thereby providing paints. The paints were compared with respect to their flowability and state of coloured film. As a result, it was found that the paint using the pigment composition according to the present invention had excellent fluidity and the coloured film from such paint also had excellent colour tone and gloss.