JPS6297990A - Fluorescent colorant for raw liquid dyed viscose rayon - 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 (Industrial Field of Application) The present invention is a solution-dyed fluorescent material for solution-dyed viscose rayon that provides rayon yarn with excellent dispersibility in scose and spinnability, as well as good gloss and clear fluorescent color tone. Regarding colorants.

(Prior art) The conventional method for producing viscose rayon is a method called dope dyeing, in which coloring agents such as pigments, sulfur dyes, vat dyes, etc. are mixed and dispersed or dissolved in a spinning solution of viscose etc. in advance. A method of producing colored rayon yarn by spinning is widely used.

Among these, water-insoluble pigments are often used as colorants in this case, and therefore, in order to improve spinnability and the gloss or color tone of the resulting rayon yarn, it is necessary to uniformly disperse the pigment in the spinning stock solution. is strongly required. On the other hand, when spinning viscose rayon, a spinning bath containing relatively high concentrations of sulfuric acid, zinc sulfate, sodium sulfate, and other salts is used, and the viscose comes into contact with these highly acidic baths during spinning. As a result, it has been pointed out that the pigments dispersed in the viscose agglomerate to form coarse particles, leading to frequent thread breakage and, in some cases, a decrease in spinnability such as blockage of the discharge holes.

In addition, when using sulfur dyes or vat dyes as colorants, the dye is solubilized by adding a reducing agent or more to the dye and then added to the viscose, but many of these dyes are stable in solution. As a result of forming coarse particles with poor properties,
This has the disadvantage of causing a decrease in spinnability.

(Problems to be solved by the invention) In this way, the colorant for solution-dyed viscose rayon is
Since dispersion and stability that can withstand harsh conditions are required, the number of pigments and dyes that can be used satisfactorily among commercially available pigments and dyes is limited. In particular, even if fluorescent dyes such as rhodamine-based basic dyes or acidic dyes are used in an attempt to obtain a rayon dye with a clear fluorescent color, the solubility in viscose is insufficient and the original brightness of the fluorescent dye is lost. There are disadvantages in that the color tone cannot be obtained or the color tone changes due to the high acid and high salt spinning bath.

Therefore, it is very difficult to obtain a coloring agent for solution-dyed viscose rayon yarn with a desired color tone, and the current situation is that a colorant that can produce solution-dyed viscose rayon yarn with a particularly vivid fluorescent tone has not yet been obtained. be.

The present invention overcomes the navigational problems associated with colorants for solution-dyed viscose rayon.

Therefore, it is an object of the present invention to develop a solution-dyed scone for rayon that provides rayon yarns that have good dispersibility in viscose, withstand high-acid, high-salt spinning baths, and have good gloss and bright fluorescent color tones. The purpose is to provide a coloring agent.

(Means and effects for solving the problems) The present invention has the following features:
Contains 0.2 to 4% by weight of fluorescent dye and has an average particle size of 0.1
This invention relates to a fluorescent colorant for solution-dyed viscose rayon made of hardened spherical fine particles of amino resin having a particle size of ~10 mic D.

Amino resins include melamine, urea, benzoguanamine,
It is a general term for resins obtained by a synthetic reaction between a compound containing an amino group such as acetoguanamine and an aldehyde represented by formaldehyde, and any combination can be used in the present invention. Among these, benzoguanamine-formaldehyde resin or benzoguanamine-melamine-formaldehyde resin is preferable in consideration of the coloring properties of fluorescent dyes as described below.

These amino resins containing benzoguanamine as an essential component are uniformly colored with fluorescent dyes, and can express the vivid color tones inherent to fluorescent dyes with good color development.

In the present invention, the amino resin contains 0.2 to 4 fluorescent dyes.
It is essential that the dye be colored by containing ffiffi%, and a desired color tone can be selected from various fluorescent dyes and used. The fluorescent dye to be used is not particularly limited as long as it can express the vivid color tone inherent to the fluorescent dye on the colored amino resin with good color development, such as basic dyes such as rhodamine and thioflavin, fluorescein and eosin. Examples include acid dyes based on diaminostilbene, fluorescent whitening agents based on diaminostilbene, and oil-soluble fluorescent dyes, which can be appropriately selected and used depending on the desired color tone and fastness characteristics.

The amount of fluorescent dye used to color the amino resin ranges from 0.2 to 4% by weight, more preferably from 0.5 to 3% by weight, based on the amino resin. 0.2% by weight
If the amount is less than 1, the coloring of the amino resin will be insufficient, and a large amount of colorant will need to be added to viscose, making it difficult to obtain uniform dispersion of the colorant. Furthermore, if the amount exceeds 4% by weight, a unique concentration quenching phenomenon occurs when coloring with the fluorescent dye, making it impossible to obtain a coloring agent having the clear fluorescent color tone inherent to the fluorescent dye. On the other hand, due to the large amount of fluorescent dye contained in the amino resin, coarse particles exceeding 10 microns are likely to be produced in the process of producing cured spherical fine particles of the amino resin.

The cured spherical fine particles of amino resin colored with a fluorescent dye (hereinafter referred to as colored resin cured spherical fine particles) used as the fluorescent colorant for solution-dyed viscose rayon of the present invention are:
It has a spherical shape with no protrusions on the particle surface, and the particle size is large and uniform. Secondary aggregation is difficult to occur and it has a high affinity with viscose, so it has excellent dispersibility in viscose. ing. In addition, because colored resin cured spherical fine particles are made of insoluble and infusible resin, they have excellent heat resistance, solvent resistance, acid resistance, alkali resistance, and color migration resistance, and can be used in high-acid, high-temperature spinning baths, and in high-temperature operations. It can fully withstand viscose rayon manufacturing processes including.

The colored resin-cured spherical fine particles having the above-mentioned excellent properties can be obtained by a known manufacturing method. As such a manufacturing method, for example,
2-27679, Special Publication No. 58-5924, Special Publication No. 59-
48007, and the method disclosed in Japanese Patent Publication No. 58-24444. Based on the methods disclosed in these documents, colored resins with excellent heat resistance, solvent resistance, acid resistance, alkali resistance, and color migration resistance, spherical shape and fairly uniform particle size, and arbitrary particle size can be produced. Hardened spherical fine particles are obtained.

The average particle diameter of the colored resin cured spherical fine particles used in the present invention is determined by considering that when spinning a single 5-denier rayon yarn, the viscose discharge hole is approximately 80 microns and the dispersibility in viscose is determined. , 0.1-10 microns,
More preferably, it is in the range of 0.1 to 2 microns. According to the known manufacturing method of the colored resin-cured spherical fine particles described above, particles with an average particle size of 0.1 to 10 microns can be easily obtained, but by appropriately selecting manufacturing conditions, a more preferable average particle size can be obtained. It is also possible to obtain a range.

The colored resin cured spherical fine particles are used as a fluorescent colorant for solution-dyed viscose rayon of the present invention by being added to and mixed with viscose or alkali cellulose. For mixing, no special mixing/crossing device is required, and an extremely simple mixing device 2 is sufficient. Furthermore, there are no particular limitations on the composition of viscose to be used as the colorant of the present invention or the spinning bath used when spinning viscose.

The amount of the fluorescent colorant for solution-dyed viscose rayon of the present invention added is 0.1 to 10 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of viscose. Furthermore, when the colorant of the present invention is added to viscose, other colorants such as pigments and dyes, and surfactants for aiding the dispersion of the colorant can also be used together.

(Effects of the Invention) The fluorescent colorant for solution-dyed viscose rayon of the present invention is composed of hardened spherical fine particles of an insoluble and infusible amino resin with a substantially uniform particle size and a high affinity for viscose. It has excellent dispersibility in ~ and spinnability, especially for single yarn 5.
Even when spinning silk of denier or less, it can be stably spun without thread breakage.

In addition, it is possible to select a desired color from among various fluorescent dyes to color the amino resin and use it as the colorant of the present invention, which cannot be obtained with conventional colorants for solution-dyed viscose rayon. Another advantage is that rayon yarn or rayon stable having a clear fluorescent color tone can be easily obtained.

Furthermore, when the fluorescent colorant for solution-dyed viscose rayon of the present invention is used, the intense luster unique to viscose rayon is weakened by the light scattering of the hardened spherical fine particles of the amino resin in the rayon thread, resulting in a very desirable soft color. A beautiful rayon yarn with luster can be obtained.

The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited in any way by these Examples.

Reference Example 1 240 g (1.3 mol) of benzoguanamine and melamine 6 were placed in a four-eye flask equipped with a stirrer, reflux condenser, and thermometer.
0Q (0.5 mol), formalin 323. with a concentration of 37%.
4c+ (4.0 mol) and 1.30 G of a 10% concentration sodium carbonate aqueous solution, and while stirring, 94-9
The reaction was carried out at a temperature of 5° C. for 5 hours.

The reaction product became hydrophobic and cloudy.

Polyvinyl alcohol (Kuraray products/PVA205)
42.0g to 521.0g of water. In the aqueous solution obtained by dissolving in OQ,
While vigorously stirring with a homomixer, the solution containing the above reaction product was added and emulsified. After cooling the emulsion to 30°C, rhodamine B1.5q and rhodamine 6GCP1.
5g was added and stirred for 15 minutes, then 4.620% of dodecylbenzenesulfonic acid was added, and the mixture was heated at 40°C, 50°C, and 70°C.
, and 90° C. for 2 hours at a time to polymerize and harden the emulsified state.

After drying the filter cake obtained by furnace-separating the emulsion after polymerization and hardening at 100°C, and heat-treating it at 150°C for 3 hours,
The mixture was crushed to obtain 392 g of hardened spherical fine particles of colored benzoguanamine-melamine-formaldehyde resin.

The thus obtained spherical fine particles were composed of a cured resin having an average particle diameter of 0.5 microns and a pink fluorescent color, and had a softening point of 300° C. or higher.

Reference Example 2 In the same flask as used in Reference Example 1, benzoguanamine 15C1 (0.8 mol) and formalin 1 with a concentration of 37% were added.
62a (2.0 mol) and 0.650 aqueous sodium carbonate solution with a concentration of 10%, and while stirring,
The reaction was carried out for 4 hours at a temperature of .degree. After that, L of optical brightener
1.5 q of JVITEX'OB (Ciba Geigy M) was added, and the mixture was stirred for 60 minutes while being maintained at 94 to 95°C, thereby coloring the reaction product.

Polyvinyl alcohol (Kuraray products/PVA205)
To an aqueous solution obtained by dissolving 10.5q in 145 g of water, a solution containing the above reaction product was added and emulsified while vigorously stirring using a homomixer, and then 2.1 cl of dodecylbenzenesulfone M was added and the mixture was heated at 50°C. , 70℃, 80℃, 9
The mixture was heated and stirred for 2 hours at each temperature of 0° C. to polymerize and harden the emulsified state.

The filter cake obtained by separating the emulsion after polymerization and hardening was dried, heat treated, and crushed in the same manner as in Reference Example 1 to obtain 1800 hardened spherical fine particles of colored benzoguanamine-formaldehyde resin.

The spherical fine particles obtained in this way are made of a hardened resin with a high white skin of an average particle size of 0.5 microns, and have a softening point of 300.
It was above ℃.

Reference Example 3 The amount of fluorescent dye used in Reference Example 1 was changed to Rhodamine B.
Colored cured spherical fine particles 410Q of benzoguanamine-melamine-formaldehyde resin were obtained in exactly the same manner as in Reference Example 1, except that 10.5 g of Rhodamine 6 G CP and 10.5 g of Rhodamine 6 G CP were used.

The thus obtained spherical fine particles were composed of a black-red resin cured product with an average particle diameter of 0.8 microns and almost no fluorescence, and had a softening point of 300° C. or higher.

Example 1 The colored benzoguanamine/melamine obtained in Reference Example 1 was added to 100 parts by weight of viscose whose composition was 8.5% by weight of cellulose, 6.0% by weight of total alkali, and 11.8% by weight of viscose. One polymerized part of cured spherical fine particles of formaldehyde resin was added and mixed thoroughly to prepare a colored viscose composition. Using this composition, the composition is sulfur M15.
0q/i Sodium Sulfate 345 Q/Jl, Zinc Sulfate 15
0/j! The fibers were spun into a spinning bath at a temperature of 60° C. at a spinning speed of 90 m/min and a dipping length of 60 α to obtain a rayon yarn of 50 denier/20 filaments. The obtained rayon yarn was a beautiful yarn with a soft and desirable luster and a bright pink fluorescent color. Furthermore, during spinning, there were no problems such as yarn breakage or clogging of the viscose discharge port.

Example 2 1 part by weight of cured spherical fine particles of colored benzoguanamine-formaldehyde resin obtained in Reference Example 2 was added to the 100-weight part of the same scose used in Example 1, and mixed well to form a colored biscoat. A course composition was prepared. Using this composition, the composition was 1100 g/l of sulfur W and 35 g/l of sodium sulfate.
0g/j! , zinc sulfate 20 CJ/1 in a first coagulation bath at a temperature of 40°C.

Next, sulfuric acid 10g/j! The regeneration was completed while the film was introduced into a second bath with a humidity of 90° C. and stretched.

The obtained rayon yarn was cut into 50 pieces and dried to obtain a rayon stable.

The resulting rayon stable had a very white skin of 5 denier. Furthermore, during spinning, there were no problems such as yarn breakage or blockage of the scose discharge port.

Comparative Example 1 Viscose 100tfif similar to that used in Example 1
In part fi, hardened spherical fine particles 1 of colored benzoguanamine-melamine-formaldehyde resin obtained in Reference Example 3 are added.
A colored scose composition for comparison was prepared by adding parts by weight and mixing well. Using this comparative composition, spinning was carried out in the same manner as in Example 1 to obtain a 50 denier/20 filament rayon yarn.

The obtained rayon yarn lacked sharpness with almost no pink fluorescent color. Furthermore, microscopic observation revealed that red coarse particles were mixed in some places in the rayon yarn.

Claims (1)

[Claims] 1. Contains 0.2 to 4% by weight of fluorescent dye and has an average particle size of 0.
．． A fluorescent colorant for solution-dyed viscose rayon consisting of hardened spherical fine particles of amino resin having a size of 1 to 10 microns. 2. The fluorescent colorant for solution-dyed viscose rayon according to claim 1, wherein the amino resin is benzoguanamine-formaldehyde resin or benzoguanamine-melamine-formaldehyde resin.