JPS6129989B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following general formula () [In the formula, R is a hydrogen atom or an optionally substituted alkyl group, alkenyl group, an optionally substituted phenyl group, an optionally substituted cycloalkyl group, X is an oxygen atom or a sulfur atom, and A is a substituted represents a benzene _ring which may be Represents an anilino group or an optionally substituted phenoxy group. n means an integer of 1 or 2. ] This invention relates to a xanthene or thioxanthene compound which is insoluble or sparingly soluble in water and a method for coloring an organic polymer material using the same. The object of the present invention is to use organic polymeric materials such as polyester or hydrophobic fiber materials such as cellulose triacetate, or thermoplastic resins such as polyethylene resin, polypropylene resin, polyvinyl chloride resin, ABS resin, and polystyrene resin. The object of the present invention is to provide a compound that colors molded articles extremely vividly and with excellent color fastness from yellow to orange-yellow. Examples of the substituents on the benzene ring (A) in the general formula () include the following. Halogen atom, preferably chlorine atom, bromine atom,
These include a straight chain or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group, a phenyl group, and the like. The −SO ₂ Z group in the above general formula () is replaced by the following formula (−) in a compound having a corresponding sulfochloride group.
It is obtained by reacting aliphatic primary amines, secondary amines, aromatic amines, or phenols represented by: The amino compounds used include the following. ammonia, methylamine, ethylamine, n
-propylamine, iso-propylamine, ethanolamine, 3-methoxypropylamine, 3
-Ethoxypropylamine, dimethylamine, diethylamine, di-n-propylamine, di-n
-Butylamine; N-methyl N-butylamine; morpholine, piperidine, benzylamine,
Examples include p-chlorobenzylamine, aniline, m-chloroaniline, p-chloroaniline, p-toluidine, p-anidine, o-anisidine, p-phenylaniline, and the like. Examples of the phenols used include the following compounds. Phenol, o-cresol, m-cresol, p-chlorophenol, m-chlorophenol, p-methoxyphenol, 2-methyl-4-
Chlorphenol, pt-butylphenol. Examples of R in the general formula () include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-methoxyethoxypropyl. , 3-ethoxyethoxypropyl, 2-hydroxypropyl, 2-hydroxyethyl, 2-methoxyethoxyethyl, 2-acetoxyethyl, 2-acetylaminoethyl, allyl, benzyl, p-chlorobenzyl, m-chlorobenzyl, Alkyl groups such as cyclohexyl groups, alkenyl groups, and even
Acid groups of aniline derivatives such as phenyl, m-chlorophenyl, p-chlorophenyl, o-tolyl, p-tolyl, p-methoxyphenyl, p-
Examples include t-butylphenyl and p-ethylphenyl groups. Particularly preferable compounds in the present invention have the formula (-a) (In the formula, R ₁ is a hydrogen atom, methyl, ethyl, n-propyl, iso-propyl, 3-methoxypropyl,
3-ethoxypropyl, 3-butoxypropyl,
3-methoxyethoxypropyl, 3-ethoxyethoxypropyl, 2-hydroxypropyl, 2-
Methoxyethoxyethyl, 2-acetoxyethylbenzyl, phenyl, m-chlorophenyl, p-
Represents a chlorophenyl, o-tolyl, p-tolyl or p-methoxyphenyl group. benzene ring
A ₁ is chlorine atom, bromine atom, methyl, ethyl,
Substituted with methoxy, ethoxy, carboxyl, methoxycarbonyl or ethoxycarbonyl groups. Z ₁ is an amino group, methylamino, ethylamino, n-propylamino, isopropylamino,
Ethanolamino, 3-methoxypropylamino, 3-ethoxypropylamino, isopropoxypropylamino, ptoxypropylamino, dimethylamino, diethylamino, morpholino, piperidino, benzylamino, anilino, m-chloroanilino, p-chloranilino, p-toluidino or p-anisidino group, phenoxy, o-methylphenoxy, m-methylphenoxy or p-t
- represents a butylphenoxy group. X represents an oxygen atom or a sulfur atom, and n represents an integer of 1 or 2). The dye represented by the general formula () is a new dye, and can be produced, for example, by any of the methods (a), (b), and (c) below. That is, (a): a compound represented by the following general formula () (in the formula, X and A mean the above) is chlorosulfonated using chlorosulfonic acid and thionyl chloride in the presence or absence of an inert solvent, and then the obtained compound having a sulfochloride group is It is condensed with a compound represented by the formula (-) Z-H (-) (in the formula, Z represents the above) to form the general formula () (In the formula, X, A, Z or n represents the above-mentioned) A compound represented by the formula (-) R-NH ₂ (-) (in the formula, R represents the above-mentioned) is obtained. This is a method for producing a compound represented by the formula () by reacting it with the compound represented by the formula (). This method is preferably carried out as follows. When a sulfochloride group is introduced into the compound of the general formula () by the action of chlorosulfonic acid and thionyl chloride, chlorosulfonation is carried out within a temperature range of 0 to 100°C, and the chlorosulfonic acid and thionyl chloride used are Although the chloride itself may be used in large excess as a solvent, it is preferably used in an amount of 1 to 5 equivalents relative to the compound of general formula (). Subsequently, the obtained chlorosulfonated product is condensed with an aliphatic or aromatic primary or secondary amine or phenol to obtain a compound of the following general formula (). The above chlorosulfonation reaction can be carried out even in the presence of an inert solvent. Preferred inert solvents include chloroform and dichloroethane. The above sulfonic acid amidation and sulfonic acid esterification are carried out at 0 to 60°C in the presence of an acid binder in a solvent such as water, an alcoholic solvent, chlorobenzene, xylene, toluene, etc. or a mixed solvent thereof.
It is carried out over a temperature range of Furthermore, by condensing the compound of the above general formula () with an aliphatic or aromatic primary amine in a hydrophilic or hydrophobic solvent within a temperature range of 50 to 150°C, the compound of the above general formula () can be obtained. is obtained. (b): General formula () (In the formula, R' represents a hydrogen atom, an optionally substituted alkyl group or alkenyl group, and A and X represent the above) in the presence or absence of an inert solvent with chlorosulfonic acid and thionyl chloride. The resulting compound having a sulfochloride group is condensed with a compound represented by the formula (-) to form a compound having the general formula (-). (In the formula, R', X, A or Z represents the above-mentioned ones.) A method for producing a compound represented by the following. and (c): the following general formula () (In the formula, Y represents an oxygen atom or >NR group, R,
(X, A, Z or n represents the above) is diazotized, ring-closed,
This is a method for producing a compound represented by the general formula (), which is characterized in that when is an oxygen atom, the compound is further reacted with a compound represented by the formula (-a). This method (c) is preferably carried out as follows. That is, the above diazotization and ring-closing reaction involves diazotizing the compound of general formula () using 1 to 1.5 equivalents of nitrosyl sulfuric acid, and diazotizing the resulting diazo solution containing copper sulfate and ferrous sulfate at 80 to 100°C. It is carried out by dropping into a solution. Or suspend the compound of general formula () in dimethylformamide and add 1 to 1.5 equivalents of sodium nitrite and 1 to 5 equivalents of concentrated sulfuric acid at -5°C to 5°C.
diazotization followed by heating the reaction solution at 60℃ to 100℃.
This is done by heating to. Preferred compounds of the general formula () are those in which X is an oxygen or sulfur atom and the benzene ring A is substituted with a chloro atom, bromine atom, methyl, ethyl, ethoxy, methoxy, carboxylmethoxycarbonyl or ethoxycarbonyl group. Among the compounds represented by the general formula (-), preferred are ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, ethanolamine, diethanolamine, 3-methoxypropylamine, and isopropoxypropylamine. , butoxypropylamine, ethoxypropylamine, dimethylamine, diethylamine, morpholine, benzylamine, aniline, m-chloroaniline,
p-chloroaniline, o-toluidine, m-toluidine, p-anisidine, phenol, o-cresol, m-cresol, p-cresol or p
-t-butylphenol and the like. Among the compounds represented by the general formula (-a), preferred are ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, 3 -(n-propoxy)propylamine,
3-(n-butoxy)propylamine, 3-isobutoxypropylamine, 2-hydroxypropylamine, 3-methoxyethoxypropylamine, 3-ethoxyethoxypropylamine, 2-
Examples include acetoxyethylamine, benzylamine, aniline, m-chloroaniline, p-chloroaniline, o-toluidine, m-toluidine, and p-toluidine. On the other hand, the compound represented by the above general formula (), which is a starting material, can be manufactured by the following general formula (). [In the formula, Y' is an oxygen atom or >N-R', W is a hydrogen atom or an acyl group, and X, A, and R' are the same as above.] The above (a)
-SO ₂ Z group is introduced according to the method of , or the following general (), () [In formulas () and (), X, Y, W, A mean the above-mentioned ones, T means a chloro atom, a bromine atom, a sulfonic acid group, or an alkali metal salt thereof, and U and U' both mean the above-mentioned ones. -SO ₂ Z group, or one of them may be a hydrogen atom and the other is an SO ₂ N group. ] It can be obtained by condensing the compound represented by the following in an appropriate solvent. When specifically dyeing hydrophobic fiber materials according to the method of the present invention, the raw material of the compound represented by the general formula () is mixed with a suitable dispersant, such as naphthalene sulfonic acid formalin condensate or lignin sulfonate sodium. It is thoroughly mixed and ground and applied to dyeing in a finely dispersed state. In addition to general dyeing, high temperature dyeing, carrier dyeing, thermosol dyeing, textile dyeing, dyeing using organic solvents, etc. are used. It is also useful to circularly soap the dyed material after dyeing. Furthermore, when coloring a synthetic resin according to the method of the present invention, the raw material of the compound represented by the general formula () is finely pulverized, or preferably finely pulverized together with metal soap, and mixed with pelletized resin and injected. Put it into the molding machine and heat it to 130~300℃ depending on the type of resin.
It can be molded at a temperature of Furthermore, it is also possible to prepare so-called masterbatches and toner colors and use these to color the resin. When polyester fiber materials are dyed using the dyeing method of the present invention, dyed products with excellent light fastness, sublimation resistance, and wet fastness can be obtained, and when synthetic resins are dyed, they have excellent heat resistance, bleed resistance, and light fastness. Excellent colored products can be obtained. The present invention will be specifically explained below with reference to Examples. In the examples, parts and % mean parts by weight and % by weight, respectively. Example 1 General formula (1-a) below 5.0 parts of the compound and 0.72 parts of sodium nitrite are suspended in 20 parts of dimethylformamide, and 7 parts of a dimethylformamide solution containing 2 parts of concentrated sulfuric acid is added dropwise.
The reaction solution is stirred at 0 to 5°C for several hours, and then gradually raised to 65 to 75°C, and stirred at that temperature until the reaction is completed. Cool, add methanol, separate the crystals at room temperature, and convert to the following formula (1) (mp = 198-200
℃) was obtained as an orange dyestuff. Elemental analysis (%) C H N S Calculated value 57.72 5.01 8.42 12.83 Actual value 57.85 5.20 8.51 12.95 15 parts of the raw material of the compound of formula (1) was mixed with 45 parts of naphthalene sulfonic acid formalin condensate, 40 parts of sodium lignin sulfonate, and water. is added to make a slurry, thoroughly mixed and ground to finely disperse it. Then dry with a spray dryer. Two parts of the dispersed dye are added to 3,000 parts of water to form a dispersion, and the pH is adjusted to 5 with acetic acid, and 100 parts of polyester fibers are immersed and dyed at 130° C. for 1 hour under pressure. The dyeing was then reductively soaped and thoroughly washed with water to give a bright orange-yellow dyeing. It was excellent in light fastness, sublimation resistance, and wet fastness. Example 2 Formula (2-a) below The following formula (2-b) obtained from the compound according to the diazotization and ring closure method of the compound (1-a) of Example 1 Compound shown and methylamine in methylcellosolve solvent in the presence of a small amount of acetic acid at 70°C to 100°C
By reacting for 7 hours at A compound (m.p 233-4°C) represented by was obtained. Elemental analysis (%) C H N S Calculated value 61.06 4.42 6.19 14.16 Actual value 61.02 4.52 6.21 14.04 15 parts of this compound was finely dispersed according to Example 1, and 20 parts of the dispersed dye was added to 1000 parts of water to create a dispersion liquid. Then, the dyed fabric was soaked in Tetoron cloth, squeezed to 60% by weight, dried once at 100°C, and then subjected to dry heat treatment at 210°C for 30 seconds.The dyed fabric was then reductively soaped, thoroughly washed with water, and dried. A clear orange-yellow colored product was obtained, and the color fastness was excellent. Example 3 The following formula (3-a) or (3-b) From the following formula (3) according to the manufacturing method of the dyestuff in Example 1 or 2. The compound represented by was obtained. Elemental analysis values: C(%) H(%) N(%) S(%) Calculated value 59.68 3.73 2.49 11.37 Actual value 59.50 3.79 2.52 11.70 Using this compound, polyester fiber was dyed in the same manner as in Example 1 to make it light resistant. A bright yellow dyed product with excellent sublimation resistance was obtained. Examples 4 to 16 According to the manufacturing method of Examples 1, 2, or 3, the raw materials of the compounds shown in the table below were obtained. Then, polyester fibers were dyed in the same manner as in Example 1 to obtain dyed products having the colors shown in the table.

【table】

[Table] Example 17 4.6 parts of chlorosulfonic acid was added dropwise to 6 parts of benzothioxanthene anhydride and 120 parts of dichloroethane at 20°C, and the mixture was gradually heated and stirred at 65-75°C for 3 hours. Add 6 parts of thionyl chloride and stir at that temperature for an additional 2 hours. The reaction product was poured into ice water, the precipitated crystals were separated, and the following formula (17-a) was obtained. A mixture of isomers shown is obtained. Furthermore, add 200 parts of acetone, 10 parts of phenol,
10 to 2 parts of caustic soda, 20 parts of potassium carbonate, and 20 parts of water
After reacting at 20°C for 10 hours, it was cooled and neutralized by adding aqueous acetic acid, and the crystals were separated to form the following formula (17-b). A mixture of isomers is obtained. Further, this was reacted with 3-methoxypropylamine according to the method for producing the raw material of the compound in Example 2, and the following formula 17 was obtained. I got it. Elemental analysis (%) C H N S Calculated value 59.68 3.73 2.49 11.37 Actual value 59.97 3.51 2.51 11.49 Using this mixture of isomers, polyester fibers were dyed in the same manner as in Example 1 to determine light resistance, sublimation resistance, moisture resistance, A green-yellow dyeing with excellent rub fastness was obtained. Example 18 A compound represented by the following formula (18) was obtained by using the production method of Example 17 but using N·N dimethylamine instead of phenol. A similar compound was also obtained using the following compound (18-a) as a starting material. Elemental analysis (%) C H N S Calculated value 57.72 5.01 8.42 12.83 Actual value 57.60 4.91 8.40 12.99 Example 1
Finely disperse the dye in the same manner as above, add 2 parts of the dispersed dye to 3000 parts of water to make a dispersion, adjust the pH to 5 with acetic acid, immerse 100 parts of Tetoron yarn, add 10 parts of methylnaphthalene carrier, and dye for 1 hour at boiling point. The dyed yarn was then reductively soaped, thoroughly washed with water, and dried. A very clear green-yellow dyed product was obtained and had excellent fastness properties. Example 19 In the production method of Example 17, benzoxanthene anhydride was used instead of benzothioxanthene anhydride, and chlorsulfonation, esterification, and
By imidization, the following formula (19) A mixture of isomers shown was obtained. Elemental analysis (%) C H N S Calculated value 64.67 3.79 2.79 6.39 Actual value 64.60 3.60 2.70 6.30 Fine dispersion was carried out in the same manner as in Example 1 using the raw material of this mixture. Add 2 parts of this dispersed dye to water.
In addition to 3000 parts of the dispersion, 100 parts of cellulose triacetate fibers are immersed and dyed at 120°C for 1 hour under pressure. The dyed material is reductively soaped, thoroughly washed and dried. A dyed product with an extremely vivid yellow edge was obtained and had excellent light fastness, sublimation fastness and wet fastness. Example 20 The following formula (20-a) The following formula (20) is obtained by chlorosulfonation and then amidation using the compound represented by as a starting material. A compound represented by was obtained. Elemental analysis (%) C H N S Calculated value 66.38 3.83 5.96 6.81 Actual value 66.52 3.60 5.68 6.30 This compound was finely dispersed in the same manner as in Example 1, and 20 parts of this dispersed compound was mixed with 520 parts of water and 400 parts of crystal gum. to make a paste.
After printing the paste on Tetoron cloth and drying it,
Steam treatment at 200℃ for 60 seconds. The dyed fabric obtained is reductively soaped, then washed with water and dried. A vivid green-yellow dyed fabric is obtained with light resistance, sublimation resistance,
It had excellent wet fastness. Examples 21 to 35 The compounds shown in the table below were obtained according to the method for producing dye base materials of Examples 17, 18, 19, and 20. Using these compounds, polyethylene fibers were dyed in the same manner as in Example 1 to obtain dyed products having the tones shown in the table.

【table】

[Table] Example 36 The following formulas (36-a), (36-b) The isomer mixture represented by the formula (36) was diazotized and ring-closed in accordance with the method for producing the raw material of the compound in Example 1, followed by imidization to obtain a mixture of compounds represented by the following formula (36). Elemental analysis (%) C H N S Calculated value 63.85 4.22 2.57 11.74 Actual value 64.09 4.32 2.43 11.70 Using this, polyester fiber was dyed in the same manner as in Example 1 to obtain a bright yellow dyed product. This had excellent light fastness and wet sublimation fastness. Example 37 The following formulas (37-a), (37-b) A compound represented by the following formula (37) was manufactured from the isomer mixture represented by the following formula (37) according to the method for manufacturing the compound of Example 2. Elemental analysis (%) C H N S Calculated value 61.06 4.42 6.19 14.16 Actual value 61.20 4.69 6.30 14.60 Polyester fibers were dyed using the mixture of compounds represented by formula (37) according to the method of Example 2 to obtain extremely clear results. A yellow dyed product was obtained. Example 38 The following formula obtained according to the manufacturing method of the dyestuff in Example 17 using 6 parts of benzothioxane anhydride, 120 parts of 1,2-dichloroethane, 7 parts of chlorosulfonic acid, and 7 parts of thionyl chloride. (38-c),
(38-d) A mixture consisting of is subjected to N-N-dimethylamidation and then methylimidation to form the following formulas (38-a) and (38-b). A mixture consisting of the compounds shown was obtained. This mixture was finely dispersed in the same manner as in Example 1.
Tetoron cloth was printed according to the method described in 20, and a very bright green-yellow dyed product with excellent fastness was obtained. Example 39 The following formula (39) A green-yellow dyed cloth with excellent color fastness was obtained by printing Tetron cloth according to the method of Example 20 using raw materials of compounds consisting of n=1 and n=2 and their isomers shown in It was done. Example 40 The following formula (40) Tetoron cloth was dyed using the raw material of the compound shown in Example 2 according to the method of Example 2, and a green-yellow dyed product with excellent light fastness, sublimation resistance, and wet fastness was obtained. The raw material of the above compound is the following formula (40-a) It was obtained by diazotizing the compound represented by and then ring-closing it. Elemental analysis (%) C H N S Calculated value 63.42 3.17 2.96 13.53 Actual value 63.64 3.24 2.59 13.77 Example 41 Formula (41) below Elemental analysis (%) C H N S Calculated value 58.97 4.27 5.98 13.68 Actual value 56.27 4.41 6.03 13.50 Example 2 using the raw material (40) of the compound shown by
A green-yellow dyed product with excellent color fastness was obtained by dyeing Tetoron cloth according to the method of . Example 42 0.1 part of the compound obtained according to Example 1 and 0.1 part of calcium stearate were mixed with 200 parts of polystyrene pellets in a rotary mixer, and then this was mixed at 200°C using an isodiexion molding machine. A yellow molded product with excellent light and heat resistance was obtained by melt-kneading. The λmax of the compounds obtained in Examples 1 to 41 in dimethyl formaldehyde was measured and the following results were obtained. (unit of λmax is nm)

【table】

Claims (1)

[Claims] 1. The following general formula () [In the formula, R is a hydrogen atom or an optionally substituted alkyl group, alkenyl group, an optionally substituted phenyl group, an optionally substituted cycloalkyl group, X is an oxygen atom or a sulfur atom, and A is a substituted _-SO2 represents a benzene ring which may be It represents a good anilino group or an optionally substituted phenoxy group. n means an integer of 1 or 2. ] A xanthene or thioxanthene compound represented by 2 The following general formula () [In the formula, R is a hydrogen atom or an optionally substituted alkyl group, alkenyl group, an optionally substituted phenyl group, an optionally substituted cycloalkyl group, X is an oxygen atom or a sulfur atom, and A is a substituted -SO ₂ Z group is bonded to a benzene ring or a naphthalene ring; It represents a good anilino group or an optionally substituted phenoxy group. n means an integer of 1 or 2. ] A method for coloring a polymeric organic material, characterized by using a xanthene or thioxanthene compound represented by: