JPS6024230B2 - Disperse dye preparation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly concentrated preparation of disperse dyes used in continuous dyeing or textile printing of synthetic fibers.

More specifically, it is a dye preparation used when continuously dyeing or printing synthetic fibers such as polyester, acetate, polyamide, and blended fabrics thereof, and is a disperse dye and a general formula R.f ratio of 2 days 4 Ume ratio 3 Day 6m × ……'1
} (In the formula, R represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an acyl group having 4 to 30 carbon atoms, or an aryl group, alkaryl group, or aralkyl group having 6 to 30 carbon atoms.

1 is an integer of 1 or more, m is 0 or an integer of 1 or more, and 1
10 m is 35 to 200, and 1/m is 2 or more.

X is a hydroxyl group or OS03M, S03M, OP0
3HM or OP03M2, where M represents an alkali metal ion or a quaternary ammonium ion. ), or the general formula R2f ÷ ratio 2 days 4 Ume ratio 3 days 6
m×]n...'2' (in the formula, R2 represents a saturated or unsaturated hydrocarbon group containing an ester group and having 4 to 60 carbon atoms, 1 is an integer of 1 or more, m is 0 or 1 or more is an integer of 10 m is 35 to 200, and 1/
m is 2 or more, and n is an integer of 1 or more.

× is a hydroxyl group, or OS03M, S03M, OP
03HM or OP03M2, where M represents an alkali metal ion or a quaternary ammonium ion. ) The present invention relates to a water-dispersible, high-concentration dye for continuous dyeing or textile printing, which contains the compound shown in (a). When synthetic fibers such as polyester, acetate, or polyamide, and their blends are continuously dyed or printed using disperse dyes that are substantially water-insoluble, they are finely pulverized in a separate process beforehand into the padding layer or printing paste, respectively. It is common practice to add and use adjusted dye preparations.

This is because if a water-insoluble, high-melting-point dye source is added unadjusted to an aqueous padding paste or printing paste, a uniform dyed product cannot be obtained. Conventionally, disperse dye preparations require the use of a dispersant in order to make the dye source into fine particles and stabilize the dispersion, and generally commercially available dye preparations do not always contain a dispersant. There is.

Further, the form of the dye preparation is powder, granule, paste, or liquid. The dye dispersant used in this dye preparation is usually an anionic surfactant, such as a formalin condensate of 8-naphthalene sulfonate, an aromatic sulfonic acid converter such as sodium lignosulfonate, or an alkylbenzene sulfonate. etc. A preparation prepared using these dispersants is added to a padding bath for continuous dyeing or a printing paste paste for printing, and after padding or printing the dyed fabric, drying at a temperature of 100 to 12,000,
If heat fixing is then carried out at 150 to 220 qo, a sufficient dyeing rate and a good dyed surface cannot be obtained (the heat fixing conditions here are generally dry heat or high-temperature steaming). The reason for this poor dyeing rate is that Buchholz et al.
hholtz. Am. DyeStuff. Report to r, May, 25, P. 418 (1964)), the dispersant contained in the dye preparation prevents the transfer of the dye to the fibers, and the reason why a good dyed surface cannot be obtained is because the dye does not transfer to the fiber surface. This is thought to be due to poor wettability.

Improvements to these shortcomings were proposed by S. Buch et al.
holtz. Am. Dyestuff. Reponer
, May, 25, P. 418 (1964)), it is said that a dye preparation containing as little dispersant as possible and ultrafine particles is preferable.

However, since a high melting point anionic activator is used as a dispersant in the dye preparation as described above, the only way for the high melting point dye to migrate to the fiber surface is by sublimation using air as a medium. For this reason, a considerably high temperature is required for dye fixation, causing sublimation loss, resulting in insufficient improvements in both dyeing rate and dyed surface, and further resulting in a deterioration in the texture of the dyed object. Another improvement has been to add nonionic surfactants to padding or printing pastes together with disperse dye preparations in which conventional anionic surfactants are used as dispersants.

Examples of the nonionic surfactant include many commercially available nonionic surfactants, such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. However, these methods cannot be said to be sufficient. In other words, the combination of the nonionic surfactant and the dye preparation causes a large amount of spec, and the dyeing rate is also highly dependent on the dye, so in practice, it is very difficult to select the nonionic surfactant at the stage of determining the formulation. . This is thought to be due to the interaction between the high melting point dispersant already contained in the dye preparation and the nonionic surfactant added afterwards. In addition, in this case, since the amount added is generally too large relative to the dye base material, a decoloring phenomenon occurs due to decomposition products of ethylene oxide. As a result of repeated research in order to improve these shortcomings, the present inventors have developed a method to replace the high-melting point anionic surfactant with a specified non-containing surfactant with a low melting point (below 100 qo) in the production stage of dye preparations. By using an appropriate amount of an ionic surfactant or a specified polyoxyalkylene-type anionic surfactant with a low melting point (10,000 or less), a very stable and highly concentrated dye dispersion can be obtained, and this stable and highly concentrated dye dispersion can be obtained. The present invention has been achieved by making it possible to improve the dyeing rate and obtain a dyed object with a good dyed surface by diluting and applying a dye dispersion to continuous dyeing or printing.

That is, the dye preparation according to the present invention has a disperse dye and a weight percentage of 30 to 15 based on the dye as follows: 1)(
In the formula, R represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an acyl group having 4 to 30 carbon atoms, or an aryl group, alkaryl group, or aralkyl group having 6 to 30 carbon atoms.

1 is an integer of 1 or more, m is 0 or an integer of 1 or more, and 1
10 m is 35 to 200, and 1/m is 2 or more.

X is a hydroxyl group or OS03M, S03M, OP0
3HM or OP03M2, where M represents an alkali metal ion or a quaternary ammonium ion. ), or a compound represented by the general formula R2f÷ratio 2 days 4 Ume ratio 3 days 6 n m×]n.・・・． ... [2' (in the formula, R2 represents a saturated or unsaturated hydrocarbon group having 4 to 60 carbon atoms containing an ester group, 1 is an integer of 1 or more, m is an integer of 0 or 1 or more, , 10m is 35 to 200, and 1/m is 2 or more, and n is 1 or more, preferably 1 to 6
is an integer.

X is a hydroxyl group or OS03M, S03M, OP0
3HM or OP03M2, where M represents an alkali metal ion or a quaternary ammonium ion.

) is a water-degradable high-concentration dye preparation for continuous dyeing or textile printing containing the compound shown in 'A saturated or unsaturated alkyl group having 1 to 20 carbon atoms as used in the present invention refers to an alkyl group having 1 to 20 carbon atoms having a straight chain, a branched chain, a multiple bond, or a non-aromatic ring, either individually or in combination. groups, or mixtures thereof, such as methyl, ethyl, propyl, phthyl, hexyl, octyl, nonyl, bentyl,
Neobentyl, bentadienyl, cyclobentadienyl, dicyclobentadienyl, tricyclobentadienyl, tetracyclobentadienyl, ethylhexyl, cyclohexyl, heptyl, decyl, dodecyl, tetradecyl, tridecyl, bentadecyl, hexadecyl, octadecyl, oleyl, heptadecyl , diisobutylenyl,
Examples include dodecylenyl, tetradecylenyl, an alkyl group derived from coconut oil, an alkyl group derived from lanolin, an alkyl group derived from tallow, and an alkyl group derived from tall oil.

The acyl group having 4 to 30 carbon atoms as used in the present invention refers to an acyl group having 4 to 30 carbon atoms and having an aromatic, linear, branched, ring, or multiple bond, or a mixture thereof. Oils stearoyl, palmitoyl, valeryl, butyryl, naphthoyl, cinnamoyl, toluoyl, benzoyl, furoyl, monobenzylbeyzoyl "tribenzyl-penzoyl, monostyryl benzoyl, distyryl benzoyl, tristyryl benzoyl or (q=
0, 1, 2 or 3 R7. R8, R9, R, o, R, .
, R, 2 is hydrogen or a methyl group (or an ethyl group) or an acyl residue of a natural resin acid such as rosin acid, such as abietic acid, pimaric acid, neoavietic acid, repopimaric acid, hydroapietic acid, dextropimaric acid, etc., or derived from tall oil. Examples of the aryl group, alkaryl group, or aralkyl group having 6 to 30 carbon atoms as used in the present invention include phenyl, naphthyl, phenylphenyl, octylphenyl, nonylphenyl, Tribenzylphenyl, dibenzylphenyl, monobenzylphenyl, tristyrylphenyl, distyrylphenyl, monostyrylphenyl, benzylphenyl phenyl, butylphenyl,
Examples include phenylethyl, benzyl, naphthylmethyl, and the like.

The ester group-containing saturated or unsaturated hydrocarbon group having 4 to 60 carbon atoms as used in the present invention is an ester of a polyhydroxy compound and a carboxylic acid having a hydroxyl group, such as castor oil. Examples of hydroxy compounds include ethylene glycol, glycerin, bentanetriol, sorbitan, sorbide, and sorbitol, but preferred are glycerin, as well as carboxylic acids and polyhydrides that do not have hydroxy groups.

It is also possible to include esters with xyl compounds in which one or more hydroxy groups remain after the hydroxyl reaction.
The alkali metals referred to in the present invention include sodium, potassium, lithium, cesium, rubidium, and the like.

The quaternary ammonium ion referred to in the present invention is not only an ammonium ion but also an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.
Ammonium ions having 1 to 4 alkyl groups having hydroxyl groups on the nitrogen atom, individually or in combination, such as trimethylamine,
The water-dispersible high-concentration dye preparation according to the present invention, which can be exemplified by ammonium salts such as triethanolamine, diethylamine, diethanolamine, monoethanolamine, triethylamine, and dimethylmonoethanolamine, can be prepared by known means as a disperse dye raw material 10. 5 to 5 percent by weight of the surfactant according to the invention and 30 to 15 percent by weight of the surfactant based on the raw dyestuff in a milling device operating continuously or discontinuously with water until the average particle size of the dye is 0.5 to 1.5 percent by weight.
It is manufactured by pulverizing it until it becomes 1 to 1r.

As the grinding device, a ball mill, colloid mill, sand mill, or pearl mill is used. The low melting point specified nonionic surfactant or the low melting point specified polyoxyalkylene type anionic surfactant used in the water-dispersible high concentration dye preparation according to the present invention can be produced by known methods.
That is, ethylene oxide and propylene oxide can be added randomly or in blocks to a compound having a hydroxyl group, and if necessary, etherification, phosphoric acid esterification, sulfuric acid esterification, or carboxylation can be carried out.

The surfactant according to the present invention is 30 to 1
A water-dispersible highly concentrated dye preparation is produced using a weight percent of 5%, but below 30% it is insufficient for fine particle dispersion, and above 150% the dyeing rate decreases when applied for dyeing. An even more preferred range is 40 to 90 weight percent.

Although the addition of anionic surfactants such as ligninsulfonic acid and formalin condensate of sodium 8-naphthalenesulfonate is outside the scope of the present invention, it is permissible to add 10% or less of the water-insoluble dye. In the compound of Shikikawa or Formula (2) according to the present invention, if the total number of added moles of ethylene oxide or ethylene oxide and propylene oxide is less than 35 moles, fine particle dispersion is poor, and when applied to textile printing, bleeding occurs. Also, 20
If the amount is more than 0 mol, fine particle dispersion will be poor and the dyeing rate will also decrease. If the ratio of the number of moles of ethylene oxide added to the number of moles of propylene oxide added is less than 2, fine particle dispersion will still be poor, and bleeding will likely occur when applied to textile printing. Also, by ethylene oxide, or a compound in which the total number of added moles of ethylene oxide and propylene oxide is less than 35 moles, or the ratio of the number of added moles of ethylene oxide to the number of added moles of propylene oxide is less than 2. Dye preparations have extremely low storage stability and cannot be sold as dye preparations. The present invention will be specifically explained below with reference to Examples, but the scope of the present invention is not limited thereto.

Example 1C. 1. 15 parts of bulk powder of Disperse Red 16 and 6 parts of ethylene oxide in n-butanol
10 parts of a nonionic surfactant to which 0 mol and 13 mol of propylene oxide were added were mixed together with 100 parts of water, and the mixture was ground in a sand mill until the particle size became 1 mm or less and taken out.

This dye preparation was a long-term stable dispersion in water. This prepared product was subjected to the application test described below. Example 2 A dye preparation prepared in the same manner using, in place of the nonionic surfactant of Example 1, parts of activator 2 in which 150 moles of ethylene oxide were added to stearyl alcohol was a long-term stable dispersion in water. there were.

This prepared product was subjected to the application test described below. Example 3 A dye preparation prepared in the same manner as in Example 1 using activator 1 Hakarito, which is prepared by adding 30 moles of ethylene oxide and 8 moles of propylene oxide to ortho phenyl phenol, instead of the nonionic surfactant of Example 1. was a long-term stable dispersion in water.

Example 4 Instead of the nonionic surfactant of Example 1, 40 moles of ethylene oxide was added to tribenzylated phenol,
A dye preparation similarly prepared using one part of an ether-type anionic activator made into a sulfate ester soda salt was a long-term stable dispersion in water.

Example 5 A dye preparation prepared in the same manner using 16 parts of an activator prepared by adding 60 moles of ethylene oxide to tall oil in place of the nonionic surfactant of Example 1 was a long-term stable dispersion in water. Met.

Example 6 A dye preparation prepared in the same manner using 8 parts of an activator prepared by adding 50 moles of ethylene oxide to stearic acid in place of the nonionic surfactant of Example 1 was a long-term stable dispersion in water. It was liquid.

Example 7 In place of the nonionic surfactant of Example 1, a dye preparation prepared in the same manner using 12 groups of activators prepared by adding 100 moles of ethylene oxide to castor oil was a long-term stable dispersion in water. It was liquid.

Example 8 Instead of the nonionic surfactant in Example 1, a similar product was prepared using 9 parts of an ether-type anionic surfactant made by adding 35 moles of ethylene oxide to nonylphenol and then converting it into potassium phosphate salt. The dye preparation was a long-term stable dispersion in water.

Example 9 C. Two parts of IDispe Dai Blue 27 bulk powder and one part of a nonionic surfactant prepared by adding 50 moles of ethylene oxide to rosin acid were mixed together with 100 parts of water, and ground in a sand mill until the particle size was 1 French or less. I took it out.

This dye preparation was a long-term stable dispersion in water. Example 10 In place of the nonionic surfactant of Example 9, a dye preparation prepared in the same manner using 12 activators prepared by adding 100 moles of ethylene oxide to lanolin alcohol was a long-term stable dispersion in water. there were.

Example 11 Instead of the nonionic surfactant of Example 9,
A dye preparation similarly prepared using a nonionic surfactant containing 120 moles of ethylene oxide and 30 moles of propylene oxide to butyl alcohol was a long-term stable dispersion in water.

Example 12 A dye preparation prepared similarly using 25 parts of an activator prepared by adding 64 moles of ethylene oxide to styrenated phenol in place of the nonionic surfactant of Example 9 was found to be stable over a long period of time. It was a dispersion in water.

Application examples in which the present invention shown in the above examples and the following comparative example are applied to continuous dyeing and textile printing will be described below.

Comparative Example 1 A dye preparation prepared in the same manner using formalin condensate 10 of sodium 8-naphthalene sulfonate in place of the nonionic surfactant of Example 1 was a long-term stable dispersion in water.

Comparative Example 2 A dye preparation prepared similarly using 12 parts of sodium ligninsulfonate in place of the nonionic surfactant of Example 1 was a slightly unstable dispersion in water.

Comparative Example 3 A dye preparation prepared in the same manner using an activator prepared by adding 10 moles of ethylene oxide to nonylphenol in place of the nonionic surfactant of Example 1 was an unstable dispersion in water.

Comparative Example 4 A dye preparation prepared in the same manner as in Example 7 using 3 parts (20% relative to dye) of the nonionic surfactant was an unstable dispersion in water.

Comparative Example 5 A dye preparation prepared in the same manner as in Example 1 using 27 parts (180% based on the dye) of the nonionic surfactant was as follows:
It was a rather stable dye preparation.

Comparative Example 6 A dye preparation prepared in the same manner as in Example 9 using 1 part of creosote oil sulfonic acid soda formalin condensate instead of the nonionic surfactant was a stable dispersion in water.

Comparative Example 7 A dye preparation prepared in the same manner as in Example 9 using 10 moles of ethylene oxide added to stearyl alcohol and 12 parts of an ether-type anionic surfactant made into sodium sulfate ester salt was slightly different. It was an unstable dispersion in water.

Comparative Example 8 A dye preparation prepared in the same manner as in Example 9 using 12 parts of a nonionic surfactant prepared by adding 15 moles of ethylene oxide to styrenated phenol instead of the surfactant was an unstable dispersion in water. .

Application test example 1 The dye preparations shown in Examples and Comparative Examples were diluted with water to prepare padding with a dye solid content of 7%/50%, and a polyester processed yarn fabric and a polyester/cotton blend of 4% Soak the broad cloth one by one, about 80%
% mangle squeezing, drying was performed at 100 qo for 3 minutes, and then dry heat treatment was performed at 200 qo for 1 minute, that is, thermosol dyeing.

Next, the dye fixed on the surface was removed by reduction washing with warm water (70 to 80 oo) containing hydrosulfite 2 days/day and Benol AX (nonionic detergent) 2 days/day, and dried. The dyeing rate of the dyed product is 1% of the dyed product with dimethylformamide.
Extracted for 20 minutes at 20 oo, and calculated by colorimetry. The level of unevenness on the dyed surface, that is, on the surface of the dyed object, was determined visually. The results are shown in Table 1. Table 1 Note) Concubine, stability 3. When left at room temperature for one month, the dye does not aggregate easily and is stable.

2. When left at room temperature for a month, some of the dye aggregates, but
If you worship it, it will be redistributed.

1. When left at room temperature for a month, the dye will aggregate and form clumps and will not be redispersed. 2. Dyed surface 3. The dyed surface is smooth and uniform2. Slight irritation is observed and the surface lacks uniformity 1. Application test example where the dyed surface becomes boxy or irritated 2 Using carboxymethyl cellulose and sodium alginate, the viscosity is 1500. p. To the printing paste adjusted to , 180 oo for 5 minutes using a high temperature steamer (HT steamer).

Thereafter, it was subjected to reduction cleaning and drying. The apparent density of the dyed object is determined from the L value of the color machine reflectance (1-wave L).
P was calculated, and comparative values were calculated for each comparative product 1 or 6 as 100%.

Bleedability, that is, the degree of pocketing at the edges, is determined by the naked eye. In addition, as for the stability of the color paste, the presence or absence of specs was determined with the naked eye to determine whether it was good or bad. The results are shown in Table 2. Table 2 Western) Husband, stability Same as Table 1 cum 2 burrito 4 sex 3. Image edges become sharp 2. Some edges of the picture are blurred 1. Ayagiwa is blurred throughout x3 Spec characteristics 3. No dye aggregation is observed2. Dye aggregation is observed in some places1. The dye aggregates are so large that they can be seen with the naked eye.

Claims (1)

[Claims] 1. A disperse dye and 30 to 150% by weight of the general formula R_1-(OC_2H_4)-(OC_3H_6
)-_mX...(1) (In the formula, R_1 is a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or 4 carbon atoms
It represents an acyl group having 6 to 30 carbon atoms, or an aryl group, alkaryl group, or aralkyl group having 6 to 30 carbon atoms. l is an integer of 1 or more, m is an integer of 0 or 1 or more,
l+m is 35 to 200, and l/m is 2 or more. X is a hydroxyl group, or OSO_3M, SO_
3M, OPO_3HM or OPO_3M_2, M
represents an alkali metal ion or a quaternary ammonium ion. ) or the general formula R_2-[
(OC_2H_4)_l]-OC_3H_6)_m-X
]_n...(2) (In the formula, R_2 represents a saturated or unsaturated hydrocarbon group having 4 to 60 carbon atoms containing an ester group, l is an integer of 1 or more, and m is an integer of 0 or 1 or more. l+m is 35 to 200, and l/
m is 2 or more, and n is an integer of 1 or more. X is a hydroxyl group, or OSO_3M, SO_3M,
OPO_3HM or OPO_3M_2, where M represents an alkali metal ion or a quaternary ammonium ion. ) A water-dispersible high-concentration dye preparation for continuous dyeing or textile printing containing the compound shown in 2 In the compound represented by formula (1), R_1 is the following formula ▲ Numerical formula, chemical formula, table, etc. , an aryloxy group, an aralkyl group, an unsaturated alkyl group, or a hydrogen atom), the water-dispersible high-concentration dye preparation according to claim 1. 3 The compound of formula (2) has the following general formula ▲ Numerical formula, chemical formula, table, etc. Represents a saturated or unsaturated alkylene group. l is an integer of 1 or more, m is 0 or an integer of 1 or more,
l+m is 35 to 200, and l/m is 2 or more. X is a hydroxyl group, or OSO_3M, SO_
3M, OPO_3HM or OPO_3M_2, M
represents an alkali metal ion or a quaternary ammonium ion) Claim 1
Water-dispersible high-concentration dye preparation described in Section 1. 4. The water-dispersible high-concentration dye preparation according to claim 3, wherein the compound of formula (2) is a compound obtained by adding 35 to 200 moles of ethylene oxide to an amount equivalent to 1 mole of castor oil. 5. The water-dispersible high-concentration dye preparation according to claim 1, wherein R_1 in the compound represented by formula (1) is a saturated or unsaturated linear alkyl group having 1 to 20 carbon atoms. 6 In the compound represented by formula (1), R_1 is the following formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_9 is a methyl group or a hydrogen atom, and p is 1, 2 or 3) Dispersible high concentration dye preparation. 7 In the compound represented by formula (1), R_1 is the following formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1_0 represents a linear saturated or unsaturated alkyl group having 3 to 29 carbon atoms) The water according to claim 1, which is an acyl group Dispersible high concentration dye preparation. 8. The water-dispersible high-concentration dye preparation according to claim 6, wherein the compound of formula (1) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 9 The compound of formula (1) is C_4H_9-(OC_2H_4)_6_0-(OC
_3H_6)_1_3-OH Claim No. 5
Water-dispersible high-concentration dye preparation described in Section 1. 10. The water-dispersible high-concentration dye preparation according to claim 1, wherein the compound of formula (1) is a compound obtained by adding 35 to 200 moles of ethylene oxide to an amount equivalent to 1 mole of rosin or tall oil.