JPS6045931B2 - Dispersant composition comprising sulfonated lignin adduct - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to dispersants comprising sulfonated lignin derivatives, and more particularly to the use of such dispersants in dyeing formulation compositions and dyeing process steps.

As used herein, the term "lignin" has its ordinary meaning and is typically used in alkaline papers, such as those obtained from Kraft, soda and other well-known alkaline pulping processes. Refers to what is recovered from the black liquor of the pulping process.

The term "sulfonated lignin" used here is
Refers to the product obtained by the introduction of sulfonic acid groups into the lignin molecule, such as can be achieved by reacting lignin with sulfite or bisulfite compounds. The term "lignosulfonate" as used herein refers to the reaction product of lignin, which is uniquely obtained during the sulfite pulping process and is a major component of the sulfite waste liquor derived from the bulging process. Finally, monosulfonated lignin materials include not only the lignin and lignosulfonate reaction products mentioned above, but also sulfite waste liquors, which may be used where appropriate (and as detailed below). ), further reactions (eg, methylolation and/or deglycosylation), purification, fractionation, etc. can be performed. Clay (
It is known that they can be used with considerable advantage as dispersants for many substances such as clays), insecticides, agricultural chemicals, dyes, etc.

However, in order to provide a satisfactory dye dispersant, it must exhibit a balance of desirable properties, in view of the fact that some properties have generally been found not to be in good balance with others. , particularly difficult problems arise. Therefore, one must usually compromise and accept a relatively low level of performance in one or more properties in order to achieve good performance in other properties. For example, in dispersants for disperse or batch dyes, the ideal dispersant would exhibit excellent thermal stability as well as low azo dye reducibility and low staining properties. It must also provide the least foaming and maximum milling effect (i.e. efficiency in achieving small particle sizes in the least amount of time), and it must also result in a low viscosity of the dye paste that is finally used. Must be. As a well-known example of a fundamental discrepancy between certain of the above properties, sulfonated lignin products, although exhibiting excellent high temperature stability, exhibit a high tendency to stain and azo dye reduction. It tends to occur at the level.

In contrast, lignosulfonates exhibit relatively low levels of azo dye reduction, but have poor thermal stability for many applications. This may not be appropriate. It has been found that, in general, milling effectiveness and thermal stability are not consistent properties, and that superiority in one of these properties is rather inferior in the other. Finally, although lignosulfonate products generally have a somewhat lower propensity to contaminate textile fabrics compared to sulfonated lignin products, in the final analysis they are less likely than currently available lignin-based dispersants or those described in the literature. None of the lignin-based dispersions in which contamination is completely satisfactorily low; most disperse dyes and pat dyes have
As either quinone dyes or azo dyes, the requirement to prevent the reduction reaction is particularly important because, if its prevention is not possible, it is necessary to compensate for the dye being consumed in the reduction caused by the dispersant. This is because an unreasonably large amount of dye must be used to achieve this.

Although many attempts have been made in the literature to improve the azo-reducing and staining properties of sulfonated lignin dispersants, these attempts generally involve blocking the free phenolic hydroxyl groups of lignin. Ta. Examples of such efforts include U.S. Pat.
No. 3139, No. 37692n and No. 3865803
There are some items listed in the specification. Although these methods are somewhat effective, they are rather expensive to implement and
And the results achieved are still not very satisfactory. Similarly, in view of the need to provide good high temperature stability (thermal stability) to enable the dyes to be used in conventional dyeing operations, some attempts have also been made to improve the thermal stability in lignosulfonate products.

Typical of such attempts is U.S. Pat.
No. 64276, which describes a dispersant obtained by cross-linking the solid content of sulfite waste liquid and the solid content of Kraft process waste liquid. Ultra-P filtration (which may be followed by desulfonation of the product) to improve thermal stability has also been attempted, and some products made by such methods are commercially available. Oxidizing and desulfonating sulfite waste (i.e., sulfite valving process waste) with air or oxygen in an alkaline medium (as in the production of vanillin) has been used in an effort to improve the thermal stability of lignosulfonate products. This is one attempt made. However, all of the above methods equally darkened the lignosulfonate and thus increased the concentration of contamination seen when it was used. Such treatments also tend to increase the azo dye reducing properties of the product. In addition to these results, the improvement of the thermal stability of the product was not very satisfactory. It is therefore a principal object of the present invention to provide novel dispersants made from sulfonated lignin materials. A further particular object of the invention is to provide dispersants exhibiting the most suitable balance of properties making them highly suitable for use as dispersants for disperse and pad dyes.

Another specific object of the present invention is to provide a sulfonated lignin dispersant that exhibits relatively low staining and azo dye reducing properties, and to provide a lignosulfonate dispersant that exhibits a greatly improved level of thermal stability. It is to be.

Yet another object of the present invention is to provide a sulfonated lignin dispersant that provides superior milling efficiency compared to similar dispersants according to the prior art.

Another object of the present invention is to provide the new dispersant, which is relatively inexpensive and easy to manufacture.

The above and related objects of the invention are such that 2-8% by weight
It has been found that this can be easily achieved by a lignin adduct of a sulfonated lignin material containing 10% of organic sulfur with about 0.05 to 4 mmol of certain hydroxylbenzyl alcohol compounds per 1y of lignin in the lignin material.

The hydroxybenzyl alcohol compound has the following general formula. In the above general formula, n is an integer of 1 to 3, and A is a substituent selected from the group consisting of hydrogen, a lower alkyl group (for example, an alkyl group containing 1 to 4 carbon atoms), and a hydroxymethyl group. be.

According to an embodiment of the invention, the adduct composition uses lignosulfonate as the sulfonated lignin material, in which case the lignosulfonate may be a methylolated derivative.

According to another embodiment, the lignin material used is sulfonated lignin. The alcohol compound used in each case is preferably monohydroxybenzyl alcohol and is preferably in an amount of at least about 0.5 mmol per y of lignin. Certain objects of the present invention are achieved by the method for preparing lignin adducts described below. The first
The step is to form a reaction aqueous mixture of the sulfonated lignin material and the hydroxyl benzyl alcohol compound. (The latter alcohol compound has the general formula described above and is used in the amounts relative to lignin as described above). Approximately 50
A temperature of ˜100° C. and a pH of about 3-12 are applied to the reaction mixture to effect the reaction of the lignin material with the alcohol compound. These reaction conditions are maintained in the reaction mixture for about 1-2 hours to substantially convert the lignin material and alcohol compound to lignin adduct. According to a preferred embodiment of the invention, the lignin material used is a sulfite waste solution (sulfite valving process waste solution) which has previously undergone a reaction to methylol most of its lignin-containing components. Most preferably, this methylolation reaction is carried out with formaldehyde.

It is particularly preferred to use an at least partially desugarized sulfite waste solution in any combination. According to another preferred embodiment of the invention, the sulfonated lignin material is about 2 to 7
It is an alkaline lignin sulfonated to an organic sulfur content of % by weight.

In all the above-mentioned methods of the invention, the alcohol compound used is from the group consisting of monohydroxyl benzyl alcohol, dihydroxyl benzyl alcohol, trihydroxyl benzyl alcohol, monohydroxyl methyl benzyl alcohol and monohydroxyl hydroxyl methyl benzyl alcohol. Preferably, monohydroxybenzyl alcohol is used to make the adduct according to the method described above. Certain of the objects of the present invention are achieved when a lignin adduct made by the method described above is provided. The effects of the present invention will be explained below with reference to examples (all 1 part and 1%
weight is based on weight).

Example 1 Softwood (coniferous wood) using valved sulfite waste liquid)
Ta.

This stuff is about 63% sodium lignosulfonate (
47% lignin, 5.5% organic sulfur, 7% methoxy group,
It contained 3.5% sodium) and 20% reducing sugars, with the remainder being inorganic salts, polysaccharides, etc. The waste liquid was reacted with sodium hydroxide at 90°C for 2 hours to return substantially all the sugars contained in the liquid to sugar acids. This reversed liquid (P
HlO. 7) contains 11 parts of solid content and 1285 parts of water, 4 (1) parts of the solid content consists of organic sugar acids and inorganic salts, and 6 (1) parts of the solid content was lignosulfonate. The lignosulfonate in the liquid was converted into methylol by reacting with formaldehyde at 70°C for 2.5 hours at a liquid solid content of 100@S (marked with 5).At the end of this reaction, only traces of formaldehyde were formed. was detected. By introducing 1.9 mmol of monohydroxyl benzyl alcohol per 1 y of lignin in the lignosulfonate during the reaction mixture, both were reacted at 100°C for 5 hours. The pH of the final reaction product solution and The viscosities are 10.95 and 4, respectively.
It was 3 centipoise (25°C). The product was spray dried and evaluated as a dispersant using the test method described below. Thermal Stability Thermal stability was evaluated as follows.

First, 100 q of dispersant was ground together with 40 g of Disperse Dye Blue 3 dye in a sand mill containing enough water to give a total weight of 250 y.

The dye and dispersant were milled using 500y standard sand at 2000 rpm for a total of 5 hours, with an additional 50y dispersant added over the last three minutes of the milling operation.

During the milling, the PH of the mixture was maintained at a value of 8 by adding a suitable amount of acetic acid. To evaluate the lignin product as a wet composition, an amount of dye paste prepared by the above method and containing 3y of solids was diluted with distilled water and 100 m
The total volume was made up to 1 and heated to 70'C.

The mixture was stirred for 1 minute and poured into a 15 cm (7) NO. using a standard aspirator and Buchner funnel. Vacuum filtered through 2 Whatman p paper. The time required for filtration and the weight of the residue on the paper were recorded. The ability of the lignin product to function as a dry composition was evaluated as follows.

The paste made above was spray dried at an inlet temperature of 120°C and an outlet temperature of 88°C. Spray dried powder 2
The paste was made into a paste with 10 ml of distilled water and the volume was then increased to 100 ml by adding the appropriate amount of water at 70°C. The resulting mixture was stirred well for 1 minute and then washed with Whatman NO. ? ! The weight of the residue and the elapsed time were recorded using P paper. The cross-temperature stability of the product was measured as follows.

70ml of the above spray-dried powder and 10ml of water.
A paste was made at ℃. 70'C to this paste
290 ml of water was added and the mixture was boiled with stirring. The boiling mixture was then strained through a cotton cloth, and the cloth was inspected to determine the weight of the residue retained thereon, and the straining time was also recorded. Table 1 below shows the data obtained in the above evaluations using the products produced as described above.

For comparison, data obtained using other commercially available dispersants are also shown. TAMOLSN is a synthetic naphthalene sulfonate dispersant commercially available from Rohm & Haas, and UFOXANE is a commercially available synthetic naphthalene sulfonate dispersant from BOrregaard, Norway.
REAX 85X is a sulfonated Kraft process lignin commercially available from WestvacO,
RSE52CP is a lignosulfonate dispersant available from American Gun Company. In Table 1 (and the tables below), solids is in %, viscosity is in centipoise, elapsed time is in seconds, and residue is M9. As is evident from the above data, the dispersant of the present invention exhibits better stability than any of the commercially known dispersants with which it has been compared, and this is reflected in terms of shearing time as well as the weight of the residue remaining on the shearing paper. shown in relation to

These results may be even more significant when compared to the sulfonated lignin compound REAX 85A dispersant, a product that is considered to exhibit excellent thermal stability and is widely used for that reason. The above data also show that, in addition to the very pronounced thermal stability exhibited by the dispersant of the present invention, it also provides a desirable reduction in the viscosity of the dye paste. Low viscosity is, of course, desirable because it facilitates processing of the paste and allows higher concentrations of solids to be used and included in the final product. Fiber Staining The fiber staining properties of the dispersant of the present invention were tested in comparison with commercially available products as follows.

A bath was prepared by dissolving 10 Da of dispersant in 250 mL of tap water, and the dispersion was neutralized with acetic acid. Five small fabric pieces each of cotton and polyester/cotton (6V35) blend were introduced into the bath, which had been previously heated to the boiling point, and kept immersed therein for one hour. The bath was then allowed to flow down the dough pieces, the dough pieces were manually squeezed to remove residual liquid, and the dough pieces were placed in a beaker. The small fabric pieces were rinsed in cold tap water for 5 minutes and finally air dried. The reflectance of each small fabric piece was measured with a glossmeter (457 nm nanometers) using standard procedures. The contamination rate was calculated using the following formula.
Contamination rate % = [(RO-R,)/RO'1X100 In the formula, R, = reflectance of fabric contaminated with dispersant, RO =
is the reflectance of a blank fabric (i.e. treated in a water bath without dispersant). The results are shown in Table 2 below.

From the above data, it can be seen that the dispersant of the present invention, compared to other commercially available dispersants except TAMOLSN:
It can be seen that the stain resistance for both cotton and cotton/polyester blend fabrics is much better.

Of course, the product is not a lignin-based dispersant;
It is therefore widely used industrially because of its particularly desirable staining properties. It is typically colorless or virtually colorless. Foaming The foam stability of the dispersants of the present invention was tested in comparison to other commercially available dispersants as follows.

1y of dispersant (based on solid content) was dissolved in 100ml of tap water, and its pH was adjusted to 5 with acetic acid.

This liquid was placed in a 250 ml graduated cylinder which was rapidly inverted five times in succession, after which the foam height (Mt) above the liquid level was measured. This was measured a second time after a 1 minute break and again after 2 minutes. The results of this test are shown in Table 3 below. This data shows that the dispersants of the present invention exhibit very desirable foaming properties.
However, the dispersant of the present invention did not perform better than all other dispersants in this example. The reducibility of the azo dye to the reduced azo dye was tested as follows.

100 mg of disperse dye Brown 1 dye were dispersed in 200 ml of distilled water with 1 g or 2 q of dispersant. Five pieces of cotton cloth were introduced into the dispersion and it was heated to 135°C.
1. Heat to that temperature. Holds time. The reflectance of the test piece was then measured using a standard method, and the dye reduction rate was calculated from that value. The dye reducing properties of several dispersants are shown in Table 4 below. These results show that the dispersant of the present invention performs better than any of the other dispersants compared. Given that MARSPERSE and UFOXANE, like the dispersants of the present invention, are lignosulfonates, the above results are particularly striking with respect to them. Example 2 The same softwood lignosulfonate solution as in the previous example, but
A liquid from a different source and containing a higher concentration of lignosulfonate was reacted with monohydroxybenzyl alcohol as in the previous example.

The milling efficiency of this product was compared to other commercially available products and evaluated as follows. Dye pastes (40% solids) made using selected dyes and dispersants in a 3:1 ratio were tested for various times using sand at a 3:1 solids to paste ratio. I ground it. 1y of the dye paste was diluted to 200ml with distilled water and the mixture was mixed with NO. 2 Whatman door paper and NO. The mixture was filtered (vacuum) in a Buchner funnel lined with 4 layers of Whatman Oki paper (typical R2x4 test). Record the offshore time and the weight of the residue on the offshore paper. Ta. In comparison with the same commercially available dispersant used in Example 1, the dispersant of the present invention was consistently superior in milling efficiency.

The dispersant of this example was milled 6 times using a low energy dye (Dispersion Yellow 54) and the residue was about 30 mg. After the same milling time the residue is about 8 in TAMOLSN
0m9, 120mg in MARASPERSE52CP,
And it was 210m9 with REAX85A.

On the other hand, using a high energy dye (Dispersion Blue 79), again after 60 minutes of milling, the dispersant of the present invention
g residue, but REAX85A. ．． MARASP
ERSE52CP and TAMOLSN yielded approximately 70 m9, 80 m9 and 120 m9 of residue, respectively.
Even when the grinding time was further extended, the performance order of grinding efficiency remained the same as above. These data not only demonstrate the superiority of the absolute milling efficiency of the dispersants of the present invention, but also show a wide range of effectiveness with dyes at the energy extremes, compared to conventional dispersants. After 60 minutes of milling, the UF'0XANE dispersant showed comparable effectiveness to the dispersant of the present invention.

However, when using Dispersed Yellow 54 dye, for example, after milling 9 powders the residues produced by [JF'0
It was Lg. A similar tendency was observed when Blue 7 footage was used. Furthermore, the dispersants of the invention always exhibit excellent viscosity in dye pastes. For example, 40% with Blue 7 Butterfly Price
When using a solid paste, the viscosity is 257 at 25°C.
It was centipoise hot. Compared to this [-JFOXA
In NE, it was 825 centipoise under the same conditions.

Example 3 Lignosulfonate (NORL from American Gun Company)
IG42) was reacted with monohydroxyl benzyl alcohol as in Example 1 and the resulting adduct was evaluated for thermal stability as in Example 1 with dispersed Flue 3 dye.

From Table 5 below, which shows data using both modified lignosulfonate and unmodified starting material, it can be seen that modification significantly improves thermal stability. Tests have shown that the modified product also shows good results in terms of staining, azo dye reduction, foaming and grinding properties.
8 Example 4゜-''” REAX85A (sulfonated Kraft process lignin)
was dissolved in water to make a 30% solution and heated at 100'C for 5 hours with about 18.5 parts of monohydroxybenzyl alcohol per part (1) part of lignin.

The initial and final pH of this reaction solution were 11 and 11.4, respectively. The reaction product was spray dried and Example 1
Thermal stability was tested as follows. The data in Table 6 below shows that reaction with monohydroxybenzyl alcohol significantly improves thermal stability, but increases the viscosity of the dye paste. Tests showed that the reaction product of this example showed satisfactory results in terms of staining properties, azo dye reducing properties, foaming properties, and grinding properties. Example 5 To demonstrate the effect of the hydroxymethyl group of hydroxybenzyl alcohol in the preparation of the dispersant of the present invention, a methylolated lignosulfonate was mixed with 1.5 mmol (per q lignin) of phenol as in Example 1. By reacting, an adduct containing no hydroxymethyl group was produced.

This product was evaluated with Disperse Blue 102 dye. dye 3
3f1 addition 25f1 standard sand 250y and water 242y
was sand milled at pH 6.5 to 7.5 for 3 hours.
After measuring the viscosity, the dye paste was placed in a 9 x 12 inch glass drying tray and dried overnight in a forced air oven at 50-600C. This dry mixture was milled into a fine pulverizer.
The dye was milled through a 027 screen and 0.87 g of the milled dye was mixed with 2.13 g of anhydrous sodium sulfate (standardized dye). This mixed dye was well pasted with tap water at 65-70° C. to form a smooth slurry, after which an additional 95 ml of tap water (same temperature) was added. This dye solution was heated to J7O'C and poured using a Buchner funnel using a 9cm (7) NO. Passed offshore on 230 Sove Angel Tomari. The elapsed time and the weight of the residue on the paper were recorded. For the 100°C thermal stability test (boiling test), the standardized dye prepared above was mixed into 100 mL of tap water and heated with live steam to a medium boiling point.

After 5 minutes, soak the dye solution in Sov Angel. NO. It was filtered through 23α paper and the weight of the residue was measured.

For the 130°C thermal stability test (bomb test), 230 ml of distilled water was charged into a brass bomb along with 0.6 da of finely ground dye.

The contents of the cylinder were heated to 90°C with constant stirring, and after securing the lid, the cylinder was placed in a 135°C oven for 1. ? It was heated for a while. After cooling to room temperature, the dye solution was reheated to 80-85°C and heated to SORB ENGEL NO. The mixture was poured onto 23O paper, and the weight of the residue was measured again. The results are shown in Table 7 below. Example 6 A soft wood sulfite waste solution subjected to sugar reversion treatment was reacted with monohydroxybenzyl alcohol in the same manner as in Example 1 without being converted into methylol.

This product, along with Disperse Blue 102 dye, was evaluated and compared to the product of Example 1 according to the procedures outlined in Example 5. The results are shown in Table 8 below. The above data show that completely satisfactory products can be obtained without methylolation of the lignosulfonate. However, when examining the paper, it is found that in some instances, speckling occurs when unmodified lignosulfonate dispersants are used. This indicates some non-uniformity of the dye particles;
Preventing this is a major advantage of methylolation. Example 7 Various amounts of dihydroxybenzyl alcohol were added to 10
Methylolated unfractionated sulfite waste liquor (30% solids) for various times at 0'C and selected pH values.
I reacted.

The various products thus obtained were evaluated for thermal stability using the Dispersion Blue 102 dye according to the method of Example 5. The results (Table 9 below) reveal the effectiveness of dihydroxybenzyl alcohol in dispersant production. The amount of benzyl alcohol used is given in millimoles per y of lignin fraction present. Tests have shown that these products have satisfactory azo dye reducing, staining, foaming and grinding properties. It is also shown that comparable results can be obtained using less dihydroxyl benzyl alcohol than the monohydroxyl compound on a molar basis. Examples 8-10 Example 8 Equimolar amounts of pyrogallol, formaldehyde and PHll
and trihydroxylbenzyl alcohol made by heating at 500C for 30 minutes was reacted with methylolated lignosulfonate at pH 7 and 1000C for 5 hours.

The ratio of benzyl alcohol nilignosulfonate is
0.0% per q of lignin contained in lignosulfonate.
The ratio was such that 9 mmol of benzyl alcohol was obtained. The pH of the product mixture is 7. The solids content was 30%. The viscosity of the product solution was 67 centipoise. Example 9 Equimolar amounts of p-cresol and formaldehyde were adjusted to pH
Alkyl-substituted monohydroxybenzyl alcohol was made by reacting at 7 and 70°C for 1 hour.

The methylolated lignosulfonate solids were reacted with the benzyl alcohol at pH 7 and 100° C. for 5 hours. Benzyl alcohol was present in the reaction mixture at a concentration of 0.9 mmol/q of lignin in the lignosulfonate. The PHL solids content and viscosity of the product solution were 7.8, 32% and 74 centipoise, respectively. Example 10 Hydroxymethyl monohydroxyl benzyl alcohol was made by reacting phenol and formaldehyde in a 1:2 molar ratio at PHll and 70'C for 2 hours.

This generated benzyl alcohol was dissolved in PHLO and at 100°C.
The mixture was reacted with sodium lignosulfonate (34% solids) for 5 hours. Benzyl alcohol was present in the reaction mixture at an initial concentration of 1.8 mmol per y of lignin in the lignosulfonate. The PH, solid content and viscosity of the obtained product were 10.4 and 34, respectively.
% and 370 centipoise. Table 10 below provides thermal stability data for each product of Runs 8-10.

These products have azo dye-reducing properties and are used as dispersants for dyes.
Shows desirable properties in staining, foaming and grindability. Reactions of other mechanisms (e.g., undoubtedly, polymerization reactions)
The main reaction between the sulfonated lignin compound and the hydroxyl benzyl alcohol compound is believed to be a type of condensation reaction that occurs at the hydroxymethyl group of the hydroxyl benzyl alcohol compound and the guaiacyl moiety of the lignin, although it can also occur.

As stated above, this reaction is generally run for 1 to 24 hours, with 4 to 8 hours usually being optimal. If the reaction time is excessive, the viscosity of the product solution and dye paste will become excessive. Of course, unduly low conversion is primarily due to inadequate reaction time. Temperatures of 50-100°C are generally used, although about 80°C or higher is generally preferred.
Too high temperatures will cause discoloration and consequent staining. Too low a temperature will require an unduly long reaction time. The reaction between the sulfonated lignin compound and hydroxyl benzyl alcohol can be carried out at a pH of 3 to 12, but preferably the pH is 5 or higher, most preferably 8 or higher.

Thermal stability of the adduct is generally best when the PH of the reaction mixture is maintained at or above 10, while the foam stability of the adduct (when using monohydroxybenzyl alcohol) is lower than PHlO. 4 was found to be the lowest. P.H.
If is too high, the pollution will be excessive. From a practical and economic standpoint, the reaction is generally carried out at atmospheric pressure. This is because using any other pressure would require a pressure-resistant device and complicate the process. However, if desired, elevated pressures can be used to advantageously increase the reaction rate. With respect to reactants, those skilled in the art will recognize not only the wide variation possible in the types of sulfonated lignin compounds suitable for the present invention, but also the molecular structure and weight of even the most specific compound (i.e., lignin itself). It will be readily appreciated that, in view of the significant differences, precise definition of the proportions of the reactants is hazardously impossible.

Therefore, the amount of modifying reagent used in the reaction is determined by the level of sulfonation and (or methylolation) present in the molecule, which is of the type typically found in sulfite waste liquors and black liquor. For example, it is specified in terms of the number of moles per 1 y of lignin, ignoring the presence of sugars, inorganic salts, sulfonated substances, etc. However, those skilled in the art will understand that variations from the specified ratio are common. , and that the presentation of such ratios is for illustrative purposes and need not be strictly adhered to in the practice of the present invention.
Regarding the paper valve-forming liquid, it has been described above that the sulfite waste liquid can be used as it is in the reaction of the present invention, but it can be used, for example, by desaccharification with sodium hydroxide, methylolation with formaldehyde, or with a suitable sulfite compound or bisulfite. The compound may be modified by sulfonation and/or sulfoalkylation, or it may be fractionated to remove certain components or recover the lignosulfonate (this recovery itself is not purified or concentrated). sell). The amount of reactants used to make the adducts of the invention is:
Adjustments may need to be made depending on the presence of other reactive components, but such adjustments will be apparent and readily available to those skilled in the art. We will discuss sugars (other inorganic salts are also present) which may be present in up to about 50% of the amount together with other inorganic salts in the sulfite waste solution.

Since sugars tend to strongly reduce azo dyes, it is often important to convert them to the corresponding sugar acids.
Also with regard to sulfonation, the amounts of 2-8% organic sulfur based on lignin shown here reflect the levels of sulfonic acid groups (expressed as sulfur) normally and inherently present in the lignosulfonates of sulfite waste streams ( i.e. 4-8%) as well as the levels normally incorporated into lignin to make it active for use in the present invention (i.e. 2-7%).
It is understood that there is a term that encompasses the following. Although we have focused on the use of monohydroxyl benzyl alcohol, the use of polyhydroxyl benzyl alcohol offers significant advantages in reducing the amount of alcohol reactant required to make an effective dispersant. .

For example, small amounts of dihydroxyl derivatives may be used, such as 0.05 mmol per y of lignin (in some cases 1
(preferably 0.1 mmol per y), but the monohydroxyl derivative (compound) is usually 0.5 mmol per y. However, these advantages are more or less offset by the high manufacturing costs of polyhydroxyl compounds. Although there are some superficial differences in the methods of producing either benzyl alcohol (eg, their pH values), such differences can be easily adjusted and compensated for. Therefore, there is no need to further explain to those skilled in the art the method for producing the adduct.
Finally, the dyes used in the specific examples above are standard commercially available products that meet the standards applicable to dyes identified by the Color Index names given. Thus, the present invention provides novel dispersants made from sulfonated lignin materials that exhibit an optimal balance of properties that are highly suitable for disperse and putt dye applications. it is obvious.

Claims (1)

[Scope of Claims] 1. A dispersant composition comprising a lignin adduct, the lignin adduct comprising a sulfonated lignin material containing 2 to 8% by weight of chemically bonded organic sulfur and the lignin of the sulfonated lignin material. 0.05 to 4 mmol per 1 g of the general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (n is an integer from 1 to 3, A is a substituent selected from hydrogen, lower alkyl group, or hydroxymethyl group). A dispersant composition characterized by being an adduct of a hydroxybenzyl alcohol compound. 2. The dispersant composition of claim 1, wherein the lignin material is a lignosulfonate and the amount of organic sulfur is from 4 to 8% by weight. 3. The dispersant composition of claim 1, wherein the lignin material is a methylolated derivative. 4. The dispersant composition according to claim 1, wherein the lignin material is a waste liquid from a sulfite pulping process. 5. The dispersant composition according to claim 1, wherein the waste liquid is substantially de-saccharified and not purified. 6. The dispersant composition of claim 1, wherein the lignin material is sulfonated lignin and the amount of organic sulfur is from 2 to 7% by weight. 7. The dispersant composition of claim 1, wherein said benzyl alcohol compound is monohydroxybenzyl alcohol present in an amount of at least 0.5 mmol per gram of lignin moiety. 8. Claim 1, wherein said adduct contains 1.0 to 2.5 mmol of said benzyl alcohol per g of lignin part.
The dispersant composition described in 1.