A modified phthalocyanine pigment, a liquid colorant and a preparation method and application thereof

Abstract

The application discloses a modified phthalocyanine pigment, a liquid colorant and a preparation method and application thereof, and belongs to the technical field of pigments and colorants. The modified phthalocyanine pigment comprises the following components in percentage by weight: phthalocyanine pigment 90-99%, pigment derivative 1-10%. The pigment derivative is prepared by sulfonating the phthalocyanine pigment and then modifying the sulfonated phthalocyanine pigment by using a compound containing an amino group and a hydroxyl group and an aromatic acid. The pigment derivative has a benzoate structure. The liquid colorant comprises the following components in percentage by weight: carrier resin 55-90%, modified phthalocyanine pigment 10-40%, and functional additive 0-5%. The liquid colorant prepared by using the modified phthalocyanine pigment has small particle size, low viscosity and good storage stability. When the liquid colorant is applied to in-situ polymerization of polyester, the colored polyester fiber prepared has uniform color, and has good breaking strength, breaking elongation, soaping fastness and rubbing fastness.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of fine chemical technology, in particular to a modified phthalocyanine pigment, a liquid colorant, a preparation method thereof and application in in-situ polymerization of polyester fiber. BACKGROUND

[0002] Synthetic fiber containing more than 85% of polyethylene terephthalate component is called polyester fiber in China, and the trade name is polyester. Polyester is a polymer obtained by polycondensation of polybasic acid and polyhydric alcohol. Direct esterification method and ester exchange method are used in polyester synthesis process. Direct esterification method has the advantages of low raw material consumption and short reaction time, and becomes the main synthesis process. The main reaction process of direct esterification method is as follows: first, esterification reaction of high-purity terephthalic acid and ethylene glycol to generate ester and water, and then polycondensation reaction of the generated ester to obtain polyester and ethylene glycol, wherein the polycondensation includes pre-polycondensation and final polycondensation.

[0003] Polyester fiber has a linear and straight molecular arrangement, high crystallinity and good orientation after stretching and setting in the spinning process, and has small intermolecular space, so it is difficult for dyes to penetrate into the fiber. There is no polar functional group such as hydroxyl group and amino group on the macromolecular chain of polyester fiber, only ester group with small polarity, so polyester fiber has poor dyeing property as a textile material. Dye molecules can only enter the interior of the fiber under high temperature and high pressure conditions for dyeing, and the dyeing process has problems such as high equipment requirement and large wastewater discharge. In-situ polymerization dyeing is to add a colorant to the polyester polymerization process to obtain a colored polyester melt to prepare colored polyester fiber or polyester masterbatch. In-situ polymerization dyeing eliminates the subsequent dyeing process, reduces the "three wastes" pollution and huge energy consumption caused by dyeing, cleaning and other processes, and is beneficial to energy saving and emission reduction in the fiber production process, and has good development prospect.

[0004] Liquid colorants for polyester coloring generally contain a carrier, a colorant, and a functional additive. The liquid colorant carrier is generally polyester, for example, the Chinese patent with publication number CN102585450A discloses a color master batch for polyester, which contains a polyol ester carrier, a colorant, and an additive, wherein the polyol ester carrier includes a fatty acid adipic acid polyol ester; the Chinese patent with publication number CN102702701A discloses a liquid color master batch for polyester products, which includes a carrier, a colorant, and a functional additive, wherein the carrier is a liquid carrier of polycaprolactone polyol; the Chinese patent with publication number CN107723831A discloses a stock solution colored polyester fiber, which is prepared by adding a colorant to a carrier polyester polyol to prepare a uniform color master solution, wherein the polyester polyol is an aliphatic polyester polyol with a molecular weight of 300-10000. The liquid colorant carrier also has literature reports using ethylene glycol, for example, the Chinese patent with publication number CN101338067A discloses a black polyester chip and a preparation method of the black polyester chip, the black polyester chip is prepared by adding a prepared carbon black color paste before the ester exchange or esterification reaction step, wherein the carbon black color paste includes ethylene glycol, carbon black, a cosolvent, and a dispersant; the US patent with publication number US2010204395A1 discloses a liquid color master batch for polyester products, which contains a polyalkylene polyol carrier, a colorant, and optional other functional additives, wherein the liquid polyalkylene polyol carrier is polyethylene glycol with a weight average molecular weight of 200-400.

[0005] Phthalocyanine pigments are commonly used colorants due to their bright color, high tinting strength, and excellent light resistance, heat resistance, acid and alkali resistance. Surface modification of phthalocyanine pigments by chlorination, sulfonation, amidation, etc. to improve the dispersibility, rheology, and flocculation of phthalocyanine pigments is an important method to improve the application performance of phthalocyanine pigments. For example, the Chinese patent with publication number CN1955227A discloses a modified phthalocyanine dyeing agent, which is prepared by first sulfonating phthalocyanine with chlorosulfonic acid and thionyl chloride, and then aminating; the European patent with publication number EP0574790A1 discloses a finishing process for phthalocyanine pigments, one of the pigment dispersants used is prepared by first sulfonating phthalocyanine, and then aminating. The British patent with publication number GB949739A discloses a solvent-resistant non-flocculating pigment mixture, which is added with 0.5-10 mole ratio of a substituted aminomethyl phthalocyanine compound, so that the pigment mixture has excellent anti-flocculation property.

[0006] There is no related technical report in the prior art that first sulfonates phthalocyanine, then modifies it with a compound containing an amino and a hydroxyl group, and an aromatic acid, and applies it to in-situ polymerization of polyester to improve the stability and dispersibility of phthalocyanine pigments in polyester. SUMMARY

[0007] The application aims to provide a modified phthalocyanine pigment, a liquid colorant and a preparation method and application thereof; the liquid colorant prepared by using the modified phthalocyanine pigment has small particle size, low viscosity and good storage stability, and is applied to in-situ polymerization of polyester, and colored polyester fibers prepared by using the liquid colorant have uniform color, and have good breaking strength, breaking elongation, soaping fastness and rubbing fastness.

[0008] To achieve the above technical purposes and effects, the application is implemented by the following technical solutions.

[0009] The application provides a modified phthalocyanine pigment, which comprises the following components in percentage by weight: 90-99% of phthalocyanine pigment and 1-10% of pigment derivative; the pigment derivative is prepared by sulfonating the phthalocyanine pigment and then modifying the sulfonated phthalocyanine pigment by using a compound containing an amino end group and a hydroxyl end group and an aromatic acid; and the pigment derivative has a benzoate structure.

[0010] The preparation process of the pigment derivative is as follows: the phthalocyanine pigment is added into chlorosulfonic acid for sulfonation reaction, and then added into thionyl chloride for chlorination reaction to obtain sulfonated phthalocyanine pigment; then the sulfonated phthalocyanine pigment is added into water, and after the pH value is adjusted by using a pH value regulator, a compound containing an amino end group and a hydroxyl end group is added, and then reaction is performed to obtain phthalocyanine pigment containing a hydroxyl group; and then the phthalocyanine pigment containing a hydroxyl group and an aromatic acid are subjected to heating reflux reaction to obtain the pigment derivative.

[0011] More specifically, the preparation process of the pigment derivative comprises the following steps.

[0012] S1: under stirring, 1 part of phthalocyanine pigment is added into 5-7 parts of chlorosulfonic acid and 2-3 parts of concentrated sulfuric acid, and stirring is performed for 30-60 min; 0.5-1 part of thionyl chloride is added, and the temperature is slowly increased to 70-120 DEG C, and reaction is performed for 4-8 h, and then the temperature is decreased, and the product is filtered, washed and dried to obtain sulfonated phthalocyanine pigment;

[0013] S2: the sulfonated phthalocyanine pigment obtained in step S1 is added into 5-10 parts of water, and the pH value is controlled to be 8.0-10.0 by using a pH value regulator, and 0.5-1 part of a compound containing an amino end group and a hydroxyl end group is added, and the temperature is maintained at 90-150 DEG C, and reaction is performed for 4-10 h, and then the temperature is decreased, and the product is filtered, washed and dried to obtain phthalocyanine pigment containing a hydroxyl group;

[0014] S3: the phthalocyanine pigment containing a hydroxyl group obtained in step S2, 0.5-1 part of an aromatic acid and 0.5-1 part of concentrated sulfuric acid are added into 5-10 parts of cyclohexane, and heating reflux reaction is performed for 2-4 h, and then the temperature is decreased, and the product is filtered, washed and dried to obtain the pigment derivative.

[0015] Preferably, the phthalocyanine pigment is any one of phthalocyanine blue and phthalocyanine green.

[0016] Preferably, the compound containing terminal amino and terminal hydroxyl is one of ethanolamine, 3-amino-1-propanol, p-amino benzyl alcohol, and more preferably ethanolamine; the aromatic acid is one of benzoic acid, phenylacetic acid, and phenylpropionic acid, and more preferably benzoic acid. The pH regulator is one of sodium hydroxide, potassium hydroxide, ammonia, sodium bicarbonate, disodium hydrogen phosphate, and triethanolamine.

[0017] Another aspect of the present application provides a liquid colorant comprising the following components in percentage by weight: carrier resin 55-90%, modified phthalocyanine pigment 10-40%, and functional additive 0-5%.

[0018] Preferably, the carrier resin is aromatic dibasic acid aliphatic glycol ester oligomer, which is prepared by esterification reaction of aromatic dibasic acid and aliphatic glycol; wherein the aromatic dibasic acid is preferably one of terephthalic acid and isophthalic acid, and more preferably terephthalic acid; the aliphatic glycol is preferably one of ethylene glycol, propylene glycol, and butylene glycol, and more preferably ethylene glycol.

[0019] Further, the aromatic dibasic acid aliphatic glycol ester oligomer is terephthalic acid ethylene glycol ester oligomer with a degree of polymerization of 1-8, and more preferably terephthalic acid ethylene glycol ester oligomer with a degree of polymerization of 1-5.

[0020] Further, the functional additive is a functional substance such as flame retardant, antioxidant, and anti-ultraviolet absorbing agent. The flame retardant is a substance such as triphenyl phosphate, tricresyl phosphate, triethyl phosphate, bromine-containing triphosphate ester, and dithio pyrophosphate; the antioxidant is a substance such as antioxidant 168, antioxidant 1010, antioxidant 1076, and antioxidant 1098; and the anti-ultraviolet absorbing agent is a substance such as benzotriazole type UV absorbing agent and benzoxazolone type UV absorbing agent.

[0021] The present application also provides a preparation method of the liquid colorant, which comprises: adding the functional additive to the carrier resin, dispersing for 30-60 min at a rotation speed of 600-2000 r / min, then adding the modified phthalocyanine pigment, continuing to disperse for 30-60 min, grinding 2-4 times by a grinder, and filtering to obtain the liquid colorant.

[0022] The application further provides application of the liquid colorant in in-situ polymerization of polyester fibers. Specifically, the liquid colorant is added in the in-situ polymerization process of polyester, and more preferably, the liquid colorant and catalyst are injected into a polyester oligomer pipeline on line, mixed with polyester oligomers from an esterification system, and then subjected to pre-polycondensation and final polycondensation reactions, and then subjected to spinning to obtain colored polyester fibers. The pre-polycondensation reaction has a reaction temperature of 245-265°C and a reaction time of 60-120 min; the final polycondensation reaction has a reaction temperature of 250-270°C and a reaction time of 90-180 min; the spinning temperature is 245-280°C; and the mass of the modified phthalocyanine pigment accounts for 1-5% of the mass of the polyester oligomer, preferably 3%. More preferably, the polyester oligomers from the esterification system and the carrier resin used for the liquid colorant are the same polymer with consistent polymerization degrees.

[0023] The application has the following beneficial effects:

[0024] The modified phthalocyanine pigment contains 1-10% of a pigment derivative prepared by sulfonating a phthalocyanine structure pigment, and then modifying the phthalocyanine structure pigment with a compound containing an amino end and a hydroxyl end and an aromatic acid to obtain a phthalocyanine pigment derivative containing a benzoate structure. The pigment derivative of the phthalocyanine structure has a similar structure to a common phthalocyanine pigment, and can promote adsorption of the pigment derivative on the surface of the pigment; meanwhile, the long chain grafted on the pigment derivative is dispersed in the carrier resin, and the grafted long chain acts as a dispersant, so that the pigment derivative has self-dispersing property, reduces the use of a dispersant, solves the problem that the traditional dispersant is desorbed from the surface of the pigment due to poor anchoring effect caused by excessively high temperature in the polyester polymerization process, and causes pigment particles to agglomerate and be not conducive to dispersion in the polyester. The pigment derivative has a benzoate structure, and has good compatibility with an aromatic dibasic acid aliphatic glycol ester oligomer, improves the flowability and dispersion stability of the pigment, and improves the dispersion stability of the phthalocyanine pigment in the in-situ polymerization process of the polyester.

[0025] The liquid colorant prepared by using the modified phthalocyanine pigment has small particle size, low viscosity and good storage stability; the modified phthalocyanine pigment is dispersed in the carrier resin to form a stable liquid dispersant, avoids flying of pigment particles in the air, and avoids dust pollution and influence on material ratio accuracy.

[0026] In the polyester fiber production process, i.e. pre-polycondensation, polycondensation and subsequent spinning process, the modified phthalocyanine pigment has good compatibility and dispersion with the system, the prepared polyester fibers have uniform color, and have good breaking strength, breaking elongation, soaping fastness and rubbing fastness.

[0027] The liquid colorant of the present application uses aromatic dibasic acid aliphatic dibasic alcohol ester oligomer as carrier resin, which can participate in subsequent reaction without removing waste liquid or impurities when adding liquid colorant in pre-polycondensation. DETAILED DESCRIPTION

[0028] The preferred embodiments of the present application are described in detail below to make the advantages and features of the present application more easily understood by those skilled in the art, so as to make the protection scope of the present application more clearly defined.

[0029] The present application provides a modified phthalocyanine pigment, which comprises the following components in percentage by weight: phthalocyanine pigment 90-99%, pigment derivative 1-10%; the pigment derivative is prepared by sulfonating phthalocyanine pigment and then modifying it with a compound containing terminal amino group and terminal hydroxyl group and aromatic acid; the pigment derivative has benzoate structure.

[0030] Specifically, the preparation process of the pigment derivative comprises the following steps:

[0031] S1: under stirring, 1 part of phthalocyanine pigment is added into 5-7 parts of chlorosulfonic acid and 2-3 parts of concentrated sulfuric acid, and stirred for 30-60 min; 0.5-1 part of thionyl chloride is added, and slowly heated to 70-120℃, and reacted for 4-8 h, then cooled, filtered, washed and dried to obtain sulfonated phthalocyanine pigment;

[0032] S2: the sulfonated phthalocyanine pigment prepared in step S1 is added into 5-10 parts of water, and the pH value is controlled to 8.0-10.0 by using a pH value regulator, 0.5-1 part of a compound containing terminal amino group and terminal hydroxyl group is added, the temperature is maintained at 90-150℃, and reacted for 4-10 h, then cooled, filtered, washed and dried to obtain phthalocyanine pigment containing hydroxyl group;

[0033] S3: the phthalocyanine pigment containing hydroxyl group obtained in step S2, 0.5-1 part of aromatic acid and 0.5-1 part of concentrated sulfuric acid are added into 5-10 parts of cyclohexane, heated to reflux for 2-4 h, then cooled, filtered, washed and dried to obtain pigment derivative.

[0034] The phthalocyanine pigment is any one of phthalocyanine blue and phthalocyanine green.

[0035] The compound containing terminal amino group and terminal hydroxyl group is one of ethanolamine, 3-amino-1-propanol and p-amino benzyl alcohol, and is more preferably ethanolamine; the aromatic acid is one of benzoic acid, phenylacetic acid and phenylpropionic acid, and is more preferably benzoic acid; the pH value regulator is one of sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, disodium hydrogen phosphate and triethanolamine.

[0036] The present application further provides a liquid colorant comprising the following components by weight percentage: carrier resin 55-90%, modified phthalocyanine pigment 10-40%, functional additive 0-5%. The carrier resin is aromatic dibasic acid aliphatic glycol ester oligomer, which is prepared by esterification reaction of aromatic dibasic acid and aliphatic glycol; the aromatic dibasic acid is preferably one of terephthalic acid and isophthalic acid, and more preferably terephthalic acid; the aliphatic glycol is preferably one of ethylene glycol, propylene glycol and butylene glycol, and more preferably ethylene glycol.

[0037] Further, the aromatic dibasic acid aliphatic glycol ester oligomer is preferably terephthalic acid ethylene glycol ester oligomer with a polymerization degree of 1-8, and more preferably terephthalic acid ethylene glycol ester oligomer with a polymerization degree of 1-5.

[0038] The functional additive is a substance with function such as flame retardant, antioxidant, anti-ultraviolet absorber, etc. The flame retardant is a substance such as triphenyl phosphate, tricresyl phosphate, triethyl phosphate, bromine-containing triphosphate, dithio pyrophosphate, etc. The antioxidant is a substance such as antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 1098, etc. The anti-ultraviolet absorber is a substance such as benzotriazole type UV absorber, benzoxazolone type UV absorber, etc.

[0039] The present application further provides a preparation method of the liquid colorant, which comprises the following steps: adding the functional additive to the carrier resin, dispersing for 30-60 min at a rotation speed of 600-2000 r / min, then adding the modified phthalocyanine pigment, continuing to disperse for 30-60 min, grinding for 2-4 times by a grinder, and filtering to obtain the liquid colorant.

[0040] The present application further provides application of the liquid colorant in in-situ polymerization of polyester fiber. Specifically, the liquid colorant is added in the process of in-situ polymerization of polyester, and more preferably, the liquid colorant and catalyst are injected on line into a polyester oligomer pipeline, mixed with polyester oligomer from an esterification system, and then subjected to pre-polycondensation and final polycondensation reaction, and then subjected to spinning to obtain colored polyester fiber. The pre-polycondensation reaction is carried out at a reaction temperature of 245-265 ℃ for 60-120 min; the final polycondensation reaction is carried out at a reaction temperature of 250-270 ℃ for 90-180 min; the spinning temperature is 245-280 ℃; and the mass of the modified phthalocyanine pigment accounts for 1-5% of the mass of the polyester oligomer, and preferably 3%. More preferably, the polyester oligomer from the esterification system and the carrier resin used for the liquid colorant are the same polymer with consistent polymerization degree.

[0041] Example 1

[0042] Modified phthalocyanine pigment A1-1: comprising 95 parts by mass of phthalocyanine blue 15:3 pigment, 5 parts by mass of pigment derivative; wherein the preparation method of the pigment derivative is:

[0043] S1: under stirring, 1 part by mass of phthalocyanine blue 15:3 pigment was added into 6 parts by mass of chlorosulfonic acid and 2.5 parts by mass of concentrated sulfuric acid, and stirred for 45 min; 0.8 parts by mass of sulfoxide chloride was added, and slowly heated to 90℃, and reacted for 6 h, then cooled, filtered, washed and dried to obtain a sulfonylated phthalocyanine pigment;

[0044] S2: the sulfonylated phthalocyanine pigment prepared in step S1 was added into 8 parts by mass of water, and the pH value was adjusted to 9.0 with a sodium hydroxide solution with a concentration of 1 mol / L, and 0.8 parts by mass of ethanolamine was added, and the temperature was kept at 120℃, and reacted for 7 h, then cooled, filtered, washed and dried to obtain a hydroxyl-containing phthalocyanine pigment;

[0045] S3: the hydroxyl-containing phthalocyanine pigment obtained in step S2, 0.7 parts by mass of benzoic acid and 0.8 parts by mass of concentrated sulfuric acid were added into 8 parts by mass of cyclohexane, and heated to reflux for 3 h, then cooled, filtered, washed and dried to obtain a pigment derivative.

[0046] Preparation of liquid colorant and colored polyester fiber:

[0047] 2 parts by mass of antioxidant 168 was added into 68 parts by mass of terephthalic acid ethylene glycol oligomer with a polymerization degree of 3, and dispersed for 45 min under the condition of a rotation speed of 1000 r / min; then 30 parts by mass of modified phthalocyanine pigment A1-1 was added, and dispersed for another 45 min; ground for 3 times in a grinder, and filtered to obtain phthalocyanine pigment liquid colorant B1-1.

[0048] To 100 parts by mass of terephthalic acid ethylene glycol oligomer with a polymerization degree of 3 from an esterification system, 10 parts by mass of phthalocyanine pigment liquid colorant B1-1 and 0.1 parts by mass of tetrabutyl titanate as a catalyst were added, and uniformly mixed, and then pre-polycondensation was carried out at 255℃ for 60 min; polycondensation reaction was carried out at 260℃ for 120 min; and colored polyester fiber C1-1 was obtained by spinning at 270℃ and a winding speed of 4500 m / min.

[0049] Example 2

[0050] Modified phthalocyanine pigment A1-2: comprising 99 parts by mass of phthalocyanine blue 15:3 pigment, 1 part by mass of pigment derivative; wherein the preparation method of the pigment derivative is:

[0051] S1: under stirring, 1 part of phthalocyanine blue 15:3 pigment was added into 5 parts of chlorosulfonic acid and 2 parts of concentrated sulfuric acid, and stirred for 30 min; 0.5 part of thionyl chloride was added, and slowly heated to 70℃, reacted for 8 h, then cooled, filtered, washed and dried to obtain sulfonated phthalocyanine pigment;

[0052] S2: the sulfonated phthalocyanine pigment prepared in step S1 was added into 5 parts of water, and the pH value was adjusted to 8.0 by using 1 mol / L potassium hydroxide solution, and 0.5 part of ethanolamine was added, and the temperature was kept at 90℃, and reacted for 10 h, then cooled, filtered, washed and dried to obtain hydroxyl-containing phthalocyanine pigment;

[0053] S3: the hydroxyl-containing phthalocyanine pigment obtained in step S2, 0.5 part of benzoic acid and 0.5 part of concentrated sulfuric acid were added into 5 parts of cyclohexane, and heated to reflux for 4 h, then cooled, filtered, washed and dried to obtain pigment derivative.

[0054] Preparation of liquid colorant and colored polyester fiber:

[0055] 5 parts of tricresyl phosphate was added in 55 parts of terephthalic acid ethylene glycol oligomer with a degree of polymerization of 1, and dispersed for 60 min under the condition of 600 r / min; then 40 parts of modified phthalocyanine pigment A1-2 was added, and dispersed for another 60 min; ground in a grinder for 4 times, and filtered to obtain phthalocyanine pigment liquid colorant B1-2.

[0056] To 100 parts of terephthalic acid ethylene glycol oligomer with a degree of polymerization of 1 from an esterification system, 7.5 parts of phthalocyanine pigment liquid colorant B1-2 and 0.1 part of tetrabutyl titanate as catalyst were added, mixed uniformly, and then pre-polycondensation was carried out at 245℃ for 120 min; polycondensation reaction was carried out at 250℃ for 120 min; and colored polyester fiber C1-2 was obtained by spinning at 270℃ and winding speed of 4500 m / min.

[0057] Example 3

[0058] Modified phthalocyanine pigment A1-3: including 90 parts of phthalocyanine blue 15:3 pigment and 10 parts of pigment derivative; wherein the preparation method of the pigment derivative is as follows:

[0059] S1: under stirring, 1 part of phthalocyanine blue 15:3 pigment was added into 7 parts of chlorosulfonic acid and 3 parts of concentrated sulfuric acid, and stirred for 60 min; 1 part of thionyl chloride was added, and slowly heated to 120℃, reacted for 4 h, then cooled, filtered, washed and dried to obtain sulfonated phthalocyanine pigment;

[0060] S2: The sulfonated phthalocyanine pigment prepared in step S1 was added to 10 parts of water, and the pH value was adjusted to 10.0 using a sodium hydroxide solution with a concentration of 1 mol / L. Then, 1 part of ethanolamine was added, and the temperature was maintained at 150°C for 4 hours. After cooling, filtration, washing, and drying, a hydroxyl-containing phthalocyanine pigment was obtained.

[0061] S3: The hydroxyl-containing phthalocyanine pigment obtained in step S2, 1 part of benzoic acid, and 1 part of concentrated sulfuric acid were added to 10 parts of cyclohexane. After refluxing at a high temperature for 2 hours, the mixture was cooled, filtered, washed, and dried to obtain a pigment derivative.

[0062] Preparation of a liquid colorant and a colored polyester fiber:

[0063] Antioxidant 1010 with a mass of 3 parts was added to polyethylene terephthalate oligomers with a degree of polymerization of 3 and a mass of 77 parts, and dispersed for 50 minutes at a rotation speed of 1500 r / min. Then, modified phthalocyanine pigment A1-3 with a mass of 20 parts was added, and the dispersion was continued for another 50 minutes. The mixture was ground in a grinder for 2 times, and then filtered to obtain phthalocyanine pigment liquid colorant B1-3.

[0064] To polyethylene terephthalate oligomers with a degree of polymerization of 3 and a mass of 100 parts from an esterification system, phthalocyanine pigment liquid colorant B1-3 with a mass of 15 parts and tetrabutyl titanate with a mass of 0.1 parts as a catalyst were added. After mixing, pre-polycondensation was performed at 255°C for 60 minutes. Then, polycondensation was performed at 260°C for 120 minutes. Finally, spinning was performed at 270°C with a winding speed of 4500 m / min to obtain colored polyester fiber C1-3.

[0065] Example 4

[0066] Modified phthalocyanine pigment A1-4: including 95 parts of phthalocyanine green 36 pigment and 5 parts of pigment derivative; wherein the preparation method of the pigment derivative is as follows:

[0067] S1: Under stirring, 1 part of phthalocyanine green 36 pigment was added to 6 parts of chlorosulfonic acid and 3 parts of concentrated sulfuric acid, and stirred for 60 minutes. Then, 1 part of thionyl chloride was added, and the temperature was slowly increased to 100°C. After reacting for 6 hours, the mixture was cooled, filtered, washed, and dried to obtain a sulfonated phthalocyanine pigment.

[0068] S2: The sulfonated phthalocyanine pigment prepared in step S1 was added to 8 parts of water, and the pH value was adjusted to 10.0 using a sodium hydroxide solution with a concentration of 1 mol / L. Then, 1 part of ethanolamine was added, and the temperature was maintained at 120°C for 7 hours. After cooling, filtration, washing, and drying, a hydroxyl-containing phthalocyanine pigment was obtained.

[0069] S3: The hydroxyl-containing phthalocyanine pigment obtained in step S2, 1 part by mass of benzoic acid, and 0.8 part by mass of concentrated sulfuric acid were added to 8 parts by mass of cyclohexane, and heated to reflux for 3 h. After cooling, filtration, washing, and drying, a modified phthalocyanine pigment A1-4 was obtained.

[0070] Preparation of a liquid colorant and a colored polyester fiber:

[0071] 1 part by mass of dithiophosphoric acid ester was added to 89 parts by mass of terephthalic acid ethylene glycol ester oligomer having a degree of polymerization of 5, and dispersed at a rotation speed of 2000 r / min for 30 min. Then, 10 parts by mass of the modified phthalocyanine pigment A1-4 was added, and the dispersion was continued for 30 min. The mixture was ground in a grinder for 2 times, and filtered to obtain a phthalocyanine pigment liquid colorant B1-4.

[0072] To 100 parts by mass of terephthalic acid ethylene glycol ester oligomer having a degree of polymerization of 5 from an esterification system, 30 parts by mass of the phthalocyanine pigment liquid colorant B1-4 and 0.1 part by mass of tetrabutyl titanate as a catalyst were added, mixed, and subjected to pre-polycondensation at 265°C for 90 min. Then, polycondensation was performed at 270°C for 120 min. Finally, the mixture was spun at 270°C at a winding speed of 4500 m / min to obtain a colored polyester fiber C1-4.

[0073] Comparative Example 1

[0074] Modified phthalocyanine pigment A2-1: including 95 parts by mass of phthalocyanine blue 15:3 pigment and 5 parts by mass of a pigment derivative; wherein the pigment derivative was prepared by:

[0075] S1: 1 part by mass of phthalocyanine blue 15:3 pigment was added to 6 parts by mass of chlorosulfonic acid and 2.5 parts by mass of concentrated sulfuric acid under stirring, and stirred for 45 min. Then, 0.8 parts by mass of thionyl chloride was added, and the temperature was slowly increased to 90°C. After reaction for 6 h, the mixture was cooled, filtered, washed, and dried to obtain a sulfonylated phthalocyanine pigment.

[0076] S2: The sulfonylated phthalocyanine pigment obtained in step S1 was added to 8 parts by mass of water, and the pH value was adjusted to 9.0 using sodium hydroxide pH adjuster. Then, 0.8 parts by mass of ethylenediamine was added, and the temperature was maintained at 120°C for 7 h. After cooling, filtration, washing, and drying, an aminolysis phthalocyanine pigment was obtained.

[0077] S3: 0.8 parts by mass of chloroacetic acid was dissolved in 10 parts by mass of anhydrous ethanol, and the pH value was adjusted to 9.0 using sodium hydroxide pH adjuster. Then, the aminolysis phthalocyanine pigment obtained in step S2 was added, and the temperature was maintained at 60°C for 6 h. Finally, the mixture was purified and dried to obtain a pigment derivative.

[0078] Preparation of liquid colorant and colored polyester fiber:

[0079] Add 2 parts of antioxidant 168 to 68 parts of polyethylene terephthalate oligomer with a degree of polymerization of 3, disperse at a rotation speed of 1000 r / min for 45 min; then add 30 parts of modified phthalocyanine pigment A2-1, continue to disperse for 45 min; grind in a grinder for 3 times, and filter to obtain phthalocyanine pigment liquid colorant B2-1.

[0080] To 100 parts of polyethylene terephthalate oligomer with a degree of polymerization of 3 from the esterification system, add 10 parts of phthalocyanine pigment liquid colorant B2-1 and 0.1 parts of tetrabutyl titanate as a catalyst, mix uniformly, and then pre-polymerize at 255℃ for 60 min; perform a polycondensation reaction at 260℃ for 120 min; and spin at 270℃ and a winding speed of 4500 m / min to obtain colored polyester fiber C2-1.

[0081] Comparative Example 2

[0082] Modified phthalocyanine pigment A2-2: comprising 95 parts of phthalocyanine blue 15:3 pigment and 5 parts of pigment derivative; wherein the preparation method of the pigment derivative is as follows:

[0083] S1: under stirring, add 1 part of phthalocyanine blue 15:3 pigment to 6 parts of chlorosulfonic acid and 2.5 parts of concentrated sulfuric acid, stir for 45 min; add 0.8 parts of thionyl chloride, slowly heat to 90℃, react for 6 h, then cool, filter, wash, and dry to obtain a sulfonylated phthalocyanine pigment;

[0084] S2: add the sulfonylated phthalocyanine pigment obtained in step S1 to 8 parts of water, adjust the pH value to 9.0 with a sodium hydroxide solution with a concentration of 1 mol / L, add 0.8 parts of ethanolamine, maintain the temperature at 120℃, react for 7 h, then cool, filter, wash, and dry to obtain a pigment derivative.

[0085] Preparation of liquid colorant and colored polyester fiber:

[0086] Add 2 parts of antioxidant 168 to 68 parts of polyethylene terephthalate oligomer with a degree of polymerization of 3, disperse at a rotation speed of 1000 r / min for 45 min; then add 30 parts of modified phthalocyanine pigment A2-2, continue to disperse for 45 min; grind in a grinder for 3 times, and filter to obtain phthalocyanine pigment liquid colorant B2-2.

[0087] To the oligomer of ethylene glycol terephthalate with a degree of polymerization of 3 from the esterification system with a mass of 100 parts, add 10 parts of phthalocyanine pigment liquid colorant B2-2, 0.1 parts of tetrabutyl titanate as a catalyst, mix uniformly, and then react at 255°C for 60 min to perform pre-polycondensation; react at 260°C for 120 min to perform polycondensation; spin at 270°C with a winding speed of 4500 m / min to obtain colored polyester fiber C2-2.

[0088] Comparative Example 3

[0089] Phthalocyanine pigment A2-3: 100 parts of phthalocyanine blue 15:3 pigment without adding pigment derivatives.

[0090] Preparation of liquid colorant and colored polyester fiber:

[0091] Add 2 parts of antioxidant 168 to 68 parts of oligomer of ethylene glycol terephthalate with a degree of polymerization of 3, disperse at a speed of 1000 r / min for 45 min; then add 30 parts of phthalocyanine pigment A2-3, continue to disperse for 45 min; grind in a grinder for 3 times, and filter to obtain phthalocyanine pigment liquid colorant B2-3.

[0092] To the oligomer of ethylene glycol terephthalate with a degree of polymerization of 3 from the esterification system with a mass of 100 parts, add 10 parts of phthalocyanine pigment liquid colorant B2-3, 0.1 parts of tetrabutyl titanate as a catalyst, mix uniformly, and then react at 255°C for 60 min to perform pre-polycondensation; react at 260°C for 120 min to perform polycondensation; spin at 270°C with a winding speed of 4500 m / min to obtain colored polyester fiber C2-3.

[0093] Performance test of phthalocyanine pigment liquid colorant

[0094] The particle size and viscosity of the prepared phthalocyanine pigment liquid colorant were tested, and the particle size and viscosity were tested after 30 days of storage. The test data are shown in Table 1.

[0095] Particle size test: The particle size of the phthalocyanine pigment liquid colorant prepared in the examples and comparative examples was tested according to the national standard “GB / T 19077-2016 Particle Size Distribution Laser Diffraction Method”. In the test results, D50 represents the smallest particle size that 50% of the measured particles can pass through.

[0096] Viscosity test: The viscosity of the phthalocyanine pigment liquid colorant prepared in the examples and comparative examples was tested according to the national standard “GB / T 15357-2014 Surface Active Agents and Detergents Rotary Viscometer Determination of Viscosity and Flow Properties of Liquid Products”.

[0097] Table 1. Test results of phthalocyanine pigment liquid colorant

[0098]

[0099] As can be seen from Table 1, the D50 of the phthalocyanine pigment liquid colorant prepared in the examples is 220-240 nm, the viscosity is 1310-1580 mPa·s, the D50 is 224-258 nm after storage for 30 days, and the viscosity is 1436-1681 mPa·s; while the D50 of the phthalocyanine pigment liquid colorant prepared in the comparative examples is 249-262 nm, the viscosity is 1790-2220 mPa·s, the D50 is 812-1225 nm after storage for 30 days, and the viscosity is 2679-4459 mPa·s. The particle size and viscosity of the phthalocyanine pigment liquid colorant prepared in the comparative examples are slightly larger than those of the examples; but the particle size and viscosity change greatly after storage for 30 days, which shows that the phthalocyanine pigment prepared in the comparative examples has poor compatibility with the carrier resin, resulting in poor storage stability.

[0100] Performance test of colored polyester fiber

[0101] The prepared colored polyester fiber was tested according to the following method:

[0102] Uniformity of color and luster: the uniformity of color and luster of the colored polyester fiber was observed, √ indicating that the color and luster were uniform and flawless; ○ indicating that the color and luster were uneven and flawed, but could be found only by careful observation; and × indicating that the color and luster were obviously uneven and flawed.

[0103] Breaking strength and elongation at break: refer to GB / T 14344-2022 “Chemical fiber filament tensile property test method”;

[0104] Soaping fastness test: the colored polyester fiber was woven into a sock belt, and the soaping fastness of the sock belt was tested according to GB / T 3921-2008 “Textile color fastness test soaping fastness”.

[0105] Rubbing fastness test: refer to GB / T 3920-2008 “Textile color fastness test rubbing fastness”, using a dyeing rubbing fastness tester to test the dry and wet rubbing fastness of the sock belt.

[0106] The test results are shown in Table 2.

[0107] Table 2. Performance test results of colored polyester fiber

[0108]

[0109] The colored polyester fiber prepared in the example has uniform color, the breaking strength is 3.8-3.9 cN / dtex, the breaking elongation is 33-35%, the soaping fastness is ≥4 grade, and the rubbing fastness is ≥4 grade. The colored polyester fiber prepared in the comparative example has uneven color and defects, the breaking strength is 2.1-2.3 cN / dtex, the breaking elongation is 22-24%, the soaping fastness is 3-4 grade, and the rubbing fastness is 3-4 grade. It can be seen that the color uniformity, breaking strength, breaking elongation, soaping fastness and rubbing fastness of the colored polyester fiber prepared in the example are all superior to those of the colored polyester fiber prepared in the comparative example.

[0110] As can be seen from the comparison between the example and the comparative example, the liquid colorant prepared by using the modified phthalocyanine pigment of the present application has small particle size, low viscosity and good storage stability, and the colored polyester fiber prepared therefrom has uniform color and good breaking strength, breaking elongation, soaping fastness and rubbing fastness.

[0111] It is apparent for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other concrete forms without departing from the spirit or essential characteristics of the present application. Thus, the embodiments should be considered in all respects as illustrative and not restrictive, and the scope of the present application is defined by the appended claims rather than the above description, and it is intended to embrace all changes falling within the meaning and range of equivalents of the claims. Any mark in the claims should not be considered as limiting the involved claims.

[0112] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the present specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A modified phthalocyanine pigment, characterized in that, The composition by weight percentage is as follows: 90-99% phthalocyanine pigment, 1-10% pigment derivative; The preparation process of the pigment derivative is as follows: phthalocyanine pigment is added to chlorosulfonic acid for sulfonation, followed by chlorination with thionyl chloride to obtain sulfonated phthalocyanine pigment; then, the sulfonated phthalocyanine pigment is added to water, the pH is adjusted with a pH adjuster, and a compound containing terminal amino and terminal hydroxyl groups is added, followed by a reaction to obtain hydroxyl-containing phthalocyanine pigment; finally, the hydroxyl-containing phthalocyanine pigment and an aromatic acid are heated under reflux to obtain the pigment derivative. The compound containing terminal amino and terminal hydroxyl groups is one of ethanolamine, 3-amino-1-propanol, and p-aminobenzyl alcohol; the aromatic acid is one of benzoic acid, phenylacetic acid, and phenylpropionic acid.

2. The modified phthalocyanine pigment according to claim 1, characterized in that, The preparation process of the pigment derivative includes the following steps: S1: Under stirring conditions, 1 part by mass of phthalocyanine pigment is added to 5-7 parts by mass of chlorosulfonic acid and 2-3 parts by mass of concentrated sulfuric acid, and stirred for 30-60 min; 0.5-1 part by mass of thionyl chloride is added, the temperature is slowly raised to 70-120℃, and the reaction is carried out for 4-8 h. After cooling, filtration, washing and drying, sulfonated phthalocyanine pigment is obtained. S2: Add the sulfonated phthalocyanine pigment obtained in step S1 to 5-10 parts by mass of water, control the pH value to 8.0-10.0 with a pH adjuster, add 0.5-1 parts by mass of a compound containing terminal amino and terminal hydroxyl groups, maintain the temperature at 90-150℃, react for 4-10 hours, and after cooling, filtering, washing and drying, obtain hydroxyl-containing phthalocyanine pigment; S3: Add the hydroxyl-containing phthalocyanine pigment obtained in step S2, 0.5-1 parts by mass of aromatic acid, and 0.5-1 parts by mass of concentrated sulfuric acid to 5-10 parts by mass of cyclohexane, heat under reflux for 2-4 hours, and then cool, filter, wash, and dry to obtain the pigment derivative.

3. The modified phthalocyanine pigment according to claim 1, characterized in that, The phthalocyanine pigment is either phthalocyanine blue or phthalocyanine green.

4. A liquid colorant, characterized in that, The product comprises the following components by weight percentage: 55-90% carrier resin, 10-40% modified phthalocyanine pigment as described in any one of claims 1 to 3, and 0-5% functional additives.

5. A liquid colorant according to claim 4, characterized in that, The carrier resin is an aromatic dicarboxylic acid aliphatic diol ester oligomer.

6. A liquid colorant according to claim 5, characterized in that, The aromatic dicarboxylic acid aliphatic diol ester oligomer is a terephthalic acid glycol ester oligomer with a degree of polymerization of 1 to 8.

7. The method for preparing the liquid colorant according to any one of claims 4-6, characterized in that, The functional additives are added to the carrier resin and dispersed for 30-60 minutes at a speed of 600-2000 r / min. Then, the modified phthalocyanine pigment is added and dispersed for another 30-60 minutes. The mixture is then ground 2-4 times and filtered to obtain a liquid colorant.

8. The application of the liquid colorant as described in any one of claims 4-6 in the in-situ polymerization of polyester fibers.

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