JPS6316518B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers. The present inventors first applied an acid chloride such as P-toluenesulfonyl chloride and an alkali agent to a fabric at a certain ratio, and then steamed the fabric to create a fiber structure consisting of cellulose fibers or cellulose fibers and synthetic fibers. He discovered that it is possible to chemically modify materials so that they can be dyed with dyes such as disperse dyes, and filed a patent application based on this knowledge. However, in this method, if a weak alkali is used as the alkali agent, the degree of modification is small, and if a strong alkali is used, modification can be achieved sufficiently, but in actual production processing, the action as an alkali agent is too strong. Because the temperature is too high, uneven reforming tends to occur. In contrast, the present inventors discovered that when a weak alkaline agent is used in combination with a strong alkaline agent, the weak alkaline agent acts as a buffer for the reaction, allowing a uniform reaction to occur and making it difficult for uneven modification to occur. and completed the present invention. That is, the present invention provides a cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers, in which (a) a strong alkaline agent is added at a weight ratio of 1 to 20% relative to the fiber structure; A weak alkaline agent (b) in an amount such that the ratio (strong alkaline agent/weak alkaline agent) is 0.5 to 2.0 (b) A compound having the structure shown below in an amount such that the molar ratio with this strong alkaline agent is 0.1 to 2.0 is applied in any order. This is a dyeing method characterized by further applying steam treatment to chemically modify the material, and then dyeing with a disperse dye. (X means -H, -NO ₂ , -CH ₃ , -SO ₂ Cl) In the present invention, the cellulose fiber structure and the mixed structure of cellulose fiber and synthetic fiber are fabrics, thread-like fibers, or It may also be a cotton-like material before it becomes thread. The strong alkaline agents mentioned in the present invention include the following. In other words, hydroxides of alkali metals or alkaline earth metals such as lithium, sodium, potassium, beryllium, magnesium, calcium, and barium are called strong alkaline agents, and from a practical standpoint, sodium hydroxide, Potassium hydroxide is highly effective. Further, the weak alkaline agents mentioned in the present invention include the following. In other words, carbonates or bicarbonates of alkali metals or alkaline earth metals such as lithium, sodium, potassium, beryllium, magnesium, calcium, barium, etc., acetates, formates, butyrates of alkali metals, etc. are used as weak alkaline agents. However, when considering practicality, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, calcium carbonate,
Calcium bicarbonate, magnesium carbonate, magnesium carbonate hydroxide, sodium acetate, potassium acetate, magnesium acetate, etc. are highly effective. In addition, the chemical modifier has the following structure,
Specifically, P-toluenesulfonyl chloride,
O-toluenesulfonyl chloride, m-toluenesulfonyl chloride, benzenesulfonyl chloride, O-nitrobenzenesulfonyl chloride, m
-Nitrobenzenesulfonyl chloride, P-nitrobenzenesulfonyl chloride, toluene-3,
4 disulfonyl chloride and the like. (X means H, --NO ₂ , --CH ₃ , or --SO ₂ Cl) Hereinafter, the modification process of the present invention will be explained with reference to the drawings. That is, FIG. 1 is a schematic diagram of an apparatus used in the modification process of the present invention, in which a cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers, that is, raw fabric 1, are passed through a lead roll _R1 to a strong alkali. The sample is introduced into an alkali treatment bath 2 containing a weak alkaline agent and a weak alkaline agent, and then squeezed with a squeezing roll 3 and dried in a drying dryer (pin tenter oven) 4 so that the amount of alkaline agent treated is uniform. Next, the raw fabric 1 is introduced into a modifier treatment bath 5 via a lead roll R ₂ , squeezed by a squeezing roll 6 so that the amount of modifier treated is uniform, and dried by a dryer 7 . Next, the treated original fabric 1
was introduced into a continuous loop steamer 8 via lead roll R ₃ for further steaming treatment.
Thereafter, the chemically modified fabric 13 is obtained by sequentially introducing it into a water washing (or hot water) bath 9, a soaping bath 10, and a washing bath 11, and then into a drying dryer (pin tenter oven) 12. In order to protect workers and equipment from hydrogen chloride gas generated during chemical reforming, a compound that makes hydrogen chloride inert can be coexisting in the steamer. This method is described, for example, in Japanese Patent Application No. 54-57867 and Japanese Patent Application No. 107897-1982. The fibers modified in this manner can be subjected to a treatment to further improve dyeability before dyeing. This method is well known, and includes, for example, dyeing the modified fabric with a resin dyeable with disperse dyes, such as aminoalkyd resin, polyamide, urethane, vinyl chloride, etc.
By treating with vinyl acetate, polyester, acrylic, acetal, polyvinyl alcohol, vinylidene chloride, vinyl acetal, styrene, polycarbonate, epoxy resin, etc., and then performing sublimation transfer printing, it is possible to further increase the density, hue, depth, etc. can. In addition, the modified fabric can be dimethylol urea, dimethylol propylene urea, dimethylol dihydroxyethylene urea, dimethylol uron, trimethylol melamine, trimethoxymethyl melamine,
Hexamethoxymethyl melamine, dimethylol methyl triazone, dimethylol ethyl triazone, dimethylol hydroxyethyl triazone, dimethylol methyl carbamate, dimethylol ethyl carbamate, dimethylol hydroxyethyl carbamate, N-methylol acrylamide, methylol glyoxal monourea, A fiber crosslinking agent such as methylolglyoxal diurea, formaldehyde, tetraoxane, glitaraldehyde, diepoxide, divinyl sulfone, 4-methoxy-5-dimethyldimethylolpropyleneurea, tetramethylolacetylene diurea, and a crosslinking catalyst such as acetic acid, maleic acid, etc. organic acids, ammonium salts such as ammonium chloride, ammonium sulfate, ammonium hydrogen phosphate, amines such as ethanolamine hydrochloride, 2-amino-2methylpropanol hydrochloride,
It is possible to improve the texture by treating with magnesium chloride, zinc sulfate, zinc chloride, magnesium nitrate, zinc borosulfate, aluminum chloride, magnesium phosphate, etc., and crosslinking with a crosslinking agent, such as a hard finish or a soft finish. can be adjusted to The dye that can be used in this method is a disperse dye with or without sublimation, and can be printed by direct printing or transfer printing, and dyeing by dipping is of course possible. In particular, when a sublimable dye is used, a dry transfer printing method is possible. <Example 1> (1) Mercerized polyester/cotton =
A 65/35 blended broadcloth was immersed in an aqueous solution in which 8% by weight of each of sodium hydroxide and sodium hydrogen carbonate was dissolved, and then the squeezing rate was
I squeezed it with a squeezing roll to make it 100%. Next, this fabric was dried in a hot air oven at 100°C, dipped in a solution of 30% by weight P-toluenesulfonyl chloride dissolved in toluene, and then squeezed at a squeezing rate of 100%. Air dried. The molar ratio of sodium hydroxide and P-toluenesulfonyl chloride on the cloth was 1.27. This treated cloth was heated to 90°C in normal pressure saturated steam at 100°C.
Steaming was performed for seconds, followed by washing with water, soaping with Marcel Setsuken, washing with water, and then drying to obtain a modified fabric. The degree of substitution (DS) of this modified fabric was calculated using the following formula (weight increase method) and was found to be 0.21. (2) Next, a transfer paper was obtained by gravure printing on a 60 g/m ² single-sided starch corded paper using an ink having the composition shown below. <Ink> [Sumikalon Red E-FBL (base powder) {manufactured by Sumitomo Chemical Co., Ltd.} 10 parts Ethyl cellulose N-7 (manufactured by Hercules Co., Ltd.) 9〃 Surfactant 1〃 Isopropyl alcohol 40〃 Ethanol 40〃〃] (3) ( Layer (2) the transfer paper on the modified cloth (1),
When transfer printing was carried out by heating and applying pressure at a temperature of 195° C., a pressure of 300 g/cm ² and a time of 40 seconds, it was possible to obtain a printed cloth with the same density of red in the polyester portion and the cotton portion. In addition, when measured by the washing fastness (A-2) method based on JIS, it was grade 5, indicating that it was a fast printed fabric. [◎ Degree of substitution (DS) = (fabric weight after treatment - fabric weight before treatment) × 162.08 / (fabric weight before treatment) × (cellulose content of cloth before treatment) / 100 × 1 / (tosyl group molecular weight-1) {degree of substitution is the average value of hydroxyl groups substituted by tosyl groups among the three hydroxyl groups present in one glucose unit of cellulose}. 162.08 is the molecular weight of one glucose unit, and 1 is the atomic weight of hydrogen. ] <Example 2> (1) In order to confirm the effect of the combined use of the weak alkaline agent of the present invention, a case where only the strong alkaline agent was used as the alkaline agent using the apparatus shown in Fig. 1. When a weak alkaline agent is used in combination with a strong alkaline agent and used as an alkaline agent. The modification stability of the two methods was compared. (2) Modification processing conditions ・ Raw fabric: polyester/cotton = 65/35 blended broad cloth, basis weight 100 g/m ²・ Treated cloth: 1.200 m/m (1.2 m) ・ Machine line speed: 25 m/min ・ Steaming time : 90 seconds in saturated steam at 100°C / Alkali agent processing amount

[Table] ・ When only a strong alkaline agent was used with p-trienesulfonyl chloride at 30% owf or more on the alkaline treated cloth for each acid chloride treatment amount, when a strong alkaline agent and a weak alkaline agent were used together The modification treatment was carried out continuously for 1000 m using each recipe, and the processing stability of the obtained modified fabric was compared and examined using the piece dyeing method. Due to uneven aperture, etc.
While it tends to appear as modification unevenness as it is, it uses a strong alkaline agent and a weak alkaline agent together, and it is 50% to 100% by weight of the strong alkaline agent.
In the case where a weak alkaline agent was added, almost no uneven dyeing or ending (difference in concentration between the end of the fabric and the beginning of the fabric) was observed on the left and right sides. On the other hand, when 24% was used in combination, almost no effect was observed. <Example 3> (1) Gravure printing was performed on 60 g/m ² single-sided starch-coated paper using an ink having the following composition to obtain a transfer paper. Dye (base powder) * 10 parts Ethyl cellulose N-7 9〃 Nonionic surfactant 1〃 Isopropyl alcohol 40〃 Ethanol 40〃 * Dye {Yellow; CIDisperse Yellow 51 Red; CIDisperse Red 60 Blue; CIDisperse Blue 73 Black; Toning Compound} (2) Mercerized polyester/cotton =
65/35 blended canvas fabric (100g/m ² )
was treated with an aqueous solution in which a certain amount of caustic soda was dissolved and weak alkaline agents of various concentrations were added and dissolved therein to obtain fabrics treated with various combinations of strong alkaline agents and weak alkaline agents.

[Table] (3) The blended fabric obtained by applying the above various alkaline agents is further immersed in a solution of P-toluenesulfonyl chloride dissolved in toluene, squeezed uniformly, and further air-dried to remove the toluene. The amount of PTSC processed was kept constant at 30%owf. (4) After that, the various treated fabrics obtained in (3) were further heated at 100°C.
After steaming under the same conditions for 2 minutes in normal-pressure saturated steam, the fabric was washed with water, further washed with a soaping solution using Marcel soap, and dried after washing to obtain various modified fabrics. Ta. (5) Next, apply the transfer paper obtained in (1) to the various modified fabrics obtained in (4) at a temperature of 195°C and a pressure of 200 g/cm ² for 35 hours.
Transfer printing was carried out under the conditions of 10 seconds, and the dye density of each was measured using a Macbeth reflection densitometer, and the following results were obtained.

【table】

[Table] As shown above, if the amount of weak alkaline agent added is too large relative to the amount of strong alkaline agent (less than 0.5 in weight ratio), the reaction becomes difficult to occur, and the dye density of the modified fabric decreases. It is acceptable to do so. Furthermore, from Example 2, in order to recognize the effect of adding a weak alkaline agent, the amount added must be 50% or more relative to the strong alkaline agent.

[Brief explanation of the drawing]

The drawings show embodiments of the invention, and FIG. 1 is a schematic diagram of an apparatus used in the reforming process of the invention. 1... raw cloth, 2... alkali treatment bath, 3...
... Squeezing roll, 4... Drying dryer, 5... Modifier treatment bath, 6... Squeezing roll, 7... Drying dryer, 8... Continuous loop steamer, 9...
Water washing (or hot water washing) bathtub, 10...Soaping bathtub, 11...Washing bathtub, 12...Drying dryer, 13...Chemically modified cloth, _R1 , _R2 , _R3 ...Reed roll.

Claims (1)

[Scope of Claims] 1. A cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers, (a) a strong alkaline agent having a weight ratio of 1 to 20% relative to the fiber structure, and a weight ratio of this strong alkaline agent; A weak alkaline agent in an amount such that (strong alkaline agent/weak alkaline agent) is 0.5 to 2.0, (b) a compound having the structure below in an amount such that the molar ratio with this strong alkaline agent is 0.1 to 2.0, in any order A dyeing method characterized by applying a dye with a disperse dye, chemically modifying the dye by further applying a steam heat treatment, and then dyeing with a disperse dye. (X means -H, -NO ₂ , -CH ₃ , -SO ₂ Cl.)