JP4131087B2 - Dye dispersant - Google Patents

Description

注1)１０段階評価
注2)◎＝better ○＝good △＝bad ×＝worse
注3)汚染性試験前の試験布の白色度：80
【００３３】
【発明の効果】
表1の結果より、本発明の染料分散剤が、従来の使用量よりも低い添加量で汚染性、還元退色性、スプレードライ適性に加え、高温分散性にも優れていることがわかる。
【００３４】
特に、本発明の染料分散剤を用いると、従来使用していた分散剤使用量の10〜50重量％を低減でき、これによって、分散染料の高濃度化が可能となり、産業上有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dye dispersant, and particularly relates to a dye dispersant containing a dispersant that is excellent in high-temperature dispersibility and that is excellent in spray drying suitability, stain resistance, and reduction fading.
[0002]
[Prior art]
Conventionally, disperse dyes have been used for the purpose of dyeing polyester fibers and the like. This is because the disperse dye itself (dye active ingredient / pigment) is insoluble or hardly soluble in water, and thus can be stably dispersed in water using a dispersant. In this case, partially desulfonated lignin sulfonic acid or naphthalene sulfonic acid formaldehyde condensate has been mainly used as a dispersant. Partially desulfonated lignin sulfonic acid shows good dyeability (high temperature dispersibility) because it disperses the disperse dye pigment in water stably during high temperature dyeing such as dyeing of polyester fibers (eg, 130 ° C.). . Moreover, when it is used as a dye dispersion, it exhibits good spray-drying suitability (the degree of generation of dye aggregates during powder drying with a spray dryer is small).
[0003]
On the other hand, naphthalenesulfonic acid formaldehyde condensate has the advantage that the color of the dispersant itself is pale yellow when in the form of a dry powder, and the degree of staining (contamination) of the dispersant to the fabric during dyeing is small. In addition, since there is no azo dye that reduces the dye as a constituent component, no reduction or fading occurs.
[0004]
However, partially desulfonated lignin sulfonic acid has a brownish brown color when it is in a dry powder form, and the dispersant tends to stain and stain the fabric at the time of dyeing, and is used for light-colored dyes. There are aspects that are difficult to do. For azo dyes, there are some components that reduce the dye as a constituent of lignin sulfonic acid, and color fading may occur.
[0005]
On the other hand, naphthalene sulfonic acid formaldehyde condensate is physically adsorbed to the disperse dye pigment, so it exhibits good dispersibility near room temperature, but desorbs from the disperse dye pigment as the temperature rises. Since the dispersion stability is lowered, the high-temperature dispersibility is remarkably inferior, and this causes uneven dyeing during high-temperature dyeing. Furthermore, there is a problem that the spray-drying property is remarkably inferior.
[0006]
In recent years, the present applicants have disclosed a formaldehyde condensate of bisphenols and sulfites as a dispersant having good spray-drying suitability, fouling properties, and reduction fading properties, and Japanese Patent Publication No. 6-74387 and Japanese Patent Laid-Open No. 11-181316. This is proposed in Japanese Patent Laid-Open No. 11-181317. However, the above-mentioned condensate has good contamination and reduction fading properties, and spray dryability is improved as compared with naphthalenesulfonic acid formaldehyde condensate, but improvement in high-temperature dispersibility has been demanded.
[0007]
In recent years, from the viewpoint of increasing the concentration of disperse dyes (increasing the proportion of the dye base in the disperse dye and reducing the proportion of the dispersant), excellent high-temperature dispersibility, spray drying suitability even with a smaller amount of use, Dispersants having staining properties and reductive fading properties are desired, but in reality the ones that satisfy these performances at a low addition rate have not been obtained.
[0008]
[Problems to be solved by the present invention]
An object of the present invention is to provide a dye dispersant which is excellent in all of contamination, reduction fading, spray drying suitability and high-temperature dispersibility even at a low addition amount.
[0009]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have determined that the reaction molar ratio of 2,2′-bis (4-hydroxyphenyl) propane, phenolsulfonic acid, sulfite, and formaldehyde is 1.0: 0.1 to 0.3: 0.4 to 0.6: 1.4 to 1.7. By using a dye dispersant characterized by containing a condensate having a weight average molecular weight of 500 to 5000, which is obtained by reacting in an aqueous solution at a high temperature, the stain resistance, reduction fading property, and spray drying suitability are all good. The present inventors have found that the dispersibility can be greatly improved and have reached the present invention.
[0010]
In the present invention, “excellent stainability” means that the degree of color stain on the fabric of the dispersant is low, and “excellent reduction fading” means that the dispersant reduces the dye and causes color fading. It means that the degree to wake up is low.
[0011]
That is, in the present invention, 2,2′-bis (4-hydroxyphenyl) propane, phenolsulfonic acid, sulfite, and formaldehyde are reacted in an aqueous reaction at a reaction molar ratio of 1.0: 0.1 to 0.3: 0.4 to 0.6: 1.4 to 1.7. Among the resulting condensates, a dye dispersant containing a condensate having a weight average molecular weight of 500 to 5,000.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the sulfite used in the present invention include sodium sulfite, sodium hydrogen sulfite, and sodium pyrosulfite.
[0013]
The present invention is obtained by reacting 2,2′-bis (4-hydroxyphenyl) propane, phenolsulfonic acid, sulfite, and formaldehyde in a molar ratio of 1.0: 0.1 to 0.3: 0.4 to 0.6: 1.4 to 1.7. Furthermore, if the conditions at the time of synthesizing the condensate are mentioned, the synthesis is carried out under aqueous conditions (solid content concentration: 20 to 50% by weight), at normal pressure or under pressure, at a temperature of 30 to 140 ° C., usually for 4 to 50 hours. . The pH during synthesis is preferably 6 to 13 (adding alkali as necessary to adjust pH), and dropping of formaldehyde is preferably performed within 1 to 2 hours. The condensation may be performed by condensing 2,2′-bis (4-hydroxyphenyl) propane and phenolsulfonic acid, and then condensing sulfite, or may be performed at once. When the reaction is carried out with the molar ratio removed, the optimum balance between the hydrophobic group and the hydrophilic group in the chemical structure of the condensate is lost, and the high-temperature dispersibility deteriorates.
[0014]
Furthermore, the thing of the weight average molecular weight of 500-5000 is preferable among the condensates obtained on the said conditions. When the weight average molecular weight is less than 500 or more than 5000, there is a drawback that the high-temperature dispersibility is deteriorated. Further, when the weight average molecular weight is less than 500, the ratio of unreacted monomers increases, and when it exceeds 5000, the viscosity of the condensate increases. In the present invention, it is necessary to adjust the weight average molecular weight of the condensate to 500 to 5000. For this preparation, fractionation by membrane treatment or the like may be performed as necessary.
[0015]
In the present invention, the weight average molecular weight is measured using gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.
[0016]
The condensate of the present invention usually includes an alkali metal such as sodium.
[0017]
When the condensate of the present invention is used as a dye dispersant, there is no problem even if it is used in combination with a conventional dye dispersant such as lignin sulfonic acid or naphthalene sulfonic acid formaldehyde condensate. The amount of these additives is appropriately determined according to the purpose, but the effect is exhibited if the condensate of the present invention is contained in an amount of 25% by weight or more based on the total dye dispersant.
[0018]
Compared to the conventional formaldehyde condensates of bisphenols and sulfites described in JP-B-6-74387, JP-A-11-181316, JP-A-11-181317 I think as follows.
[0019]
2,2′-bis (4-hydroxyphenyl) propane, phenolsulfonic acid, sulfite, and formaldehyde in a reaction molar ratio of 1.0: 0.1 to 0.3: 0.4 to 0.6: 1.4 to 1.7 Among them, for the condensate having a weight average molecular weight of 500 to 5000, the reaction molar ratio and the weight average molecular weight are within the extremely limited range among the conventional condensates. Furthermore, phenolsulfonic acid is introduced. By doing so, it is believed that the balance between the hydrophobic group and the hydrophilic group in the chemical structure of the condensate becomes more optimal, and that the present invention exhibits very high temperature dispersibility.
[0020]
【Example】
EXAMPLES Hereinafter, although this invention is explained in full detail according to an Example, this invention is not limited by this. In the examples of condensate synthesis, “parts” indicating the blending amount indicates parts by weight. The weight average molecular weight was abbreviated as Mw.
[0021]
Synthesis example 1
A predetermined amount of the following substances was charged into a reactor equipped with a stirrer, a reflux device, a formaldehyde aqueous solution dropping device, and a temperature controller.
・ 2,2'-bis (4-hydroxyphenyl) propane 1.00 mol [228.3 parts]
・ Phenolsulfonic acid 0.15 mol [26.1 parts]
・ Sodium hydrogen sulfite 0.55 mol [57.3 parts]
・ Sodium hydroxide 1.00 mol [40.0 parts]
・ Water [820.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and 1.40 mol of formaldehyde (113.5 parts of 37% formaldehyde aqueous solution) was added dropwise over 2 hours, followed by reaction at 95 ° C. for 30 hours to produce the condensate of Synthesis Example 1 (Mw = 4000).
[0022]
Synthesis example 2
In the same manner as in the preparation of the condensate of Synthesis Example 1, the following substances were charged in predetermined amounts.
・ 2,2'-bis (4-hydroxyphenyl) propane 1.00 mol [228.3 parts]
・ Phenolsulfonic acid 0.25 mol [43.5 parts]
・ Sodium sulfite 0.60 mol [62.5 parts]
・ Sodium hydroxide 1.00 mol [40.0 parts]
・ Water [870.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and 1.60 mol of formaldehyde (129.7 parts of 37% aqueous formaldehyde solution) was added dropwise over 1 hour, followed by reaction at 85 ° C. for 20 hours to obtain the condensate (Mw) of Synthesis Example 2. = 2000).
[0023]
Synthesis example 3
In the same manner as in the preparation of the condensate of Synthesis Example 1, the following substances were charged in predetermined amounts.
・ 2,2'-bis (4-hydroxyphenyl) propane 1.00 mol [228.3 parts]
・ Sodium hydrogen sulfite 0.75 mol [78.1 parts]
・ Sodium hydroxide 0.30 mol [12.0 parts]
・ Water [740.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and then 1.65 mol of formaldehyde (133.8 parts of 37% aqueous formaldehyde solution) was added dropwise over 1 hour, followed by reaction at 95 ° C. for 30 hours to produce the condensate of Synthesis Example 3 (Mw = 4500).
[0024]
Synthesis example 4
In the same manner as in the preparation of the condensate of Synthesis Example 1, the following substances were charged in predetermined amounts.
・ 4,4'-dihydroxydiphenylsulfone 1.00 mol [250.3 parts]
・ Phenolsulfonic acid 0.25 mol [43.5 parts]
・ Sodium hydrogen sulfite 0.60 mol [62.5 parts]
・ Sodium hydroxide 2.00 mol [80.0 parts]
・ Water [1000.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and then 2.00 mol of formaldehyde (162.2 parts of a 37% aqueous formaldehyde solution) was added dropwise over 2 hours, followed by reaction at 85 ° C. for 20 hours to obtain the condensate of Synthesis Example 4 (Mw = 1500).
[0025]
Synthesis example 5
In the same manner as in the preparation of the condensate of Synthesis Example 1, the following substances were charged in predetermined amounts.
・ 2,2'-bis (4-hydroxyphenyl) propane 1.00 mol [228.3 parts]
・ Phenolsulfonic acid 0.05 mol [8.7 parts]
・ Sodium sulfite 0.70 mol [72.9 parts]
・ Sodium hydroxide 0.40 mol [16.0 parts]
・ Water [760.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and then 1.50 mol of formaldehyde (121.6 parts of 37% aqueous formaldehyde solution) was added dropwise over 1 hour, followed by reaction at 90 ° C. for 20 hours to give a condensate (Mw = 2000).
[0026]
Synthesis Example 6
In the same manner as in the preparation of the condensate of Synthesis Example 1, the following substances were charged in predetermined amounts.
・ 2,2'-bis (4-hydroxyphenyl) propane 1.00 mol [228.3 parts]
・ Phenolsulfonic acid 0.20 mol [34.8 parts]
・ Sodium sulfite 0.60 mol [62.5 parts]
・ Sodium hydroxide 1.00 mol [40.0 parts]
・ Water [850.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and 1.40 mol of formaldehyde (113.5 parts of 37% aqueous formaldehyde solution) was added dropwise over 1 hour, followed by reaction at 65 ° C. for 15 hours to obtain the condensate (Mw = 400).
[0027]
Synthesis example 7
In the same manner as in the preparation of the condensate of Synthesis Example 1, the following substances were charged in predetermined amounts.
・ 2,2'-bis (4-hydroxyphenyl) propane 1.00 mol [228.3 parts]
・ Dihydroxybenzene 0.10 mol [11.0 parts]
・ Sodium hydrogen sulfite 0.75 mol [78.1 parts]
・ Sodium hydroxide 0.40 mol [16.0 parts]
・ Water [780.0 parts]
The solid-liquid mixture was heated to 90 ° C. with stirring, and then 1.50 mol of formaldehyde (121.6 parts of 37% aqueous formaldehyde solution) was added dropwise over 2 hours, followed by reaction at 90 ° C. for 20 hours to give a condensate (Mw = 1500).
[0028]
High temperature dispersibility test Naphthalenesulfonic acid formaldehyde condensate and dye base (CIDisperse Red 60) were added to a 1: 3 solids weight ratio of water, stirred, and then mixed with a juicer mixer and sand grinder (glass The dye base is atomized by using beads) to obtain a dye crushing liquid (solid content 20% by weight).
Next, to this various dispersants (solid content equivalent 0.4g), this dye crushing liquid (solid content equivalent 0.8g) and water were added, adjusted to pH 5.0 with acetic acid, made up to 250ml, and charged into the dyeing pot. . Next, a dyeing holder in which 10 g of a polyester jersey cloth was wound around an inner cylinder was put into a dyeing pot and dyed with a color pet dyeing machine (manufactured by Nippon Dyeing Machine Co., Ltd.) (130 ° C., 10 minutes). After dyeing, the fabric was cooled rapidly, and the polyester jersey cloth was immediately taken out, washed with water, and dried overnight at room temperature. After drying, the degree of dye agglomerates adhering to the fibers of the polyester jersey cloth was visually evaluated on a 10-point scale. The results are shown in Table 1. In the table, Rank 10 indicates that no aggregates are observed in the best evaluation, and Rank 1 indicates that the aggregates are significantly adhered in the worst evaluation.
The dispersants used in the tests were the condensates of Synthesis Examples 1 to 7, partially desulfonated lignin sulfonic acid as a control example (using Nippon Paper Co., Ltd. Vanillex RN, hereinafter abbreviated as LIG), naphthalene sulfonic acid. Formaldehyde condensate (Nippon Paper Co., Ltd. Vaniol HD-200 is used, hereinafter abbreviated as NSF).
[0029]
Spray dry suitability test A spray dry suitability test was conducted on LIG and NSF as the condensates of Synthesis Examples 1 to 7 and a control sample. The test method is as follows.
Add water to a 1: 0.5 solid content weight ratio of the dye base (CIDisperse Red 60) and dispersant, stir, and then finely atomize the dye base with a juicer mixer and sand grinder (using glass beads). A crushed liquid (solid content 30% by weight) is obtained. Next, this was filtered through a filter cloth (Tetron / Cotton blended cloth, manufactured by Color Dyeing Co., Ltd.), and after removing the one having a large particle size, it was dried by spray drying to obtain a powder (inlet temperature 105 to 150 ° C. , Outlet temperature 50-75 ° C). After that, a spec test was conducted. The spec test is an index for evaluating spray dry suitability. Specifically, 10 g of the above spray-dried powder is redissolved in 500 ml of warm water (40-60 ° C.) with stirring, and the resulting aqueous solution is filtered with a filter cloth (Tetron / Cotton blended cloth), and aggregates when dried The presence or absence of was visually evaluated. The less the aggregate adheres to the cloth, the better the spray-drying suitability. The results are shown in Table 1.
[0030]
Contamination test LIG and NSF contamination tests were performed on the condensates of Synthesis Examples 1 to 7 and a control sample. The test method is as follows.
A predetermined amount (660 mg in terms of solid content) of the dispersant was collected, water was added, and the pH was adjusted to 5.0 using acetic acid, and then the total amount was adjusted to 250 ml. After charging into a color pet dyeing machine together with 8g of test cloth (cotton cloth) and dyeing at 130 ° C for 1 hour, the test cloth is dried and measured for whiteness with a whiteness meter (Murakami Color Co., Ltd.). did. The test results obtained are shown in Table 1.
[0031]
Reduction fading test The reduction fading tests of LIG and NSF were performed as the condensates of Synthesis Examples 1 to 7 and a control sample. The test method is as follows.
Water was added to the azo-based disperse dye base and the dispersant (400% by weight with respect to the dye base), and the pH was adjusted to 5.0 with acetic acid. After being charged into a color pet dyeing machine together with 8 g of polyester jersey cloth and dyed at 130 ° C. for 1 hour, the test cloth was dried and compared for reduction fading. The results obtained are shown in Table 1.
[0032]
[Table 1]

Note 1) 10-level evaluation Note 2) ◎ = better ○ = good △ = bad × = worse
Note 3) Whiteness of test cloth before contamination test: 80
[0033]
【The invention's effect】
From the results shown in Table 1, it can be seen that the dye dispersant of the present invention is excellent in high-temperature dispersibility in addition to contamination, reduction fading property, and spray drying suitability at an addition amount lower than the conventional use amount.
[0034]
In particular, when the dye dispersant of the present invention is used, it is possible to reduce 10 to 50% by weight of the amount of dispersant used conventionally, which makes it possible to increase the concentration of the disperse dye and is industrially useful.

Claims (1)

Weight average obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane, phenolsulfonic acid, sulfite, and formaldehyde in a reaction molar ratio of 1.0: 0.1 to 0.3: 0.4 to 0.6: 1.4 to 1.7 in an aqueous solution A dye dispersant comprising a condensate having a molecular weight of 500 to 5,000.