JPS591748B2 - Dyeing and printing methods for hydrophobic fibers - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula (I) CH2C<,2 (I)2,>-■~-ku5<Y~ (wherein, X1, X2, Y1, and Y2 are each hydrogen atom,
R1 and R3 each represent a halogen atom, a lower alkyl group or a lower alkoxy group, each of which may be a substituted alkyl group, and R2 represents an alkylene group having 3 to 10 carbon atoms.

This is a method for dyeing and printing hydrophobic fibers, which is characterized by using two or more different types of styryl dyes shown in ).

Styryl dyes are generally bright greenish-yellow dyes with excellent light fastness, but they have the disadvantage of low sublimation fastness and PH
It has the disadvantage of being inferior in sensitivity, that is, resistance to decomposition against changes in pH during dyeing.

Among these drawbacks, sublimation fastness has been improved to some extent by introducing polar groups or increasing the size of dye molecules. However, since the PH sensitivity has not yet been improved, excellent reproducibility cannot be obtained in actual dyeing, and styryl dyes have a molar absorbance as high as quinophthalone dyes and are bright. However, it has not yet become widely used. As a result of intensive research and examination on styryl-based disperse dyes with excellent PH sensitivity, the present inventors found that the styryl-based dye represented by the general formula (1) above can solve the above-mentioned drawbacks, and has excellent sublimation resistance and light resistance. The present inventors have discovered that this is a yellow disperse dye with excellent water fastness and other fastness properties.

However, the dyes represented by the general formula (1) alone do not have sufficient build-up properties, so after further detailed study on this point, dyes represented by the general formula (1) but with different structures were found. It was discovered that the use of two or more types, preferably three or more types, provides excellent build-up properties, and the present invention was completed.

The important point to note here is that when two types of the above dyes are used, the density is almost twice as high as when using them alone, when three types are used, the density is almost three times as high, and when four types are used, the density is almost four times as high. This is something that can be done.

This fact is an entirely unexpected result, and its practical utility is extremely high. Examples of the dye of general formula (1) used in the present invention include the following compounds.

Among these dyes, dyes in which R2 is -C5H, O- or -C6Hl2- are particularly preferably used industrially. The styryl dye of the present invention can generally be produced as follows.

First, general formula n) (where Rl, R2, R3, Xl, X2
, Yl, and Y2 have the same meanings as above.

) is formylated by Vilsmeier reaction to give dialdehyde ().

This dialdehyde () is combined with malonitrile and a basic catalyst,
For example, in the presence of ammonia, dimethylamine, diethylamine, piperidine, piperidine acetate, sodium or potassium alcolade, and if necessary using a solvent such as methanol, ethanol, benzene, toluene, xylene, chloroform, carbon tetrachloride, etc. , preferably by applying heat to react to obtain the dye of general formula (1).

The dye represented by general formula (1) is 10 to 90% each.
They can be mixed in a conventional manner in a ratio of .

In carrying out the present invention, two or more different types of dyes represented by the general formula (1) are ground into fine particles and dispersed in an aqueous medium together with a suitable dispersant.

The dispersed dye is used in the form of a paste or in the form of a powder by spray drying or the like. Using the thus obtained dye composition, hydrophobic fibers are immersed in an aqueous medium at a temperature of 105°C or higher, preferably 11°C under pressure.
Dye at 0-140°C. Dyeing can also be carried out in the presence of a carrier such as o-phenylphenol or trichlorobenzene in a relatively high mud state, such as boiling water.
In addition, the dye dispersion was printed on cloth, heated at 150 to 230°C,
So-called thermosol dyeing, which involves dry heat treatment for 30 to 60 seconds, is also possible.

On the other hand, in the case of textile printing, the dye dispersion is kneaded with a suitable sizing agent, printed on cloth, and dyed by steaming or thermosol treatment. A solvent dyeing method using an organic solvent such as trichlorethylene or perchlorethylene as a dyeing medium is also possible. ) According to the method of the present invention, hydrophobic fibers such as synthetic and semi-synthetic fibers, such as cellulose acetate fibers, especially polyester fibers, have excellent dyeability, PH sensitivity (decomposition resistance), sublimation resistance and light resistance, It can also be dyed or printed in bright yellow with good reproducibility.

In addition, the dye of the present invention can be used for the dyeing of polyester fiber fibers and artificial leather, which have been increasing in recent years.
Shows particularly excellent dyeing properties compared to conventional styryl dyes.
Furthermore, the dye of the present invention has excellent PH sensitivity while P
Because it easily decomposes when the pH exceeds H7 and reaches PH9 or higher,
Cotton contamination in T/C blend dyeing is removed by alkaline washing.
It also has the advantage of being easy to remove.

In addition, alkaline resist dyeing is also possible in textile printing. next,
In order to clarify the effects of the present invention, the above formulas (1) and (2)
, (3) Exhaust dyeing of polyester fibers using the dye (3)
130°C, 1 hour, bath ratio 1:30, treatment bath containing anionic surfactant 29/e), (1), (2)
, when dyes (3) are used alone, when dyes (1) and (2) are mixed at a ratio of 1:1, and when dyes (1), (2), and (3) are mixed at a ratio of 1:1:1. The dyeing rate when mixed and used is shown in Table 1.

From Table 1, it is clear that when used in combination, there is a significant effect on improving build applicability. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

In the text, parts represent parts by weight. Example 1 1 part of the dye of the formula (1) and 1 part of the dye of the formula (2),
5 parts of formalin condensate of naphthalene-β-sulfonic acid,
The dispersion obtained by mixing with 3 parts of sodium ligninsulfonic acid and 20 parts of water and milling in a ball mill for 20 hours is spray-dried to obtain 10 parts of a dye.

1 part of the dye obtained in this way is added to 3,000 parts of water together with 100 parts of spun polyester yarn and dyed for 60 minutes at 130 DEG C. under pressure. After dyeing, the dyed product was washed in hot water, further washed with reduction, and dried to obtain the most vivid and durable yellow dyed product of Color Baliyu. Moreover, the concentration is significantly higher than that of a dyed product obtained by dyeing in the same manner using two parts each of dye (1) or dye (2) alone. Example 2 The same results were obtained by dyeing in the same manner as in Example 1, except that dye (3) was used instead of dye (2).

Example 3 One part of each of the dyes of formulas (1), (2), and (3) above was mixed and dyed and treated in the same manner as in Example 1.

A bright and strong yellow dyeing was obtained. Its concentration is
It is significantly larger than that of a dyed fabric obtained by dyeing in the same manner using three parts each of dyes (1), (2), and (3).

Example 4 Three dyes of formulas (1), (3), and (4) were each used.
Each part was dispersed in 3,000 parts of water using an appropriate amount of dispersant.

After adding 3 parts of sodium alginate, a polyester cloth was soaked and squeezed with a mangle until the weight increased by 60%.
90℃ at 200℃ after intermediate drying using a heat lice dryer
Dry heat treatment was performed for seconds. After the thermosol color development was completed, the cloth was subjected to reduction washing, washing with water, and drying.

The dyed product thus obtained exhibited a bright yellow color and had excellent fastness properties.

The density of the dyed product was significantly superior to that obtained by dyeing in the same manner using 10 parts of each of dyes (1), (3), or (4) individually.

Example 5 When one part of each of the dyes of formulas (5), (6), and (7) is mixed and treated in the same manner as in Example 1, a bright and strong yellow dyed product is obtained. teeth,(
5), (6), and (7) for dyed fabrics obtained by dyeing in the same manner using three parts each of dyes,
It is significantly large.

Example 5 One part of each of the dyes of formulas (1), (8), and (9) was taken and mixed with 5 parts of a formalin condensate of naphthalene-β-sulfonic acid, 2 parts of sodium ligninsulfonate, and 20 parts of water. The dispersion obtained by milling in a ball mill for 20 hours is diluted with water to adjust the dye content to 20%.

This paste is used to make a printing paste with the following recipe. Print this old printing paste onto polyester cloth and dry at 13°C.
Steam for 30 minutes.

After washing and drying, a yellow printed cloth with excellent clarity and density is obtained.

The concentration is 3 each of dyes (1), (8), and (9).
This is significantly larger than the printed fabric obtained by dyeing the dye in the same manner when used alone.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula,
_1, X_2, Y_1, and Y_2 each represent a hydrogen atom, halogen atom, lower alkyl group, or lower alkoxy group, R_1 and R_3 each represent an alkyl group that may be substituted, and R_2 represents an alkylene group having 3 to 10 carbon atoms. represents. ) A method for dyeing and printing hydrophobic fibers, characterized by using two or more different types of styryl dyes. 2 In general formula (I), R_2 is -C_5H_1
The dyeing and printing method according to claim 1, which is _0- or -C_6H_1_2-.