Abstract:
The present invention provides a trisazo dye represented by the formula: ##STR1## [wherein A is a phenyl group substituted with at least one substituent selected from the group consisting of an amino group, a substituted amino group and a hydroxyl group, B is a substituted or non-substituted phenyl group, X is a group of the formula: ##STR2## Q is a group of the formula: ##STR3## (wherein n is 1 or 2), and M is hydrogen, alkali metal, aliphatic alkyl ammonium or alkanol ammonium]. An aqueous ink composition and a process for the producing a concentrated solution containing the trisazo dye are also disclosed.

Description:
FIELD OF THE INVENTION 
     The present invention relates to a novel trisazo dye. More particularly, it relates to an aqueous ink composition containing the trisazo dye and a process for producing a concentrated solution containing the trisazo dye. 
     BACKGROUND OF THE INVENTION 
     Heretofore, as a writing ink or jet printing ink used for recording on materials to be recorded (e.g. paper, etc.) or an ink for dyeing fibers, hides and the like, various polyazo dyes have been employed. 
     The polyazo dye consists mainly of a direct dye and, therefore, the dyeing process is simple and fastness is comparatively excellent. Polyazo dyes having such advantages are widely employed in the industry. 
     However, regarding the polyazo dye, there are problems to be solved. Firstly, there is a problem as to chemical properties, because excellent chemical properties such as stable solubility of dye, stability of concentrated dye solution with time and stability of dye density with time are required for dyes which are sued for writing inks. 
     Secondly, there is a problem of safety, because safety of chemical substances has recently been noted and dyes having excellent safety and which have no bad influences upon a human body are required. 
     As dyes wherein dyeing properties and fastness are improved, for example, benzidine or benzidine derivative based black trisazo dyes or polyazo dyes (e.g. C.I. Direct Black 19, C.I. Direct Black 154, C.I. Direct Black 168, etc.) have been widely used. However, these dyes pose question about safety for the human body because the Ames test gives false positive or positive results. 
     On the other hand, useful as polyazo black dyes wherein safety for humans is improved, are for example, food colors (e.g. recording solution wherein Food Black 2 is used as a recording agent, etc.), 4,4&#39;-diaminodiphenylamine-2-sulfonic acid (substituent for benzidine) based trisazo dyes, stilbene tetrakisazo dyes having no amino group in their molecular structure and the like. However, aqueous inks wherein these dyes are used have poor water and light resistance of writing and, therefore, dyeing properties and fastness are inferior. 
     Polyazo dyes which satisfy the above properties have never been obtained. 
     Further, a water-soluble dye can be separated from aqueous systems by means such as aciding-out, salting out and the like. However, it is difficult to obtain a dye having high purity because of inclusion of an inorganic salts upon separation, whereby, various problems are caused. For example, when a dye having low purity is used for an aqueous writing ink, there is a disadvantage in that the ink is not consistently fed to a pen point. Also, when a dye of low purity is used for a jet printing ink, clogging of outlet orifice may occur. 
     OBJECTS OF THE INVENTION 
     One object of the present invention is to provide a trisazo dye having excellent chemical properties (e.g. dyeing properties, fastness, hue, solubility, etc.) and safety. 
     Another object of the present invention is to provide an aqueous ink composition containing the trisazo dye. 
     Still another object of the present invention is to provide a process for producing a highly purified trisazo dye concentrated solution. 
    
    
     These objects as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following description with reference to the following drawings. 
     BRIEF EXPLANATION OF DRAWINGS 
     FIG. 1 is a graph illustrating a visible spectrum of a trisazo dye of one embodiment of the present invention. 
     FIG. 2 is a graph illustrating a visible spectrum of a trisazo dye of another embodiment of the present invention. 
     FIG. 3 is a graph illustrating a liquid chromatography of a trisazo dye of one embodiment of the present invention. 
     FIG. 4 is a graph illustrating a liquid chromatography of a trisazo dye of another embodiment of the present invention. 
    
    
     SUMMARY OF THE INVENTION 
     According to the present invention, there is provided a trisazo dye represented by the formula: ##STR4## wherein A is a phenyl group substituted with at least substituent selected from the group consisting of an amino group, a substituted amino group and a hydroxyl group, B is a substituted or non-substituted phenyl group, X is a group of the formula: ##STR5## wherein n is 1 or 2, and M is hydrogen, alkali metal, aliphatic alkyl ammonium or alkanol ammonium], an aqueous ink composition containing the trisazo dye and a process for producing a concentrated solution containing the trisazo dye. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The trisazo dye of the present invention is an azo dye having a bond group of the formula: ##STR6## which is introduced into a molecular structure by tetrazotization of 1,4-bis(4-aminophenoxy)benzene or 1,3-(4-aminophenoxy)benzene. 
     The dye of the formula (I) of the present invention is obtained by a process including the steps of: 
     tetrazotizing 1,4-bis(4-aminophenoxy)benzene or 1,3-(4-aminophenoxy)benzene (1 mol) of the formula: ##STR7## wherein R is as defined above, by a normal method to obtain a tetrazonium salt (step 1); 
     adding an aqueous solution containing 1 mol of a compound of the formula: ##STR8## (e.g. 1-amino-8-naphthol-3,6-disulfonic acid, etc.) to the resulting tetrazotized solution to conduct coupling (step 2); 
     adding a diazotized diazo component B (1 mol) to the reaction solution to obtain a disazo dye (step 3); 
     adding a coupling component A (1 mol) to the reaction solution to conduct coupling to obtain a trisazo dye (step 4); and 
     concentrating and purifying the resulting reaction solution (step 5). 
     The reactions or operation conditions used in the above steps 1 to 5are known to the art. 
     Preferred examples of the diamino compound used in the step 1 include 1,4&#39;-bis(4-aminophenoxy)benzene and 1,3-bis(4-aminophenoxy)benzene. 
     Preferred examples of the coupling component used in the step 2 inlcude 1-amino-8-naphthol-3,6-disulfonic acid (hereinafter referred to as &#34;H acid&#34;), 1-amino-8-naphthol-4,6-disulfonic acid (hereinafter referred to as &#34;K acid&#34;), 1-amino-8-naphthol-4-sulfonic acid (hereinafter referred to as &#34;S acid&#34;), 4-amino-8-naphthol-6-sulfonic acid (hereinafter referred to as &#34;M acid &#34;), 3-amino-8-naphthol-6-sulfonic acid (hereinafter referred to as &#34;J acid&#34;), 2-amino-8-naphthol-6-sulfonic acid (hereinafter referred to as &#34;γacid&#34;) and the like. It is preferred to use H acid, K acid, S acid and J acid, particularly H acid. 
     Preferred examples of the diazo component B used in the step 3 include non-substituted or substituted anilines, e.g. aniline, o-, m- and p-toluidine, o-, m- and p-xylidine, anisidine, cresidine, p-nitroaniline, p-chloroaniline, ethylaniline, p-(sec-butyl)aniline, etc. and aminobenzene derivatives such as aminobenzenesulfonic acids, e.g. orthanilic acid, methanilic, sulfanilic acid, etc. It is particularly preferred to use aniline, sulfanilic acid and p-(t-butyl)aniline. 
     Preferred example of the coupling component A used in the step 4 include phenol derivatives, e.g. o-, m- and p-aminophenol, resorcin, catechol, cresol, 4-t-butylphenol, 4-hydroxyanisole, chlorophenol, acetylaminophenol, etc.), N,N-diethylaniline, N-(β-oxyethyl)aniline and N,N-di(β-oxyethyl)aniline. It is particularly preferred to use m-aminophenol and resorcin. 
     The trisazo dye of the present invention thus obtained has the same light resistance as that of a benzidine or tolidine azo dye as well as excellent water resistance (water resistance of writing) in comparison with the above azo dye, and is superior in solubility in an aqueous medium. Further, the trisazo dye of the present invention is a nontoxic trisazo dye which gives negative results in a back mutation test using an organism, which is generally known as a test method for evaluating toxicity, i.e. AMES test (mutation test). 
     The sulfonic group in the trisazo dye of the present invention can be converted into an alkali metal or ammonium salt, like several azo dyes having the sulfonic group. Further, it can also be converted into an amine salt with fatty amine or alkanolamine. 
     As the amine used for preparing the trisazo dye of the present invention, for example, there are aliphatic amines, e.g., butylamine, dibutylamine, sec-butylamine, di-t-butylamine, n-, iso-, sec- and t-amylamine, hexylamine, pentylamine, octylamine, 2-ethylhexylamine, di-(2-ethylhexyl)amine, dodecylamine, etc.; alicyclic amines, e.g. cyclohexylamine, di-cyclohexylamine, etc.; alkoxyalkylamines, e.g. 3-ethoxypropylamine, di-(3-ethoxypropyl)amine, 3-butoxypropylamine, octooxypropylamine, 3-(2-ethylhexyloxy)propylamine, etc.; alkanol group-containing amines, (e.g. ethanolamine, diethanolamine, triethanolamine, N-cyclohexyl-N-ethanolamine, N-dodecylimino-di-ethanol, etc. and the like. 
     By converting the sulfonic group in the trisazo dye of the present invention into an amine salt, a water-soluble or alcohol-soluble dye can be prepared depending upon the kind of the above basic compound. 
     In the preferred embodiment of the present invention, a reverse osmosis method is used in step 5 of concentrating and purifying a solution which contains the trisazo dye of present invention obtained in the steps 1 to 4. By the concentration/purification step, the conventional problem which is caused by inclusion of impurities upon separation of the water-soluble dye is solved. 
     The reverse osmosis method is a concentration method employing a phenomenon wherein a solvent is transferred through a semipermeable membrane from a concentrated solution side to a dilute solution side by applying a pressure larger than the osmotic pressure to the concentrated solution side which is partitioned from a dilute solution by the semipermeable membrane. 
     Preferred examples of the semipermeable membrane used in the concentration/purification step include reverse osmosis membranes (e.g. acetylcellusole membrane, synthesized high polymeric composite membrane, chargeable synthesized polymeric composite membrane, etc.). 
     The concentration/purification step in the present invention is conducted by cycling a reaction solution containing trisazo dye of the present invention obtained in the steps 1 to 4 while applying a pressure of about 4 to 8 Kgf/cm 2  to one side of a pressure resistant acrylic vessel which is partitioned by the semi-permeable membrane, until the conductivity of permeated water becomes 1 μs or less. 
     According to the concentration/purification step using the reverse osmosis method, the concentration of the dye solution is optionally controlled to 10 to 20% by weight. The concentrated solution of the dye thus obtained has high purity and is stable for a long period of time. Preferably, the concentrated solution of the present invention is a trisazo dye solution, which comprises 15% by weight of a trisazo dye of the formula (I) and 85% by weight of a medium (water). 
     The present invention also provides an aqueous ink composition comprising a trisazo dye of the formula (I) and an aqueous medium. 
     As the preferred examples of the aqueous organic solvent used for the aqueous ink composition of the present invention, for example, there are lower alcohols such as monovalent alcohols e.g., ethanol, n-propanol, iso-propanol, n-butanol, diacetone alcohol, etc.; monoalkyl ethers of diols, e.g. ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, etc.; monoacetates of diols, e.g. ethylene glycol monoacetate, polypropylene glycol monoacetate, etc.; benzyl alcohol; cyclohexanol; divalent alcohols, e.g., glycols such as ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, butanediol, etc.; trivalent alcohols, e.g. glycerin, trimethylolpropane, 1,2,6-hexanetriol, etc.; dioxane; N-methyl-2-pyrrolidone; ethyl lactate and the like. It is particularly preferred to use low toxic or nontoxic iso-propanol, ethylene glycol, propylene glycol monoalkyl ether, N-methyl-2-pyrrolidone and the like. 
     The preferred amount of the organic solvent in the aqueous ink composition of the present invention is 5 to 95% by weight, preferably 10 to 80% by weight, more preferably 15 to 30% by weight, based on the total weight of the ink composition. 
     The amount of the trisazo dye in the aqueous ink varies depending upon the application of the ink and is not specifically limited. It is preferred that the amount is generally 5 to 10% by weight for a ball-point pen, 5 to 15% by weight for a marking pen and 3 to 10% by weight for a jet recording ink. 
     According to the purpose to be included, there can be used a suitable amount of additives which are normally used, for example, water-soluble resins (e.g. low condensate of vinyl pyrrolidione, water-soluble alkyd resin, water-soluble acrylic resin, etc.), alcohol-soluble resins (e.g. alcohol-soluble phenol resin, acrylic resin, styrene maleic resin, ketone resin, etc.), preservatives, pH adjustors, surfactants and the like. 
     The aqueous ink composition of the present invention thus obtained can be used for various inks having excellent dissolution stability and stability in addition to writing ink and jet recording solution, and the resulting writing thereof has good fastness. Further, when the aqueous solution of the trisazo dye obtained by the process of the present invention is used for dyeing cellulose fibers or hides, build-up property is excellent and fast dyeing can be conducted. 
     The following Examples and Comparative Examples further illustrate the present invention in detail but are not construed to limit the scope thereof. In the Examples and Comparative Examples, all &#34;parts&#34; are by weight unless otherwise stated. 
     EXAMPLE 1 
     1,3-Bis(4-aminophenoxy)benzene (29.3 parts, 0.1 mols) was dissolved in concentrated hydrochloric acid (25 parts) and water (150 parts) with heating and the mixture was tetrazotized by adding a 36% aqueous solution of sodium nitrite (42.5 parts, 0.2 mols) at 0° C. To the resulting tetrazotized solution was added an aqueous solution of H acid (36.4 parts, 0.1 mols), followed by stirring at 5° to 10° C. for 2.5 hours. Thereafter, this solution was adjusted to pH 3.6 to 4.0 with a 10% aqueous solution of sodium carbonate, followed by additional stirring at 5° to 15° C. for 17 hours. Then, this solution was adjusted to pH 8.3 to 8.6 with a 20% solution of sodium carbonate. A solution of aniline (9.3 parts, 0.1 mols) as a diazo component B which was diazotized in advance was added to the solution and stirred at 5° to 15° C. for 5 hours. Then, a solution obtained by dissolving m-aminophenol (10.9 parts, 0.1 mols) into water (150 parts) was further added to the solution and stirred overnight to complete the reaction. 
     The resulting dye-containing solution was concentrated and purified using a chargeable synthesized polymeric composite membrane (trade name of &#34;NTR7410&#34;, manufactured by Nitto Denko Co.) as a reverse osmosis membrane according to a reverse osmosis method comprising pressing a dye-containing solution side at a pressure of about 4 to 8 Kgf/cm 2  to obtain a concentrated dye solution. 
     The concentrated solution containing the trisazo dye thus obtained was concentrated and dried to obtain 89 g of a black dye. By high performance liquid chromatography (HPLC) and visible absorption spectrum analysis, it was confirmed that the resulting dye is a dye having a structure of the following formula. A maximum absorption wavelength (nm) of a visible absorption spectrum of the dye solution and hue of the dye are also shown. ##STR9## 
     λ max  (nm): 438, 586; Greenish black color 
     The evaluation results of writing of the dye are shown in Table. 1 and those of Ames test are shown in Table. 1 and Table. 2. Further, a visible spectrum is shown in FIG. 1 and a liquid chromatography is shown in FIG. 3. 
     Liquid chromatography analysis was conducted under the following conditions. 
     1. Column: NUCLEOSIL 10C8 4.0*200 mm 
     2. Carrier; 
     
         ______________________________________Transfer phase(Solution A)  CH.sub.3 CN   10      ml         H.sub.2 O     90      ml         CH.sub.3 COOH 20      μl         KH.sub.2 PO.sub.4                       0.02    N(Solution B)  CH.sub.3 CN   10      ml         H.sub.2 O     90      mlGradient conditionInitial condition         →      Final conditionSolution A 80%         25 min.       Solution B 20%Solution B 20%              Solution A 80%______________________________________ 
    
     3. Flow rate: 1.5 ml/min. 
     4. Column temperature: 45° C. 
     5. Sensing wavelength: 600 nm 
     6. Preparation of sample: 
     A concentrated solution (200 μl) was dissolved in DMF (5 ml) and the resulting solution (200 μl) was dissolved in a carrier solution (5 ml) to obtain a sample solution for analysis. By using this sample solution (10 μl), analysis was conducted. 
     EXAMPLES 2 AND 3 
     According to the same manner as that described in Example 1 except for using components A and B shown in Table. 1 in place of aniline as a diazo component B and m-aminophenol as a coupling component A, dyes of Examples 2 and 3 were obtained. Analysis was conducted according to the same manner as that described in Example 1. It was confirmed that the resulting dye has a structure of the following formula, respectively. A maximum absorption wavelength (nm) of a visible absorption spectrum of the dye solution and hue of the dye are also shown. ##STR10## 
     λ max  (nm): 438, 586; Greenish black color ##STR11## 
     λ max  (nm): 438, 586; Greenish black color 
     The evaluation results of writing of the dyes are shown in Table. 1 and those of Ames test are shown in Table. 1 and Table. 2. 
     EXAMPLE 4 
     According to the same manner as that described in Example 1 except for using 1,4-bis(4-aminophenoxy)benzene (0.1 mols) in place of 1,3-bis(4-aminophenoxy)benzene (0.1 mols), a concentrated dye solution was obtained. 
     A dye content was concentrated and dried from the obtained concentrated solution containing a trisazo dye to obtain a black dye (80 g). Analysis was conducted according to the same manner as that described in Example 1. It was confirmed that the dye has a structure of the following formula. A maximum absorption wavelength (nm) of a visible absorption spectrum and hue of the dye are also shown. ##STR12## 
     λ max  (nm): 438, 588; Greenish black color 
     The evaluation results of writing of the dye are shown in Table 1 and those of Ames test are shown in Table. 1 and Table. 2. A visible spectrum of the dye is shown in FIG. 2. 
     EXAMPLE 5 TO 8 
     According to the same manner as that described in Example 4 except for using components B and A shown in Table. 1 in place of aniline as a diazo component B and m-aminophenyl as a component A, dyes of Example 5 to 8 were obtained. Analysis was conducted according to the same manner as that described in Example 1. It was confirmed that the resulting dyes have a structure of the following formula, respectively. A maximum absorption wavelength (nm) of a visible absorption spectrum and hue of the dye are also shown. ##STR13## 
     λ max  (nm); 438, 588; Greenish black color ##STR14## 
     λ max  (nm): 438, 588; Greenish black color ##STR15## 
     λ max  (nm): 438, 588; Greenish black color ##STR16## 
     λ max  (nm): 438, 588; Greenish black color 
     The evaluation results of writing of each dye are shown in Table. 1 and those of Ames test are shown in Table. 1 and Table. 2. 
     EXAMPLE 9 
     According to the same manner as that described in Example 1 except for using K acid in place of H acid, a dye was obtained. Analysis was conducted according to the same manner as that described in Example 1. It was confirmed that the resulting dye has a structure of the following formula. A maximum absorption wavelength (nm) of a visible absorption spectrum and hue of the dye are also shown. ##STR17## 
     λ max  (nm): 438, 586; Greenish black color 
     The evaluation results of writing of the dye are shown in Table. 1 and those of Ames test are shown in Table. 1 and Table. 2. 
     EXAMPLES 10 AND 11 
     According to the same manner as that described in Example 5 except for using S acid and J acid in place of H acid, dyes of Examples 10 and 11 were obtained. Analysis was conducted according to the same manner as that described in Example 1. It was confirmed that the resulting dye has a structure of the following formula, respectively. A maximum absorption wavelength (nm) of a visible absorption spectrum and hue of the dye are also shown. ##STR18## 
     λ max  (nm): 438, 586; Greenish black color ##STR19## 
     λ max  (nm): 438, 580; Greenish black color 
     The evaluation results of writing of each dye are shown in Table. 1 and those of Ames test are shown in Table. 1 and Table. 2. 
     COMPARATIVE EXAMPLES 1 TO 3 
     According to the same manner as that described in Example 1 except for using aromatic diamines and components B and A shown in Table. 1 in place of aniline as a disazo component B and m-aminophenol as a coupling component A, dyes of Comparative Examples 1 to 3 were obtained. Analysis was conducted according to the same manner as that described in Example 1. It was confirmed that the resulting dyes have each structure of the following formula, respectively. Hue is also shown. ##STR20## 
     The evaluation results of writing of each dye are shown in Table. 1 and those of Ames test are shown in Table. 1 and Table. 2. 
     EVALUATION METHOD OF WRITING 
     Light resistance: The resulting dye was dissolved in a 5% aqueous diethylene glycol solution to obtain a 3% dye solution. The solution was extended over a writing paper A (JIS P-3201) with an applicator (25μ) to form a drawndown paper, which was exposed to sunlight for one month. A degree of discoloration was compared with that before testing. 
     Water resistance: The drawndown paper was air-dried for one day and dipped in tap water. Then, a deflection density was measured by a Macbeth densitometer (manufactured by Colmorgen Co. as TR-927) to compare with that before testing. 
     EVALUATION CRITERIA 
     Light resistance: 
     A: Little discoloration is observed. 
     B: Discoloration is observed. 
     C: Discoloration is severe. 
     Water resistance: 
     A: Reflection density is more than 70% of that before testing. 
     B: Reflection density is 50 to 70% of that before testing. 
     C: Reflection density is less than 50% that before testing. 
     EVALUATION METHOD OF AMES TEST 
     Regarding various specimen solutions respectively containing trisazo dyes obtained in Examples 1 to 11 to the present invention and dyes of Comparative Examples 1 to 3, the number of mutant colonies was determined using strains TA98. A ratio of the number of colonies determined by Ames test to a control was shown in Table. 2. When the ratio is less than 2, it is &#34;negative&#34; and, when the ratio is more than 2, it is &#34;positive&#34;, and the results are shown in Table. 1. 
     In Table. 2, the column (-) shows the ratio when no drug metabolic active enzyme S-9 is added, and the column (+) shows the ratio when a drug metabolic active enzyme S-9 is added. 
     
         ______________________________________Component         Amount (parts by weight)______________________________________Deionized water   35Propylene glycol  15Concentrated solution             50of Example 1Surfactant (Unidine DS-401)             1Preservative      0.1______________________________________ 
    
     A black ink for an aqueous ball point pen was made according to the above formulation and a writing performance was examined. Smooth writing was available for a long period of time, and light and water resistance of writing was excellent. 
     EXAMPLE 13 
     
         ______________________________________Component       Amount (parts by weight)______________________________________Deionized water 35Ethylene glycol 10Diethylene glycol           5Concentrated solution           50of Example 3Preservative    0.2______________________________________ 
    
     A black ink for a marking pen was made according to the above formulation and a writing performance was examined. Smooth writing was available for a long period of time, and light and water resistance of writing was excellent. 
     EXAMPLE 14 
     
         ______________________________________Component       Amount (parts by weight)______________________________________Deionized water 70Diethylene glycol           10Sodium benzoate 0.1Concentrated solution           20of Example 7______________________________________ 
    
     A black jet recording ink was made according to the above formulation and a recording performance was examined using a commercially available ink-jet printer. Printing could be conducted without clogging of orifice, and light and water resistance of the recorded literature/image was excellent. 
     STABILITY OF CONCENTRATED SOLUTION WITH TIME 
     Each concentrated solution obtained in Examples 1 to 8 was charged in a 50 ml glass sample bottle, respectively. Then, stability with time was evaluated, using an incubator (manufactured by Sanyo Denki Co.). In a test (temperature range: -5° to 50° C.; repeat time: 60 minutes; test period: 3 months), precipitation of the dye and change of properties of the concentrated solution were not observed. 
     
                                           TABLE 1__________________________________________________________________________      Novel trisazo dye  Writing evaluation      Aromatic           Water                              LightComponent A      diamines           Component B                  Component C                         resistance                              resistance                                   AMES evaluation__________________________________________________________________________Ex. 1    m-Amino      *1   Aniline                  H acid A    B    Negative    phenolEx. 2    Resorcin      *1   Aniline                  H acid B    B    NegativeEx. 3    Resorcin      *2   p sec  H acid A    B    Negative           ButylanilineEx. 4    m-Amino      *1   Aniline                  H acid A    B    Negative    phenolEx. 5    Resorcin      *2   Aniline                  H acid B    B    NegativeEx. 6    Resorcin      *2   p-sec- H acid A    B    Negative           ButylanilineEx. 7    Resorcin      *2   o-Toluidine                  H acid A    B    NegativeEx. 8    m-Amino      *2   Sulfanilic                  H acid B    B    Negative    phenol      acidEx. 9    m-Amino      *1   Aniline                  K acid A    B    Negative    phenolEx. 10    Resorcin      *2   Aniline                  S acid A    B    NegativeEx. 11    Resorcin      *2   Aniline                  J acid A    B    NegativeComp.    m-Phenylene      *3   Aniline                  H acid B    B    PositiveEx. 1    diamineComp.    m-Amino      *4   Aniline                  H acid C    B    PositiveEx. 2    phenolComp.    Resorcin      *3   Sulfanilic                  H acid C    B    PositiveEx. 3           acid__________________________________________________________________________ *1: 1,3Bis(4-aminophenoxy)benzene *2: 1,4Bis(4-aminophenoxy)benzene *3: oTolidine *4: Diaminodiphenylsulfone 
    
     
                       TABLE 2______________________________________Ames test results  Concentration of substance to be  tested (μg/plate)  S 9  20       78     313    1250 5000______________________________________Ex. 1    -      0.76     0.86 0.86   0.76 0.71    +      1.13     0.94 1.06   0.53 0.59Ex. 2    -      1.07     1.20 1.02   1.16 1.28    +      1.34     1.19 1.39   1.28 1.27Ex. 3    -      0.76     0.86 0.86   1.10 0.95    +      1.32     1.79 1.59   0.76 0.56Ex. 4    -      0.88     0.79 0.96   1.15 0.92    +      1.04     1.23 0.99   0.88 0.90Ex. 5    -      0.89     0.95 0.63   0.79 0.68    +      0.93     1.04 0.86   1.04 0.57Ex. 6    -      1.01     1.04 1.16   0.97 0.91    +      1.01     1.00 0.98   0.84 0.84Ex. 7    -      0.95     1.00 0.80   0.80 1.00    +      0.94     0.89 1.00   1.05 1.05Ex. 8    -      1.05     1.08 0.93   1.03 1.12    +      0.94     0.92 0.92   0.93 1.03Ex. 9    -      0.85     0.65 0.75   0.60 1.15    +      1.05     1.00 1.16   1.00 0.53Ex. 10   -      1.03     1.01 0.84   1.02 0.97    +      0.91     0.92 0.85   1.09 0.90Ex. 11   -      0.96     1.00 0.81   1.04 1.35    +      1.25     1.64 1.34   0.64 1.07Comp.    -      0.72     0.68 0.84   0.76 0.96Ex. 1    +      1.92     2.35 2.50   1.50 0.85Comp.    -      1.10     1.52 1.29   1.38 3.38Ex. 2    +      5.26     26.3 9.11   1.23 1.61Comp.    -      0.92     1.00 2.56   3.56 0.96Ex. 3    +      1.20     2.24 4.16   1.12 0.16______________________________________