JPS5831186A - Dyeing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fiber structures and structures containing cellulose fibers.

Previously, attempts have been made to dye cellulose fibers well using dyes such as disperse dyes that do not originally have the ability to dye cellulose fibers.
1734, Japanese Patent Publication No. 50-12389, Japanese Patent Publication No. 50-38
213, JP 50-90788, JP 50-295
52, etc., JP-A-50-18778, which is mainly carried out by fiber processing methods, and which chemically modifies cellulose fibers that usually have no affinity for disperse dyes.
Methods such as Japanese Patent Application Laid-Open No. 51-99185 are mentioned. However, although these fiber processing methods described above are possible by using relatively simple equipment, the dyeing property lacks sharpness and the color fastness, especially the wet fastness, is not good. On the other hand, conventionally known methods for chemically modifying cellulose fibers have poor workability due to the irritation and odor of the chemicals themselves, and require very expensive equipment investment. In order to solve these problems, the inventors first added an alkali agent and an acid chloride such as P-toluenesulfonyl chloride to cellulose fibers or a cellulose fiber-containing structure in an arbitrary order, and then
Furthermore, chemical modification is performed by applying steam heat treatment or dry heat treatment,
Thereafter, he invented a dyeing method that involves direct or transfer printing using disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc., and applied for a patent. Furthermore, an invention has also been filed in which the present invention can be further simplified by applying the acid chloride in an emulsified state in water. The present invention is a further improvement of the conventional inventions in that it is more effective and has improved productivity, and is characterized by particularly excellent color fastness.

That is, in the present invention, an aromatic sulfonic acid chloride having the following general formula is added to a cellulose fiber structure and a cellulose fiber-containing structure by applying an alkali agent of Ichikawa's 1 to 20 in advance to the cellulose. By adding 5 to 40% of the weight of the fibrous structure and cellulose fiber-containing structure and then performing steam heat treatment or dry heat treatment, the cellulose fJ1 string 1'f'+ structure and cellulose fiber-containing structure are An aromatic sulfonyl group consisting of the following general formula is introduced into cellulose fibers, and then disperse dyes, oil-soluble dyes,
The dyeing power θ2 is characterized by direct or transfer printing using mordant dyes, basic dyes, vat dyes, etc.

(However, n, +, and R2 are alkyl groups) As a method for attaching an aromatic sulfonic acid chloride represented by the above general formula to cellulose fiber structures and cellulose fiber-containing structures to which an alkaline agent has been applied in advance, , a method in which the aromatic sulfonic acid chloride is immersed in a solution diluted with a suitable solvent and squeezed with a squeezer such as Mangle to give the required amount, or an emulsion in water is prepared using a surfactant and a thickener. It is possible to apply a coating using a coating machine such as a rotary screen, or to leave it in a gaseous atmosphere of the acid chloride for a predetermined period of time. According to the present invention, a dyed product having extremely superior color fastness compared to a dyed product obtained by dyeing a cellulose fiber Mt after esterification such as acetylation, benzoylation, tosylation, etc. is obtained. Furthermore, by introducing an aromatic sulfonyl group having the above structure into the cellulose fibers and then treating them with a disperse dye dyeable resin, it is possible to obtain even better color burrs, and furthermore, By introducing such an aromatic sulfonyl group and then treating it with a fiber crosslinking agent and a crosslinking catalyst, an extremely fast dyed product can be obtained.

In addition, in the present invention, it is necessary to introduce such aromatic sulfonyl groups into the cellulose fibers to a degree of substitution of 02 to 05.

The degree of substitution here means the average value of hydroxyl groups substituted by aromatic sulfonyl groups among the three hydroxyl groups present in one glucose unit of cellulose, and in reality,
It is calculated by the gravimetric method as follows:

Here, 162.08 is the molecular weight of 1 glucose unit, and 1 is the atomic weight of hydrogen.

In the present invention, the reason why it is necessary to set the degree of substitution to 02 to 0.5 K is that the degree of substitution must be set to 02 to 0.5 K from the viewpoint of color development and fastness after dyeing.
This is because it was confirmed that it is necessary to carry out the following steps, and that the degree of substitution needs to be 0.05 or less in view of the texture and hygroscopicity of the fibers.

The alkaline agents used in the present invention include, for example, alkaline agents such as lithium, sodium, potassium, beryllium, magnesia, calcium, barium, and strontium, as well as aromatic sulfonic acid chlorides used in the present invention. For example, m-xylene-2-sulfonylchloride IJ)
e, O-xylene-3-sulfonylchlori)", P-
Xylene-2-sulfonyl chloride is an aromatic sulfonic acid chloride having the general formula shown below.

(However, 几1 and R2 are alkyl groups) In the method of adding an aromatic sulfonic acid chloride having the above general formula to a cellulose fiber structure and a cellulose fiber-containing structure that have been previously provided with an alkali agent. Suitable solvents used in the immersion method include aromatic organic solvents such as benzene, toluene, xylene, trichloroethylene, tetrachloroethylene, 1,1,1-)I
When applying as an emulsion in water using a nonflammable solvent such as J-dichlorothane, a surfactant, and a thickening agent, use a viscous 1 wet O embryo 8-3j18G. Coating method, spray coating method, air knife coating method, flow coating method, gravure coating method, rotary screen method, etc. can be performed.

Furthermore, in the present invention, resins that are dyeable with disperse dyes include aminoalkyd resins, boritimide, urethane, vinyl chloride, vinyl acetate, polyester, acrylic, acetal, polyvinyl alcohol, vinylidene chloride, vinyl acecool, and styrene. , polycarbonate, epoxy resin, etc.

Furthermore, in the present invention, the fiber crosslinking agent includes, for example, dimethylol urea, dimethylol globylene urea, dimethylol dihydroxyethylene urea, dimethylol uron, l-rimethylol melamine, trimethoxymethyl melamine, and dimethylol methyltriamine. Azone, dimethylol ethyl triazone, dimethylol hydroxyethyl triazone, dimethylol methyl carbamate, dimethylol ethyl carbamate, dimethylol hydroxyethyl carbamate, N-methylol acrylamide,
Methylolglyoxal monourea, methylolglyoxal diurea, formaldehyde, tetraoxane, glitaraldehyde, diepoxide, divinylsulfone, 4-methoxy-5-dimethyldimethylolpropyleneurea, tetramethylolacetylene diurea, etc., and the crosslinking catalyst is, for example, acetic acid. , organic acids such as maleic acid, ammonium salts such as ammonium chloride and ammonium sulfate, ethanolamine hydrochloride, 2-amino-2-
These include amines such as methylpropanol hydrochloride, magnesium chloride, zinc nitrate, zinc chloride, magnesium nitrate, zinc borofluoride, aluminum chloride, and magnesium phosphate.

Hereinafter, the present invention will be further explained in detail with reference to Examples.

[Example-1] (1) Mercerized polyester/cotton = 65
/35 blended broad cloth was immersed in a 10% sodium hydroxide water bath, squeezed with a squeezing roll to a squeezing rate of 90%, and dried in a pin tenter oven. Next, this woven fabric was immersed in a 30% toluene solution of P-xylene-2-sulfonyl chloride, squeezed with a squeezing roll to a squeezing rate of 00%, and air-dried. Thereafter, the fabric was left in saturated steam at 100° C. for 2 minutes, then saw-pink, washed with hot water, washed with water, and dried to obtain a modified fabric. The degree of substitution was 026.

(2) Next, a transfer paper was obtained by gravure printing on a 605'/m'' single-sided starch-coated paper using an ink having the composition shown below.

Ink〉 (3) (Modified cloth K (11) (Overlaid transfer paper 21, temperature 195°C, pressure 3oog7crfl, time 4
When transfer printing was carried out by heating and applying pressure for 0 seconds, a red dyed cloth with the same density in the polyester fiber portion and the cotton portion was obtained. Next, using this dyed cloth, wash a test (
, TIS L-0844), sweat test (J Engineering sl-
-0848) was grade 5 due to discoloration and fading, and grade 4 to 4 due to contamination.
A robust value of grade 5 was obtained.

[Example-2] (1) A modified fabric was obtained as in Example-1. Next, this modified fabric was immersed in a solution with the following formulation (a), and then the squeezing rate was 8.
Squeeze to 0%, dry at 100℃ for 2 minutes, and then dry at 150℃ in the next step.
Baked for 3 minutes at 10°C.

(b) Prescription (2) Next, a transfer paper was prepared as in Example-1.

The modified fabric (3H1) was overlaid with the transfer paper (2), and when the transfer was performed by heating and pressurizing at a temperature of 195°C, a pressure of 600 g/i, and a time of 40 seconds, the polyester fiber part and the cotton part It was possible to obtain a dyed cloth with medium-red density, coloring, and depth.

Next, this dyed cloth was used for a washing test (JISL4-08
44), a sweat test (JTS L-0848) was performed, and extremely robust values of 5th grade for discoloration and fading and 5th grade for staining were obtained.

[Example-ro]

(1) A modified fabric was obtained as in Example-1. Next, this modified fabric was dyed in an autoclave at 130°C for 20 minutes at a bath ratio of 1/60 using a dye bath with the following recipe (a).
A very densely dyed cloth was obtained in which the polyester fiber portion and the cotton portion were of the same blue color.

(a) Prescription (2) Next, using the dyed fabric obtained in (1), a washing test (
JIS L-oa44), sweat test (, rrs IJ
- oalls), it was grade 5 due to discoloration and fading, and grade 4 due to contamination.
A robust value of ~5 grade was obtained.

[Example-4] (1) Mercerized polyester/cotton = 65
A blended broadcloth cloth designated as 735 was immersed in a 10% aqueous sodium hydroxide solution, and then squeezed using a squeezing roll to achieve a squeezing rate of 90%.

Next, the alkali-applied cloth was coated with an emulsion in water according to the following formula (a) with a number of lines of 40 lines/inch and a nickel plate thickness of 150μ.
, with a rotary screen plate with a porosity of 50%, and then in a pin tenter oven at 100°C and 90°C.
After heating for seconds, a modified cloth was obtained through soaping and water washing steps.

(a) Prescription (2) 60,! i'/m2 single-sided starch
1. Transfer paper was obtained by gravure printing on paper using ink having the following composition.

*Dye (3HI) modified fabric and (2) transfer paper are layered and heated at 195°C, pressure 300.9/d, and time 40.
When transfer printing was carried out by heating and applying pressure under conditions of 2 seconds, a printed cloth with uniform density in the polyester fiber portion and the cotton portion was obtained. Next, this printed fabric was used for a washing test (Jl:S L
-0844), sweat test (JISL-o84B) was conducted, and a fastness value of 5th grade for discoloration and fading and 4th to 5th grade for staining was obtained.

[Example-5] (1) Scouring raw cotton, then immersing it in a 10% aqueous sodium hydroxide solution, dehydrating and drying it, and then immersing it in a 30% toluene solution of P-xylene-2-sulfonyl chloride. Then, after removing the solvent, heat at 80°C using an open
, heated for 5 minutes, and then further subjected to saw pink and water washing steps to obtain modified cotton.

(Modified cotton 2H+1 was dyed at 130°G for 120 minutes at a bath ratio of 1/30 in an autoclave using a dye bath with the following recipe.

(3) Next, 05g of the dyed cotton obtained in (2) was placed in a bag made by sewing two 6crn x 6crn multi-line woven fabrics together, and this was used as a sample for a washing test (JISL-0844
), a robust value of 4th to 5th grade for discoloration and fading and 4th to 5th grade for staining was obtained.

[Example-6] (1) Mercerized polyester/cotton = 65
/ 55 knitted fabric (10% hydroxide)) After immersing in IJum aqueous solution and squeezing at a squeezing rate of 80%, it was left as it was in a P-xylene-2-sulfonyl chloride gas atmosphere for 10 minutes, and then soaped. A modified fabric was obtained through a water washing process.

(When the modified fabric obtained with 2H1+ was transfer-printed by the method described in Example 4, an extremely clear printed fabric with the same density in the polyester fiber portion and cotton portion was obtained.

Next, this printed fabric was used for a washing test (JIS L-08
44), a sweat test (JIS L-0848) was conducted, and a fastness value of 5th grade for discoloration and 4th to 5th grade for staining was obtained.

Claims (4)

[Claims] (1) An aromatic sulfonyl group consisting of the following general formula is introduced into cellulose fibers in cellulose fiber structures and cellulose fiber-containing structures, and then disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes A dyeing method characterized by direct or transfer printing. (2) The method according to claim (1), wherein the transfer printing is dry transfer printing using a heat transferable dye such as vaporizable or melt-transferable dye. (3) The method according to claims (1) to (2), characterized in that after introducing the aromatic sulfonyl group, the method is further treated with a resin that is dyeable with disperse dyes. (4) The method according to claims (1) to (3), which further comprises treating with a fiber crosslinking agent and a crosslinking catalyst after introducing the aromatic sulfonyl group.