JPH02145808A - Liquid colorant for mass-coloring of polyamide fiber - 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 coloring agent for polyamide fibers, and more particularly to a liquid coloring agent for materials having good compatibility with polyamide.

[Conventional technology]

BACKGROUND ART Conventionally, dope-dyed yarns have been widely used for general clothing and industrial materials because of their ability to omit the dyeing process. Furthermore, since spun-dyed yarn is superior in terms of its weather resistance and fastness, demand from the market has been increasing in recent years.

However, polyamide spun-dyed yarn is rarely used in only a single color in clothing or industrial material applications.

For this reason, there is a need to manufacture spun-dyed yarns of various colors, but the conventionally used masterbatch addition method requires cleaning of the supply system when changing colors, cleaning of the extruder or conduit, etc. This has the major disadvantage of reducing productivity.

Therefore, instead of using the masterbatch addition method, a method is being considered for polyester fibers, in which a liquid colorant is supplied from the middle of the Merck, making it easier to change colors without staining the extruder with colorant (for example, Unexamined Japanese Patent Publication 1986-45
689, JP 60-45690, JP 63-92719, JP 63-117071, etc.).

As shown in these conventional techniques, as a medium that is liquid at room temperature, has heat resistance of 250 to 300°C, which is the melt spinning temperature of polyamide and polyester, and can disperse pigments and dyes, There are low molecular weight polyesters and polyethers with a molecular weight of 1.000 to 4,000,
It has no compatibility with polyamide, and when it is mixed into polyamide and spun, it separates and scatters during discharge, making it impossible to achieve satisfactory spinning.

On the other hand, low-molecular-weight polyamides that are compatible with polyamides cannot be used because they do not have the heat resistance to enable melt spinning.

[Problem to be solved by the invention]

The present invention was made against the background of the problems of the prior art, and is made of polyamide fibers that are compatible with polyamides and have good productivity and are suitable for producing multicolored spun-dyed yarns that have sufficient spinning stability. The purpose is to provide a coloring agent for raw materials.

[Means to solve the problem]

The present invention is characterized in that pigments and/or dyes are combined with -X-M at the end or in the middle (wherein -X-M is selected from the group of sulfonates, phosphate ester salts, sulfate ester salts and carboxylate salts). at least one anionic hydrophilic group, M represents an alkali metal or alkaline earth metal)
Liquid polyester and/or having a hydrophilic group represented by
or liquid polyether, and has a resistance of 3,000 at room temperature.
This is a liquid coloring agent for polyamide fiber raw material, which is characterized by being a liquid of less than a poise and having compatibility with polyamide.

Pigments and/or dyes used in the present invention are not particularly limited, and include commonly used organic pigments such as azo, phthalocyanine, perinone, perylene, and anthraquinone; carbon black; Examples include inorganic pigments such as ultramarine, red iron oxide, and titanium oxide; and dyes such as azo, perinone, and anthraquinone. As the colorant of the present invention, it is preferable to use only a pigment or a combination of a pigment and a dye.

The present invention is made by blending the pigment and/or dye with a liquid polyester and/or polyether as a dispersion medium having a specific parent wood group.

In general, as a dispersion medium that is liquid at room temperature and capable of dispersing pigments at a high concentration, molecular ml obtained by reacting a dibasic organic acid and a dihydric alcohol as described in JP-A No. 60-45689 is used. , 000 to 4.000, such as adipic acid and 1.000 to 4.000. There are those synthesized from 3-butylene glycol, adipic acid and ethylene glycol, and sebacic acid and propylene glycol.

Similarly, as described in JP-A-63-120767, there are liquid polyethers such as polyethylene glycol dilaurate and polyethylene glycol dioleate.

However, although these materials are liquid at room temperature and can disperse pigments at high concentrations and have properties as dispersants, they lack compatibility with polyamides and cannot be used as liquid adhesive agents for polyamide fibers. The current situation is that it is not suitable.

Therefore, as a result of extensive research, the present inventors have found a dispersion medium that is liquid at room temperature, capable of dispersing pigments or dyes at high concentrations, and is compatible with polyamide. While maintaining pigment dispersibility with the basic component low molecular weight polyester or polyether,
By introducing an anionic hydrophilic group such as sulfonate, phosphate ester salt, sulfate ester salt, or carboxylate salt into the terminal or middle part, the interaction between the dispersion medium and polyamide increases, improving compatibility. This is what I found possible.

Generally, polyamide easily forms hydrogen bonds due to its basic structure and has a strong affinity for water, that is, it has hydrophilic properties. Therefore, if an anionic hydrophilic group is introduced into the hydrophobic component, such as liquid polyester or liquid polyether, the compatibility with polyamide can be improved.

Among those exhibiting anionic hydrophilic groups, the 10H group of low molecular weight polyester, which is liquid at room temperature,
For example, when a metal salt of an organic sulfonic acid is introduced by reacting a carboxylic acid with a metal salt terminal of an organic sulfonic acid, -
The compatibility with the polyamide is improved due to the electronegativity between the 3O,-M group and the polyamide, the shielding effect of the main polyester, and the like.

-3o3- When making effective use of the interaction of the M group with the polyamide and taking into account the steric and electronic distance between the low molecular weight polyester main chain and the polyamide main chain, alkali metals and alkaline earth metals are effective as M. In particular, a sodium atom is preferred.

Furthermore, as R, those having aromatic or aliphatic hydrocarbons in the skeleton are effective, but aromatic ones are more effective due to their shielding effect and steric hindrance effect, and R has a carbomethoxy group at the meta position. Sodium benzenesulfonate is preferred.

Pigments and/or dyes and liquid polyester and/or
Alternatively, the weight ratio with liquid polyether is 30 to 5,000 parts by weight of liquid polyester and/or liquid polyether to 100 parts by weight of pigment and/or dye.

The liquid colorant used for the above polyamide must have a viscosity of 3,000 voids or less.

The reason is that polyamide used for industrial materials or general clothing has a melt viscosity of 800 to 800
This is because if the viscosity of the liquid coloring agent mixed into the polyamide is too high, it will be difficult to disperse.

The liquid colorant of the present invention preferably contains 10 to 100 parts by weight of a copper compound based on 100 parts by weight of the pigment and/or dye. Even if spun-dyed polyamide fibers are spun-dyed to take advantage of their excellent weather-fastness, if a copper compound is not present, the polyamide itself will be degraded by light and its strength will deteriorate significantly, resulting in improved weather-fastness (improved fading resistance). ). This copper compound is
It is not necessary to mix it into the liquid colorant side, but it can be mixed into the polyamide side, but it is preferable to add it to the polyamide side together with the liquid colorant addition device because it can simplify the production process.

As the copper compound, copper halides, copper sulfate, copper acetate, etc. are used, but cuprous halides are preferred, and cuprous iodide is particularly preferred.

Further, as a copper precipitation inhibitor, it is preferable to add potassium iodide, 2-mercaptobenzimidazole, etc. in an amount equivalent to or more than the amount of the digested compound, preferably 2 to 5 times the amount, at the same time as the copper compound.

〔Example〕

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

Comparative Example 1 and Example 1 280 parts by weight of low molecular weight liquid polyester polyol (A) with a molecular weight of 2,200 synthesized from adipic acid, n-bentanediol and ethylene glycol, 95 parts by weight of phthalocyanine green, and 5 parts by weight of carbon blank. and a liquid coloring agent (■) consisting of 20 parts by weight of cuprous iodide, or the liquid polyester polyol (A
) with sodium 3,5-dicarbomethoxysulfonate under reduced pressure to form a liquid polyester polyol (B) which is bonded to 28
A spun-dyed polyamide yarn was spun using a liquid coloring agent (ff) consisting of 0 parts by weight, 95 parts by weight of phthalocyanine green, 5 parts by weight of carbon black, and 20 parts by weight of cuprous iodide.

Here, as polyamide, m-cresol [
Using a nylon 6 polymer with η) = 1.34, liquid colorant (1) or (I) was added to 100 parts by weight of polyamide.
2 parts by weight, 4 parts by weight or 8 parts by weight of I) were metered and injected into the molten nylon part of the polymer introduction pipe, and 30 stages of static mixers (KEX type) were incorporated from the downstream side to mix them. It was discharged from a spinneret, subjected to spinning, stretching, and crimping, and wound up into wine goo. The spinning temperature was 255°C.

Table 1 shows the spinning conditions of colorants (1) and (II) at this time.

As is clear from Table 1, colorant (1) lacks compatibility with nylon, so if it is mixed in at 2 parts by weight, yarn production is possible, but over time stains of liquid polyester appear around the nozzle. When 4 parts by weight was mixed, stretching yarn breakage was observed, and when 8 parts by weight was mixed, yarn breakage occurred during spinning, and stable yarn spinning was not possible.

On the other hand, colorant (n) has compatibility with nylon, so even if 2 to 8 parts by weight is mixed in, no yarn breakage is observed during spinning, drawing, or crimping, and the colorant (n) does not cause yarn breakage around the spinneret nozzle. Stable yarn spinning was possible without staining over time.

(Margins below) Table 1 When producing polyamide spun-dyed yarn, there are no problems such as separation of the liquid colorant at the spinneret, staining of the spinneret, poor spinnability, etc., and stable polyamide spongy-dyed yarn can be produced. In particular, the obtained spun-dyed yarn has good weather fastness and weather resistance deterioration.

Claims (7)

[Claims] (1) Pigments and/or dyes and -X-M at the end or in the middle (where -X-M is selected from the group of sulfonates, phosphate ester salts, sulfate ester salts and carboxylate salts) At least one kind of anionic hydrophilic group, M
is a liquid polyester and/or a liquid polyether having a hydrophilic group represented by (indicates an alkali metal or alkaline earth metal), is a liquid with a poise of 3,000 poise or less at room temperature, and is compatible with polyamide. A liquid coloring agent for polyamide fiber base material, characterized by having the following characteristics: (2) 30 to 30 parts of liquid polyester and/or liquid polyether to 100 parts by weight of pigment and/or dye
The liquid coloring agent for polyamide fiber base material according to claim 1, containing 5,000 parts by weight. (3) Hydrophilic group -X-M is sulfonate -R-SO_3M
(Here, R is an aromatic or aliphatic hydrocarbon group and may have a substituent.) The liquid coloring agent for polyamide fiber base material according to claim 1 or 2. (4) The hydrophilic group -X-M is -R-SO_3M (here, R
is an aromatic or aliphatic hydrocarbon group which may have a substituent);
Liquid coloring agent for polyamide fiber base material according to 2 or 3. (5) The liquid coloring agent for polyamide fiber base material according to claim 3 or 4, wherein R in the sulfonate -R-SO_3M is ▲a numerical formula, a chemical formula, a table, etc.▼, and M is a sodium atom. (6) The liquid coloring agent for polyamide fiber base material according to claim 1, 2, 3, 4 or 5, which contains a copper compound. (7) The liquid coloring agent for polyamide fiber base material according to claim 6, wherein the copper compound is a cuprous halide.