JP2505810B2 - Coloring agent for undiluted viscose rayon - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention provides a stock solution dyeing for viscose rayon, which is excellent in dispersibility in viscose and spinnability and gives rayon yarn having good gloss and a clear black tone. Regarding agents.

(Prior Art) As a conventional method for producing viscose rayon, a method called undiluted solution dyeing, that is, a pigment in a spinning dope solution such as viscose is previously
A method of producing a colored rayon yarn by widely mixing or dispersing a colorant such as a dye and then spinning the mixture is widely used.

Among these, as the colorant in this case, a water-insoluble pigment is often used, and therefore, in order to improve the spinnability and the gloss or color tone of the rayon yarn obtained, the pigment is uniformly dispersed in the spinning dope. Is strongly required. On the other hand, when spinning viscose rayon, a spinning bath containing a relatively high concentration of sulfuric acid, zinc sulfate, sodium sulfate, etc. is used. As a result, it has been pointed out that the pigment dispersed in the viscose causes agglomeration to form coarse particles, resulting in frequent occurrence of yarn breakage and, in some cases, clogging of discharge holes, which lowers the spinnability. .

(Problems to be Solved by the Invention) As described above, the colorant for the undiluted viscose rayon is required to have dispersion / stability that withstands severe conditions. Among them, the number of those that can be used favorably is limited. In particular, when carbon black (hereinafter referred to as CB) is used as a colorant to obtain a black rayon yarn, the dispersibility in viscose is poor and a rayon yarn having a uniform color tone cannot be obtained. There is a particularly serious problem that the spinning property is deteriorated, such as yarn breakage or clogging of the discharge hole.

Therefore, it is very difficult to obtain a colorant for a viscose rayon dyed with a black tone, and the fact is that a colorant that gives a viscose rayon yarn dyed with a vivid black tone has not yet been obtained. Is.

The present invention solves the above-mentioned problems associated with a colorant for undiluted viscose rayon.

Therefore, an object of the present invention is to provide a dyeing solution for viscose rayon which has good dispersibility in viscose, withstands a spinning bath of high acid and high salt, and gives rayon yarn having good gloss and a clear black tone. To provide the agent.

(Means and Actions for Solving Problems) As a result of intensive studies by the present inventors, by treating CB with a specific resin, good dispersibility in viscose and high temperature and high temperature were achieved. The present invention has been completed by finding that a colorant for undiluted dyeing viscose rayon which can endure a salt spinning bath and gives rayon yarn having good gloss and a clear black tone can be obtained.

That is, the present invention is for a stock solution dyed viscose rayon comprising CB treated with poly (oxazoline) (a) and / or poly (oxazoline) modified product (b) (both are collectively referred to as polymer (A)). It relates to a colorant.

As the CB in the present invention, a CB produced by a usual method such as a contact method, a furnace method, a thermal method or the like can be used. Particularly, a carboxyl group or a hydroxyl group and / or a quinone as a functional group on the CB surface is used. When the CB having a group is used, the affinity with the polymer used for the treatment of the CB in the present invention is particularly excellent, so that the treated CB obtained by being able to be treated uniformly and with high binding property
The colorant for viscose rayon dyed with undiluted solution obtained by using is preferable because it has improved characteristics.

In the present invention, the polymer (A) used for the surface treatment of CB is obtained by ring-opening polymerization of 2-oxazoline monomer, if necessary, using alkyleneimine or alkylene oxide as a copolymerization component, or by ring-opening polymerization and subsequent modification. A polymer, the main chain of which is a general formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are independently halogen,
It is an alkyl, aralkyl, phenyl or substituted phenyl group. ), Which contains a ring-opened unit of a 2-oxazoline monomer. The molecular weight thereof is preferably in the range of 100 to 100,000 in order to obtain a colorant for viscose rayon with undiluted solution excellent in various properties, and particularly high molecular weight is preferable.

Poly (oxazoline) (a) of polymer (A)
As specific examples of, for example, poly (2-methyl-2-oxazoline), poly (2-ethyl-2-oxazoline),
Poly (2-isopropyl-2-oxazoline), poly (2-phenyl-2-oxazoline), poly (2-cyclohexyl-2-oxazoline), (2-methyl-2-
Oxazoline-2-ethyl-2-oxazoline) copolymer, (2-ethyl-2-oxazoline-2-phenyl-
(Oxazoline) copolymer, (2-ethyl-2-oxazoline-2-cyclohexyl-2-oxazoline) copolymer, (2-ethyl-2-oxazoline-ethyleneimine) copolymer, (2-ethyl-2- Examples thereof include oxazoline-propylene oxide) copolymers and (2-phenyl-2-oxazoline-tetrahydrofuran) copolymers, and one or more of these can be used.

The poly (oxazoline) modified product (b) of the polymer (A) is obtained by modifying the poly (oxazoline) (a), and specific examples thereof include poly (2
-Methyl-2-oxazoline), poly (2-ethyl-2)
-Oxazoline), poly (2-phenyl-2-oxazoline), etc., partial hydrolysates, these partial hydrolysates, (2-ethyl-2-oxazoline-ethyleneimine) copolymers, etc., and ethylene oxide, propylene oxide, etc. Examples thereof include graft reaction products with alkylene oxides, and one or more of these can be used.

Among them, poly (oxazoline) (a) obtained by using one or two or more kinds selected from 2-ethyl-2-oxazoline, 2-phenyl-2-oxazoline and 2-cyclohexyl-2-oxazoline as a main component, and The modified poly (oxazoline) (b) obtained by modifying the poly (oxazoline) (a) is industrially easy to obtain and has a large treatment effect, which is desirable. As described above, in obtaining the polymer (A) in the present invention, an alkyleneimine typified by ethyleneimine, propyleneimine and the like, an alkyleneoxide typified by ethylene oxide, propylene oxide and the like within the range not departing from the object of the present invention and others Cyclic monomers such as tetrahydrofuran may be used as a copolymerization component of the 2-oxazoline monomer, but these cyclic monomers are preferably used in an amount of 50 mol% or less based on all monomers.

In order to obtain CB treated in the present invention, for example, a method of stirring and mixing CB and polyoxazoline (a) and / or modified polyoxazoline (b) or a method of polymerizing a 2-oxazoline monomer in the presence of CB As a specific embodiment, for example, (1) one or more kinds of CB and one or more kinds of polymer (A) are mixed at 0 ° C to 400 ° C, preferably 20 ° C to 350 ° C. (2) One or more CBs and one or more polymers (A) are mixed in a suitable solvent with stirring under a temperature condition, and the surface treatment is carried out at 0 ° C to 400 ° C, preferably 20 ° C to 350 ° C. ℃
(3) A monomer having 2-oxazoline as an essential component is subjected to ring-opening polymerization in the presence of one or more kinds of CB in a suitable solvent, and further modified if necessary. Examples of the method include, but in the present invention, the methods (1) and (2) are preferable for the following reasons. That is, according to the methods (1) and (2), the CB in the secondary agglomerated state is crushed to primary particles or a state close to the primary particles during processing, and thus the obtained CB has a fine and uniform particle size. Is. Moreover, since the polymer (A) is prepared in advance, it is easy to control the molecular weight suitable for dispersion. as a result,
The CB treated by the methods (1) and (2) is dispersed in the viscose rayon stock solution with a high degree of dispersibility and affinity, so that a rayon yarn having excellent spinnability, good gloss and a clear black tone is obtained. You can get it.

In obtaining the treated CB in the present invention, the ratio of CB and the polymer (A) is not limited, but the surface treatment of the CB is performed uniformly to firmly bond the CB and the polymer (A), and the obtained treated CB is obtained. In order to further improve the dispersibility of the viscose rayon stock solution, the ratio of CB to the polymer (A) is by weight.
100/1 to 100/1000 is preferable, 100/5 to 100/500
It is more preferable to set the range to.

The CB thus treated with the polymer (A) can be directly used as the colorant for the undiluted dyeing viscose rayon of the present invention. If necessary, a conventional additive such as a coloring agent for the undiluted viscose rayon, for example, can be used. Wetting agent, antistatic agent,
Surfactants, pigments, dyes, etc. may be appropriately contained.
These additives may be added at the time of treating the CB with the polymer (A) or after the treatment.

The colorant for undiluted viscose rayon of the present invention is used by adding and mixing it with viscose or alkali cellulose. When mixing, no special mixing / kneading device is required, and the order of mixing is not limited, but it is easiest and preferable to previously disperse the colorant for undiluted dyeing viscose rayon in water before mixing.

In addition, there is no particular limitation on the composition of the spinning bath for spinning viscose or viscose, which is the target of the colorant for viscose rayon dyed undiluted solution of the present invention.

When the colorant for undiluted solution viscose rayon of the present invention is added to viscose and used, a colorant such as another pigment or dye, or a surfactant for assisting dispersion of the colorant may be used together.

(Effect of the invention) Since the concentrate for dyeing viscose rayon of the present invention is composed of CB treated with the polymer (A), it has excellent dispersibility in viscose and spinnability, and particularly 5 denier single yarn. Even when spinning the following fine products, the yarn can be stably spun without yarn breakage, and rayon yarn having good gloss and a clear black tone can be obtained.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The parts and percentages in the examples represent parts by weight and percentages by weight, unless otherwise specified.

Reference Example 1 40 parts of poly (2-ethyl-2-oxazoline) having a weight average molecular weight of 200,000 and MA-100R as CB (Mitsubishi Kasei Co., Ltd.)
20 parts with a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and kneading them under the conditions of 160 ° C. and 100 rpm for reaction, cooling, pulverizing, and coloring for the undiluted dyeing viscose rayon of the present invention I got an agent. This is a coloring agent (A).

Reference Example 2 In the same manner as in Reference Example 1 except that poly (2-ethyl-2-oxazoline) was used instead of poly (2-ethyl-2-oxazoline), poly (2-methyl-2-oxazoline) having a weight average molecular weight of 80,000 was used. A colorant for course rayon was obtained. This is designated as a colorant (B).

Reference Example 3 2-Ethyl-2-oxazoline 90 parts and 2-phenyl-
A mixture of 30 parts of an oxazoline copolymer (weight average molecular weight of 50,000) obtained from 10 parts of 2-oxazoline, 30 parts of Asahi # 60 (manufactured by Asahi Carbon Co., Ltd.) as CB and 240 parts of water, and glass beads having a diameter of 1 mm. Was wet-dispersed with Dynomill (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain an aqueous dispersion of the colorant for viscose rayon of the undiluted solution of the present invention. This is designated as a colorant (C).

Reference Example 4 20 parts of poly (2-ethyl-oxazoline) having a weight average molecular weight of 200,000 was dissolved in 80 parts of deionized water, 2.1 parts of concentrated hydrochloric acid was added, and the reaction was carried out at a temperature of 100 ° C. for 7 hours. After distilling off propionic acid, the mixture was diluted with water to give poly (2-ethyl-
A 20% aqueous solution of 2-oxazoline) partial hydrolyzate hydrochloride was obtained.

A 20% aqueous solution of the above-mentioned poly (2-ethyl-2-oxazoline) partial hydrolyzate hydrochloride was treated with anion exchange resin Amberlite IRA-410 (manufactured by Organo Corporation), dried and pulverized to obtain poly (2 -Ethyl-2-oxazoline) partial hydrolyzate was obtained.

Coloring for undiluted solution viscose rayon of the present invention in the same manner as in Reference Example 1 except that the above poly (2-ethyl-2-oxazoline) partial hydrolyzate was used instead of poly (2-ethyl-2-oxazoline). I got an agent. This is a coloring agent (D).

Reference Example 5 After 50 parts of a 20% aqueous solution of the poly (2-ethyl-2-oxazoline) partial hydrolyzate hydrochloride obtained in Reference Example 4 was reacted with 5 parts of ethyleneimine at a temperature of 80 ° C. for 4 hours. After drying and pulverizing, an ethyleneimine graft product of poly (2-ethyl-2-oxazoline) was obtained.

25 parts of an ethyleneimine grafted product of the above poly (2-ethyl-2-oxazoline) and 35 parts of MA-600 as CB were kneaded and reacted under the conditions of 150 ° C. and 100 rpm using a Labo Plastomill, followed by cooling, The mixture was pulverized to obtain a stock dyeing viscose rayon colorant of the present invention. This is designated as a colorant (E).

Examples 1 to 5 Viscose composition is cellulose 8.5%, total alkali 6.0
%, Hottenroth 11.8 viscose in Reference Examples 1-5
Colored viscose compositions were prepared by adding the colorants (A) to (E) obtained in 1. in an amount of 3% CB relative to viscose and mixing them well. With this composition, the composition is 15% sulfuric acid.
50 g denier / 20 filament rayon yarn was obtained by spinning 0 g / l, 345 g / l of sodium sulfate, and 15 g / l of zinc sulfate into a spinning bath at a temperature of 60 ° C. at a spinning speed of 90 m / min and an immersion length of 60 cm.

The obtained rayon yarn was a clear black yarn with gloss. In addition, during spinning, no troubles such as yarn breakage and clogging of the viscose discharge holes occurred.

Examples 6 to 9 Colorants (A) and (D) obtained in Reference Example 1 and Reference Example 4 were added to the same viscose as used in Examples 1 to 5 so that CB was 10%. The colorant (C) obtained by dispersing in water and the colorant (C) obtained in Reference Example 3 was added to CB against viscose.
Was added and mixed well to prepare a colored viscose composition. With this composition, the composition is sulfuric acid
100g / l, 350g / l sodium sulfate, 20g / l zinc sulphate at 40 ℃
Was spun into the first coagulation bath.

Then, the regeneration was completed while introducing into a second bath of sulfuric acid 10 g / l at a temperature of 90 ° C. and stretching. The obtained rayon yarn was cut into 50 mm and dried to obtain rayon staple.

The rayon staple obtained had a very high blackness of 5 denier. Further, during spinning, no trouble such as yarn breakage or clogging of the viscose discharge hole was generated.

Comparative Examples 1-2 Untreated CB MA-100R (manufactured by Mitsubishi Kasei Co.) and MA-100R were added to the same viscose as used in Examples 1-5.
A colored viscose composition for comparison was prepared by adding an amount of CB which was 3% to viscose to be dispersed in water so that B was 10% and mixing them well. Using this comparative composition, spinning was carried out in the same manner as in Example 1 to obtain 50 denier / 20 filament rayon yarn.

The obtained rayon yarn lacked black uniformity, and it was confirmed by microscopic observation that black coarse particles were mixed in places in the rayon yarn. In addition, yarn breakage sometimes occurred during spinning.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sadanori Sano 5-8 Nishimitabicho, Suita City Examiner, Central Research Laboratory, Nippon Catalysis Chemical Co., Ltd. Shigemi Sawamura (56) Reference JP-A 63-270767 (JP, A)

Claims (4)

(57) [Claims] 1. A colorant for undiluted viscose rayon comprising carbon black treated with poly (oxazoline) (a) and / or modified poly (oxazoline) (b). 2. A treated carbon black is obtained by stirring and mixing the carbon black with a poly (oxazoline) (a) and / or a modified poly (oxazoline) (b) under a temperature condition of 0 ° C. to 400 ° C. The coloring agent for viscose rayon of undiluted solution according to claim 1, which is obtained. 3. Poly (oxazoli) (a) is 2-ethyl-
Claim 1 which is obtained by using one or more kinds of 2-oxazoline monomers selected from 2-oxazoline, 2-phenyl-2-oxazoline and 2-cyclohexyl-2-oxazoline as a main component. The coloring agent for viscose rayon of undiluted solution according to the above item. 4. The poly (oxazoline) modified product (b) is 2-
Poly (oxazoline) obtained by using as a main component one or two or more 2-oxazoline monomers selected from ethyl-2-oxazoline, 2-phenyl-2-oxazoline and 2-cyclohexyl-2-oxazoline.
The colorant for undiluted viscose rayon according to claim 1, which is a modified product of (a).