JPS6020515B2 - Method for improving dyeability of cellulose fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving the dyeability of cellulose fibers, and more specifically, by chemically modifying cellulose fibers, the dyeability with hydrophobic dyes, particularly disperse dyes, can be improved. It is in granting.

Conventionally, it has been reported in Tokusei No. 50-18778 and Japanese Unexamined Patent Publication No. 50-35476 that affinity for disperse dyes can be imparted by chemically modifying cellulose fibers by acetylation, benzoylation, etc. It is known from
However, it is not only economically disadvantageous because the reaction efficiency is low and a large amount of modifier is required, but also the quality effect is uneven and the degree of substitution is higher than necessary as a whole to obtain uniform dyeing properties. It has disadvantages such as requiring The present inventors have conducted intensive research to solve the above-mentioned drawbacks, and as a result, have arrived at the method of the present invention.

That is, the present invention is characterized in that cellulose fibers are treated with an aromatic acylating agent and an aromatic epixy compound in the presence of a basic catalyst. When using the method of the present invention, due to the synergistic effect of using both processing agents in combination, the dyeability can be significantly improved compared to products treated with each compound alone.

Another major feature of the treated fabric according to the present invention is that the uniformity of the modification effect is excellent, so that uniform and clear dyeing can be obtained even at a low quality level. It is unclear why aromatic epoxy compounds, which are not effective in improving cloth dyeability when used alone, exhibit superior effects when used in combination with aromatic acylating agents, but aliphatic epoxides are ineffective. This was a complete surprise. Aromatic acylating agents used in the present invention include penzoyl chloride, penzoyl bromide, parachlorobenzoyl chloride, orthochlorobenzoyl chloride,
Paranitrobesoyl chloride, metanitrobenzoyl chloride, 2,4-dinitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride, 2,4,6-trinitrobenzoyl chloride, 3,4,5-triodobenzoyl chloride, chloride Penzoyl halides or their derivatives such as paramethoxybenzoyl, aromatic sulfonic acid chlorides such as toluenesulfonyl chloride and naphthalenesulfonyl chloride, aromatic acid anhydrides such as benzoic anhydride, etc. These can be used alone or in combination of two or more.

Particularly preferred, however, is penzoyl chloride or its derivatives. In addition, the aromatic epoxy compounds used in the present invention include aromatic carboxylic acids such as 2,3-epoxypropyl benzoate, bis(2,3-epoxypropyl)isophthalate, and bis(2,3-epoxypropyl)phthalate. Epoxypropyl ester, 2,3-epoxypropyl benzyl ether, 2,3-epoxypropyl phenyl ethyl ether, 2,3-epoxypropyl phenylpropyl ether, phthalyl alcohol bis(2,3- epoxypropyl ether, phenyl-
2,3-epoxypropyl ether, naphthyl 2,3
-Epoxypropyl ether, Pis(2,3-epoxypropyl)resorcinol, Tris(2,3-epoxypropyl)phloroglucinol, 2,2-pis[para(
2,3-epoxypropoxy)phenyl]propane, 2
In addition to epoxypropyl ethers of phenols such as 12,4,4-tetrakis(2,3-epoxypropoxy)piphenyl, N-N-bis(2,3-epoxypropyl)aniline, 4-(1・2-epoxyethyl)
Examples include 1-1,2-epoxybenzene, styrene oxide, and their precursors, which may be used alone or in combination of two or more.

However, epoxypropylene esters of aromatic carboxylic acids, epoxypropylene styrene oxides of aromatic alcohols or phenols are preferred, especially phenyl-2,3-epoxypropyl ether, bis(2
-3-epoxypropyl) phthalate and 2,3-epoxypropyl benzoate are particularly preferred. The amount of aromatic acylating agent and aromatic epoxy compound used depends on the processing method, processing conditions, etc., but the total concentration of both modifiers is usually 10% or more, and the total amount applied to the fiber is usually 5 to 60%.
% by weight, preferably from 10 to 4% by weight. Further, the ratio of the aromatic acylating agent and the aromatic epoxy compound used is usually 0.05 to 5 mol, preferably 0.1 to 2 mol, per 1 mol of the aromatic acylating agent. . Furthermore, basic catalysts used in the present invention include hydroxides such as sodium, potassium, lithium, cesium, rubidium, and barium, inorganic bases such as carbonates, phosphates, and silicates, trimethylamine, triethylamine, pyridine, Examples include dimethylaniline, tertiary amines such as 1,4-diazabicyclo-2,2,2-octane, and organic bases such as quaternary ammonium hydroxide. It is selected and used as appropriate.

The amount used is determined by the type and concentration of the modifier used, the treatment method, reaction conditions, etc. To explain the treatment method of the present invention in more detail, in many cases, the aromatic acylating agent also serves as a solvent for the aromatic epoxy compound, so a solvent is not particularly necessary. The agent is appropriately diluted with a solvent before use.

Solvents used include toluene, benzene, petroleum ether, kerosene, trichloroethane, and trichloride. loethylene,
Examples include, but are not limited to, dichloromethane, ethyl ether, acetone, and tetrahydrofuran. Cellulose fibers are impregnated with a solution containing both additives by any method, and then impregnated with a basic catalyst, and then treated at room temperature by batch-up or warming, or if heated by dry heat or wet heat. modified. Also, the order of impregnation may be reversed. Furthermore, if the basic catalyst is in particular a tertiary amine, catalyst and modifier can also be used interchangeably. Usually, the temperature of the modifier solution and the catalyst solution is preferably 5 to 5,000, and the modifier solution and the catalyst solution are preferably applied by a pad method. In this case, the reduction ratio is preferably 10% by weight or less from the viewpoint of uniformity of processing. Of course, it is also possible to partially impart a modifier and/or catalyst for partial teaching.
In the present invention, cellulose fibers include not only 100% cellulose fiber products such as cotton, viscose rayon, polynosic rayon, copper ammonium rayon, and linen, but also cellulose fibers such as Isobatsu, polyester, and acetate. ,polyamide,
Refers to products mixed with synthetic or semi-synthetic fibers such as polyvinyl alcohol. Its form may be cotton, thread-like material, knitted fabric, non-woven fabric, rug, etc., but cloth is particularly preferred. The treated fabric thus obtained has an excellent affinity for hydrophobic dyes, especially disperse dyes.
Regular printing using disperse dyes, transfer printing, as well as dip dyeing,
Even in pad dyeing etc., it can be dyed robustly and vividly. In addition, in the case of a mixture of disperse dye beamable synthetic fibers and cellulose fibers, it is of course possible to dye both at the same time with the same dye. The present invention will be explained below with reference to Examples.

Note that parts and % in the examples indicate parts by weight and % by weight. Example 1 Cotton broadcloth, which had been desized, scoured, and bleached in a conventional manner, was soaked in a solution consisting of 2 parts of penzoyl chloride, 2 parts of epoxypropyl benzoate, and 6 parts of benzene, until the squeezing rate was 60%. After squeezing out the liquid, the sample was then immersed in a 25% aqueous sodium hydroxide solution to give a squeezing rate of 70%, and then left under tension at room temperature for 6 minutes.

Thereafter, it was washed with methanol, further washed with scratches, and dried. At the same time, Comparative Example 1 is a solution of 4 parts of penzoyl chloride and 60 parts of benzene, Comparative Example 2 is a solution of 4 parts of epoxypropyl benzoate and 6 parts of benzene, and Comparative Example 3 is a solution of 2 parts of epoxypropyl-2-ethylhexane. The same procedure as in Example 1 was carried out using a solution consisting of 2 parts of penzoyl chloride, 2 parts of benzene, and 6 parts of benzene. The resulting treated fabric was coated with C. 1. Using a printing ink containing Dispersed Red 6050 Y/Y and Methyl Cellulose 25 Y/Y, the transfer paper obtained by printing with a screen printing machine is layered and heated at 210 qo for three cycles of tochi sand for sublimation transfer printing. did. The results are shown in Table 1. Table I From Table 1, it can be seen that the treated fabric of the present invention using a combination of penzoyl chloride and epoxypropyl benzoate gives a dyed product with excellent color development and good sharpness.

Furthermore, the fastness and texture were also extremely good. Especially comparative example 2
The fact that when treated with epoxypropyl benzoate alone, almost no color develops, but when used in combination with penzoyl chloride, it exhibits a remarkable dyeing property improvement effect is thought to be due to the synergistic effect of both treatments. This synergistic effect was not obtained with the aliphatic epoxy compound of Comparative Example 3, but was unique to aromatic epoxy compounds, which is completely surprising. Note that the apparent color density is a value obtained by converting the Z value of the trithic value into K/S. Example 2 A jersey striped fabric made of polyester/cotton (65/35) blended yarn was mixed with 15 parts of rosemethoxybenzoyl chloride and 2.3 parts of di(2.3
- Soaked in a solution consisting of 15 parts of epoxypropyl phthalate and 7 parts of toluene, then soaked in shark liquid to give a reduction ratio of 60%, and then soaked in pyridine to give a reduction ratio of 60%.
After adding shark liquid to a concentration of 0%, it was heat-treated with millet at 100 qo for 5 minutes.

After that, an aqueous solution containing 2 to 8 hours of nonionic surfactant was added.
It was washed at 0qo for 30 minutes, then washed with hot water and dried. Also,
Comparative Example 4 is a solution consisting of 3 parts of paramethoxybenzoyl chloride and 7 parts of toluene, and Comparative Example 5 is a solution consisting of 2 parts of di(2 parts).
・Processing was carried out in the same manner as in Example 2 using a solution consisting of 3 parts of 3-epoxypropyl phthalate and 7 parts of toluene.

The obtained treated fabric was treated with C. 1. Disperse Blue-183
Immerse in a solution consisting of 30 ml of polyester and sodium alginate for 2 t/s, squeeze the liquid to a squeezing rate of 65%, and
5 at 3000 Current sand, dry for a while, then 2 at 19500
After heat treatment for 9 seconds, the sample was soaped for 2 steps at 7000°C with an aqueous solution containing 2 times a day of a nonionic surfactant.

As a result, the fabrics treated according to the present invention were dyed uniformly and in deep colors with the Kyodo dye for cotton fibers and polyester fibers.
On the other hand, in the comparative example, the cotton fibers were not dyed sufficiently and had a marbling tone as a whole, which was completely lacking in commercial value. Example 3 Polyester norayon (55/45) blended puff.

Phosphorus was immersed in a solution consisting of 25 parts of metanitrobenzoyl chloride, 25 parts of phenyleboxypropyl ether and 5 parts of white kerosene, and the liquid was squeezed to a squeezing rate of 60%. % trimethylamine aqueous solution,
After squeezing the liquid to a squeezing rate of 70%, it was dried at room temperature, then subjected to dry heat treatment at 150 qo for 2 minutes, washed with running water, and then heated at 50°C for 1 hour with an aqueous solution containing a nonionic activator.
The wound was soaped for 0 minutes, washed and dried. The resulting treated fabric was coated with C. 1. 902 parts of Dispersed, 3.6 parts of sodium alginate, 1 part of sodium metanitrobenzenesulfonate
170 parts and 93.4 parts of water.
After being treated with superheated steam at .degree. C. for 10 minutes, it was washed with hot water, and further subjected to reduction cleaning at 70.degree. C. for 2 G minutes with an aqueous solution consisting of hydrosulfite/hydrosulfite, washed with water, and dried.

As a result, both the rayon part and the polyester part were printed uniformly and vividly in deep red using the same dye. Example 4 The same procedure was carried out except that cotton broadcloth was used as a liquid containing a total of 4 bases of penzoyl chloride and epoxypropyl benzoate and 6 bases of benzene, with the exception of changing the proportion of both cost-modifying agents used. The fabric was processed using the same machine as Example 1, and then the obtained treated fabric was transfer printed on the same machine as Example 1.

The results are shown in Table-2. Table 2 Although it depends on the total concentration of stimulant used, Table 2 shows that a synergistic effect can be obtained when the molar ratio of penzoyl chloride and epoxypropyl benzoate is 1:0.06 to 5. .

Claims (1)

[Scope of Claims] 1. A method for improving the dyeability of cellulose fibers, which comprises treating cellulose fibers with an aromatic acylating agent and an aromatic epoxy compound in the presence of a basic catalyst. 2. The method according to claim 1, wherein the aromatic acylating agent is benzoyl chloride or a derivative thereof. 3. The method according to claim 1, wherein the aromatic epoxy compound is an epoxypropyl ester of an aromatic carboxylic acid, an epoxypropyl ether of an aromatic alcohol, an epoxypropyl ether of phenols, or styrene oxide. 4. The method according to claim 1, characterized in that 0.05 to 5 moles of the aromatic epoxy compound are used in combination with 1 mole of the aromatic acylating agent.