KR100848220B1 - Multi functional surfactant for polyester dyeing - Google Patents

Abstract

A multi functional surfactant for dyeing a polyester is provided to raise the dispersibility and dyeability of the dispersive dyes by preventing the oligomer, the metal ion and the pH change from generating in the process. A multi functional surfactant for dyeing a polyester consists of an oligomer remover of 17-30 wt% as the reactant of an ethylene-oxide/propylene-oxide copolymer and a TPA(TerePhthalic Acid), a metal ion blocker of 20-30 wt% as the reactant of an acrylic acid and a propylene-oxide added ester compound, a naphthalene of 5-10 wt%, a buffer solution of 22-40 wt%, and water as the remainder. The rate of the ethylene-oxide and the propylene-oxide in the oligomer remover is 70:30 to 95:5. The oligomer remover has the pH value of 6.5-7.5, acid value of less than 5, weight averaged molecular weight of 500-3000, and the non-ionic property. The rate of the ethylene-oxide and the propylene-oxide in the metal ion blocker is 70:30 to 95:5. The metal ion blocker has the pH value of 6.5-7.5, non-volatile ingredient of 60-70%, weight averaged molecular weight of 2000-20000, and the negative-ionic property.

Description

Multifunctional Surfactant For Polyester Dyeing

The present invention relates to a multifunctional dispersant for dyeing polyester to remove oligomers mainly generated in the dyeing and processing process of polyester, to block metal ions in a dye bath, and to improve dispersibility of disperse dyes.

In general, after the alkali weight loss processing of the dyeing process of the polyester fabric is subjected to washing and removal of the weight loss decomposition products through the washing process. However, if a weight loss park group is added to the dyeing machine during the dyeing process, and the salt bath is adjusted to acidic condition, the soluble DST, which is a weight loss product, is changed to an insoluble TPA type oligomer, thereby degrading the quality, dispersibility, and level of dye.

In addition, in the dyeing of the dye, in addition to the disperse dye, an anionic surfactant of lignin sulfonate and a nonionic surfactant such as polyoxyalkylene glyceryl ether fatty acid, a dispersing agent and a homogenizing agent are added. Rather, dispersibility and homogenization are deteriorated, resulting in agglomeration of dyes, generation of stains and color differences on dyeings, and discoloration.

Therefore, in order to improve the dyeability of high-performance polyester fabrics and the quality of products to meet the increasing demands of various textile materials today, oligomer removers or metal ion blockers that can prevent defects caused by inorganic salts in oligomers and salt baths And it is essential to use a dispersing agent, leveling agent, etc. that can minimize the discoloration phenomenon of the dyeing and the color difference between the dye lot (lot).

Therefore, according to the present invention, it is possible to remove oligomers mainly generated in the dyeing and processing process of polyester, to block metal ions in the salt bath, to improve dispersibility of the disperse dyes, and to maintain a constant pH. It is a technical problem to provide a multifunctional dispersing agent for polyester dyeing.

Therefore, according to the present invention, 17 to 30% by weight of the oligomer remover of Chemical Formula 1, which is a reactant between ethylene oxide / propylene oxide copolymer and TPA, and the metal ion blocking agent of Chemical Formula 2, which is a reactant of acrylic acid and ethylene oxide / propylene oxide addition ester, 30% by weight, naphthalene dispersant 5 to 10% by weight, buffer solution 22 to 40% by weight and the remainder is provided a multi-functional dispersant for polyester dyeing, characterized in that it comprises water.

[Formula 1]

(n is an integer from 10 to 30, m is an integer from 2 to 10.)

[Formula 2]

(x is an integer from 50 to 300, y is an integer from 5 to 50, n is an integer from 5 to 15, and m is an integer from 1 to 10.)

Hereinafter, the present invention will be described in more detail.

The present invention relates to a multifunctional dispersant for dyeing polyester to remove oligomers mainly generated in the dyeing and processing process of polyester, to block metal ions in a dye bath, and to improve dispersibility of disperse dyes.

The multifunctional dispersant for dyeing the polyester of the present invention is an oligomer remover of Formula 1, which is a reactant between ethylene oxide / propylene oxide copolymer and TPA, and a metal ion sequestrant of Formula 2, which is a reactant of acrylic acid and ethylene oxide / propylene oxide addition ester, naphthalene Dispersants, buffers and water.

The oligomer remover of Formula 1, which is a reactant between ethylene oxide / propylene oxide copolymer and TPA, which is a component of the multifunctional dispersant for dyeing of the present invention, may have the performance of the dispersant together with the oligomer removal ability. The oligomer remover copolymer and terephthalic acid of propylene oxide (hereinafter referred to as PO) and ethylene oxide (hereinafter referred to as EO) having a property of increasing dispersibility as shown in Chemical Formula 3 The reaction is carried out using paratoluene sulphonic acid (PTSA) as a catalyst for 10-15 hours while stirring the temperature to 240-250 ° C. while adding nitrogen to the reactor into which the reactor is charged. When the value (AV) falls below 5, the water is added at a rate of 50%, cooling starts, and below 40 ° C., the reaction is obtained by completing the reaction. During the reaction, the EO / PO copolymer is added in excess.

[Formula 1]

(n is an integer from 10 to 30, m is an integer from 2 to 10.)

[Formula 3]

In the oligomer remover, the ratio of ethylene oxide and propylene oxide is preferably 70:30 to 95: 5. The increase in the ratio of EO in the EO / PO copolymer increases water solubility and increases oligomer removal but decreases dispersibility. The opposite happens when the proportion of PO increases. Therefore, by adjusting the ratio of EO and PO as described above, it is possible to optimally express the oligomer removal ability and the dispersion ability.

The oligomer remover is preferable because it has a dispersing ability similar to the structure of the oligomer generated using a pH 4 ~ 6, AV (Acid Value) 5 or less, a weight average molecular weight of 500 ~ 3,000 and nonionic.

In addition, the metal ion sequestrant represented by the following Chemical Formula 2, which is a component of the multifunctional dispersant for dyeing of the present invention, uses a reactant of acrylic acid and ethylene oxide / propylene oxide addition ester.

[Formula 2]

(x is an integer from 50 to 300, y is an integer from 5 to 50, n is an integer from 5 to 15, and m is an integer from 1 to 10.)

In general, the metal ion sequestrant is composed of acrylic acid, whereas the metal ion sequestrant of the present invention has the property of increasing dispersibility as shown in the following Chemical Formula 4 in order to retain the performance of the dispersant in addition to the metal ion sequestration ability. EO / PO addition esters with PO are used to react with acrylic acid for radical polymerization.

[Formula 4]

In order to prepare the metal ion sequestering agent of the present invention, water was added to the reactor at a rate of 50% as in Chemical Formula 4, and then the temperature was adjusted to 50 to 60 ° C., and the acrylic acid and the EO / PO addition ester were 70:30 to The catalyst (ammonium persulphate, APS) is added while slowly dropping at a ratio of 95: 5. At this time, since an exothermic reaction occurs, the temperature is adjusted to 100 to 120 ° C. while cooling with cooling water, and reacted for 6 to 8 hours. After the reaction was completed, the temperature was cooled to 40 ° C., and sodium hydroxide was added to neutralize it. When neutralization is completed, the pH is measured to confirm neutrality, and then the reaction is completed to obtain a metal ion sequestrant of the present invention.

The ratio of ethylene oxide and propylene oxide in the EO / PO addition ester is preferably 70:30 to 95: 5 as an optimal ratio having both metal ion blocking ability and dispersing ability. The metal ion sequestrant is pH 6.5 ~ 7.5, non-volatile content 60 ~ 70%, weight average molecular weight 2,000 ~ 20,000 is preferably anionic, because it is a structure that exhibits both the metal ion blocking ability and the dye and oligomer dispersing power at the same time. to be.

The naphthalene dispersant which is another component of the present invention has a dye dispersing action, and specifically, naphthalene sulfonic acid may be used. In addition, the buffer solution for stabilizing the pH of the multi-functional dispersant for dyeing polyester may be specifically used an organic acid.

The multifunctional dispersant for dyeing the polyester of the present invention is a metal of formula (2) which is 17-30% by weight of an oligomer remover of formula (I) which is a reactant between ethylene oxide / propylene oxide copolymer and TPA, and acrylic acid and ethylene oxide / propylene oxide addition ester 20-30% by weight of an ion blocker, 5-10% by weight of a naphthalene dispersant, 22-40% by weight of a buffer solution and water as the remainder, and mixed according to the above ratios. Force and effect as a buffer solution can be expressed evenly.

Multifunctional dispersing agent for dyeing of the present invention is characterized in that the pH 2 ~ 5, the sugar content 20 ~ 50 and oligomer removal force 4-5 grade, metal ion blocking power 4-5 grade and dispersibility 4-5 grade, dyeing of polyester By supplying to the salt bath during the processing process to remove the oligomers mainly generated in the dyeing process, and to block the metal ions in the dye bath, while improving the dispersibility of the disperse dyes, it has the effect of maintaining a constant pH.

Hereinafter, the following examples are given as non-limiting examples of the multi-functional dispersing agent for dyeing of the present invention and a method for producing the same.

[Synthesis Cases 1-3]

1. Synthesis of oligomer remover

The EO / PO copolymer having the EO / PO ratio and molecular weight shown in Table 1 was injected into a reactor capable of heat stirring and gas filling with a weight of 2.1 molar ratio (g) to TPA and a molecular weight of 166.13 and 300 g of TPA having a physical property of more than 99.0%. After stirring, the temperature was adjusted to 240 ° C. while adding nitrogen. At this time, para toluene sulphonic acid (PTSA) was used as a catalyst, and an excessive amount of EO / PO copolymer was added thereto. After reacting for 12 hours, the acid value (A.V.) was measured and dropped to 5 or less, water was added at a rate of 50%, cooling started, and the reaction was completed at 40 ° C. or lower.

division ethylene oxide rate (%) propylene oxide rate (%) Molecular weight (M.W) Synthesis Example 1 90 10 1,500 Synthesis Example 2 85 15 1,000 Synthesis Example 3 80 20 1,000

2. Performance evaluation of synthesized oligomer remover

The oligomer remover synthesized in Synthesis Examples 1 to 3 measured A.V., A.V. is an abbreviation of acid value and uses a neutralization titration method as a value indicating the number of mg of KOH required to neutralize the free fatty acid contained in 1 g of the sample. In the present invention, the residual degree of terephthalic acid (TPA) which is a raw material after synthesis of the oligomer remover is shown.

In addition, the synthesized oligomer remover was measured for appearance, pH, ionicity, non-volatile content, oligomer removal ability, dispersibility, respectively. The performance of the oligomer remover synthesized according to the ratio and molecular weight of EO and PO in each synthesis example was measured as shown in Table 2 below.

 Appearance was shown by sensory evaluation, pH was measured by using a pH-meter (HORIBA, F-24). Ionicity was measured in accordance with KS M 0009 Drying Loss Test Method 1 in the 'Standardization of Environmentally Friendly Dyeing Preparation' report published by the Korea Dyeing Research Institute in 1998.

The oligomer removal ability was added to the oligomer and oligomer remover / dispersant together and then filtered by 98 ℃ × 10 minutes to evaluate the grade of the material remaining on the filter paper. The higher the grade, the better the oligomer removal ability because there is no remaining material in the filter paper.

  Dispersibility is the disperse dye C.I. The oligomer remover / dispersant was added to the Disperse Blue 56 saline solution, treated at 130 ° C. for 40 minutes, cooled, filtered at 98 ° C., and the degree of filter paper residue was evaluated. The higher the grade, the better the dispersibility as there is no residue of the filter paper.

division Exterior pH Ionic Nonvolatile matter (%) A.V. Oligomer Removability (Grade) Dispersibility (grade) Synthesis Example 1 Transparent viscous liquid 5.2 Non-ion 55.0 2.2 5 5 Synthesis Example 2 Transparent viscous liquid 5.1 Non-ion 51.2 2.2 5 5 Synthesis Example 3 Transparent viscous liquid 5.3 Non-ion 55.9 2.5 5 5

As a result of the physical property measurement, the compounds showed weak acidity, non-ion, and non-volatile content of about 5% at pH 5, and AV was 2.1-2.5, indicating that terephthalic acid (TPA), which is a raw material of the synthesis, was almost used for the reaction. It was found that it has an excellent oligomer removal ability.

[Synthesis 4 to 6]

1. Synthesis of Metal Ion Blocker

Into the reactor to add dropping and cooling water, water was added at a rate of 50% and the temperature was adjusted to 60 ° C. Acrylic acid was used by LG Chemical Co., Ltd. Received from SFC Co., Ltd., acrylic acid and EO / PO addition ester were added dropwise at a ratio of 8: 2. At this time, a catalyst (ammonium persulphate, APS) was added. Since exothermic reactions occur, the reaction temperature was adjusted to 120 ° C. for 8 hours while cooling with cooling water. After the reaction was completed, the temperature was cooled to 40 ° C., and sodium hydroxide was added to neutralize the reaction. When neutralization was completed, the pH was measured to confirm neutrality, and then the reaction was completed to obtain a metal ion sequestrant as shown in Table 3.

division ethylene oxide rate (%) propylene oxide rate (%) Molecular weight Synthesis Example 4 95 5 400 Synthesis Example 5 90 10 400 Synthesis Example 6 85 15 400

2. Performance Evaluation of Synthetic Metal Ion Blockers

The performance of the metal ion sequestrant synthesized according to the ratio and molecular weight of EO and PO was measured as shown below.

The metal ion sequestrant showed the unreacted rate in% through HPLC analysis. In the reaction rate measurement through HPLC analysis, the reaction rate of acrylic acid was examined to determine whether the raw materials were used for the reaction after the synthesis of the metal ion sequestrant. As the detector, an ultraviolet absorbance photometer and a column having a diameter of 4.6 mm and a length of about 15 cm were filled with silica gel octadecylated in a 5 μm liquid chromatograph. The temperature was 40 ° C., and the mobile phase used water and acetonitrile in a ratio of 1: 1, and the flow rate was set at 1.0 ml / min. Appearance, pH, ionicity, non-volatile content, and dispersibility were measured as in Synthesis Examples 1 to 3, respectively.

Metal ion blocking power was measured by dividing the metal ion blocking power for Ca, Mg and the metal ion blocking power test for Fe. The metal ion blocking ability test for Ca and Mg was performed by adding buffer and EBT indicator to 50 ml of tap water (hardness of about 70ppm), and then putting the synthesized metal ion blocking agent into the burette to measure the amount of metal ion blocking agent consumed. . If the amount consumed represents a value of 2ml or less, it can be seen that the metal ion blocking power is excellent. To test the metal ion blocking ability of Fe, add tap water (hardness of about 70ppm) and metal ion blocking agent / dispersant, and after stirring, add FeCl ₃ · 6H ₂ O 10% solution and 50% NaOH solution sequentially and then stir for 30 minutes. The grade was determined by comparing precipitation, turbidity, and clarity with standing in. Higher grade means no precipitation and clearer and better performance.

division Exterior pH Ionic Nonvolatile matter (%) Unreacted rate of acrylic acid (%) Metal ion containment force (grade) Dispersibility (grade) Synthesis Example 4 Transparent viscous liquid 7.4 Negative ion 65.2 0.3 5 5 Synthesis Example 5 Transparent viscous liquid 7.5 Negative ion 66.6 0.1 5 5 Synthesis Example 6 Transparent viscous liquid 7.5 Negative ion 65.7 0.2 5 5

As a result of the measurement, the composites showed neutral, anion and non-volatile content of about 65% of pH 7, and the unreacted percentage of acrylic acid (%) was 0.5% or less, which was almost all used for the reaction. The metal ion blocking power was very good from the above results.

[Examples 1-5]

1. Manufacturing of Multifunctional Dispersants

According to the composition ratio of Table 5 and mixed by using a homo-mixer to obtain a multifunctional dispersant.

Example 1 Example 2 Example 3 Example 4 Example 5 water 20.0 20.0 20.0 20.0 20.0 Naphthalene Dispersant 5.0 5.0 5.0 5.0 5.0 Synthesis Example 1 25.0 - - - - Synthesis Example 2 - 25.0 - 25.0 25.0 Synthesis Example 3 - - 25.0 - - Synthesis Example 4 - - - 20.0 - Synthesis Example 5 20.0 20.0 20.0 - - Synthesis Example 6 - - - - 20.0 Buffer 30.0 30.0 30.0 30.0 30.0 Total (% by weight) 100.0 100.0 100.0 100.0 100.0

2. Evaluation of Physical Properties of Multifunctional Dispersants

The appearance, pH, sugar content, oligomer removal ability, dispersibility, and metal ion blocking power of the composite multifunctional dispersant obtained in Examples 1 to 5 were measured, and the results are shown in Table 6. Appearance, sugar content, pH, oligomer removal power, dispersibility, metal ion blocking power were the same as in Synthesis Examples 1 to 6, and the sugar content was measured by digital refractometer (ATAGO, PR101, PR301).

division Exterior pH Sugar content (%) Oligomer Removability (Grade) Dispersibility (grade) Metal ion containment force (grade) Example 1 Brown transparent liquid 3.0 35.5 5 4 5 Example 2 Brown transparent liquid 3.0 35.3 5 5 5 Example 3 Brown transparent liquid 3.0 35.3 4 5 5 Example 4 Brown transparent liquid 3.0 35.0 5 4 5 Example 5 Brown transparent liquid 3.0 35.0 5 5 4

As a result of the above evaluation, the performance of the multifunctional dispersants of Examples 1 to 5 was similarly excellent, but Example 2 showed the best performance among them. That is, when the oligomer remover having a molecular weight of 1,000 and a ratio of PO of 15% and a metal ion blocking agent having a molecular weight of 400 and a ratio of 10% of PO were found, the optimum requirements of the multifunctional dispersant were satisfied.

According to the present invention, a multifunctional dispersant which removes oligomers mainly generated in the dyeing and processing process of polyester, blocks metal ions in a salt bath, improves dispersibility of a disperse dye, and maintains a constant pH Could provide.

Claims (6)

17-30 wt% of the oligomer remover of Formula 1, which is a reactant between ethylene oxide / propylene oxide copolymer and TPA, 20-30 wt% of the metal ion sequestrant of formula 2, which is a reactant of acrylic acid and ethylene oxide / propylene oxide addition ester, naphthalene A multifunctional dispersant for polyester dyeing, comprising 5 to 10 wt% of a dispersant, 22 to 40 wt% of a buffer solution, and water as the remainder. [Formula 1]

(n is an integer from 10 to 30, m is an integer from 2 to 10.) [Formula 2]

(x is an integer from 50 to 300, y is an integer from 5 to 50, n is an integer from 5 to 15, and m is an integer from 1 to 10.) The multifunctional dispersant for polyester dyeing according to claim 1, wherein the ratio of ethylene oxide and propylene oxide in the oligomer remover is 70:30 to 95: 5. According to claim 1, wherein the oligomer remover pH 4.0 ~ 6.0, AV (Acid Value) 5 or less, the weight average molecular weight of 500 ~ 3,000, characterized in that the non-ionic polyester multifunctional dispersant. According to claim 1, wherein the ratio of ethylene oxide and propylene oxide in the metal ion blocking agent is a multifunctional dispersant for polyester dyeing, characterized in that 70:30 ~ 95: 5. The method of claim 1, wherein the metal ion blocking agent pH 6.5 ~ 7.5, non-volatile content 60 ~ 70%, weight average molecular weight 2,000 ~ 20,000, and multifunctional dispersant for polyester dyeing, characterized in that the anionic. The method of claim 1, wherein the multi-functional dispersing agent for dyeing is characterized in that the pH 2-5, the sugar content 20-50 and the oligomer removal force 4-5 grade, metal ion blocking force 4-5 grade and dispersibility 4-5 grade Multifunctional dispersant for dyeing polyester.