JPH07118927A - Additive-containing composition for compounding to polyamide resin stock solution - Google Patents

Abstract

PURPOSE:To obtain the additive-containing composition having improved compatibility with a polyamide and capable of producing a polyamide fiber having excellent drawability. CONSTITUTION:An additive-containing composition for compounding to a polyamide resin stock solution is obtained by mixing (A) 100 pts.wt. of an additive, e.g. a dying pigment with 30-5000 pts.wt. of a carboxylic group-containing liquid polyester having a molecular weight of 500-3500 and an acid value of >=10.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive-containing composition for blending a polyamide-based resin stock solution, and in particular, it is blended with a polyamide-based resin in a molten state, mixed and molded to uniformly disperse the additive. The present invention relates to an additive-containing composition for blending a polyamide-based resin stock solution, which is suitable for obtaining the above-mentioned polyamide molded product.

[0002]

2. Description of the Related Art Conventionally, undyed colored yarns such as polyester and polyamide can be omitted in the dyeing process as compared with general dyed yarns.
It is also excellent in terms of weather resistance and robustness. These stock solution coloring methods include a method of adding a colorant during the polymerization reaction, a masterbatch method of adding a masterbatch in which dyes and pigments are dispersed in a polymer at a high concentration to a natural resin, and further a dye and pigment are directly added to the polymer. There are known dry coloring methods and the like. However, each of these methods requires a large amount of money and labor for cleaning because the contamination area in the production process is wide. Therefore, when producing multiple colors, there is a demerit that the productivity is significantly reduced. Therefore, in the resin molding process, a fixed amount of liquid colorant is supplied just before the discharge part of the molten resin (polyester or polyamide) and pressed into the molten resin to minimize the contaminated area and facilitate color change. Are being investigated for polyester and polyamide.

As a liquid colorant used when the polyamide is undiluted by being pressed into a molten polyamide,
(1) Containing an isoindolinone pigment, a stearic acid metal salt, and a dispersion medium such as liquid polyester, polyol, and liquid polyester ether (JP-A-63-927).
No. 17), (2) additives such as dyes and pigments and modifiers, and the general formula —OC (R ₁ COO) _k (R ₂ O) ₁ — (however,
R ₁ and R ₂ are C _{2 to} C ₄ alkylene groups, k is a positive integer, l
Is 1 or 2) and has an acid value of 3 or less and a hydroxyl value of 3
A liquid dispersion medium having a preferable range of 0 to 50 (Japanese Patent Laid-Open No. 2-175918) is known.

However, since they are not compatible with polyamide, it is difficult to disperse them uniformly in the resin, and there is a problem in the uniformity and stability of resin strength. Therefore, a dispersion medium having an improved compatibility, such as one composed of a dye / pigment and a liquid polyester and / or a liquid polyether having an anionic hydrophilic group at a terminal or an intermediate portion (JP-A-2-145808), has been investigated. However, it is the fact that commercial production has not been reached because it is difficult to maintain the quantitative supply with a pump and to control the water content.

[0005]

The present invention has been made against the background of the above-mentioned problems of the prior art. Even when blended with a molten polyamide, it has compatibility with the polyamide and stable moldability, particularly An object of the present invention is to provide an additive-containing composition for blending a polyamide-based resin stock solution having spinnability.

[0006]

That is, the present invention is characterized in that it comprises an additive (A) consisting of a dye / pigment and / or a modifier, and a liquid carboxyl group-containing polyester (B). It is an additive-containing composition for blending a polyamide resin stock solution.

The dye / pigment used in the present invention is not particularly limited, and it is selected from organic pigments, inorganic pigments and dyes and does not cause thermal decomposition when added to a polyamide resin in a molten state. Any of them can be used.

The modifier used in the present invention is a known auxiliary agent for polyamide-based resins such as metal soaps, ultraviolet absorbers, flame retardants, stabilizers, reinforcing agents, antistatic agents, antibacterial agents and conductive agents. The agent is not particularly limited as long as it does not cause thermal decomposition when added to the molten resin.

The dispersion medium for these additives used in the present invention is a carboxyl group-containing polyester having a basic skeleton of polyester and containing a carboxyl group at the terminal or intermediate portion thereof. No particular method is required for the synthesis of the carboxyl group-containing polyester as long as the carboxyl group can be introduced into the structure. As the acid component for synthesizing such a polyester, in addition to aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and succinic acid, if necessary, oleic acid, lauric acid, phthalic acid, trimellitic acid, etc. You may use together as an acid component. Alcohol components include ethylene glycol, diethylene glycol, 1.4. Butanediol, neopentyl glycol, 1.6. A diol such as hexanediol or n-pentanediol can be used, but is not particularly limited. Glycerin, if necessary
You may use together, such as trimethanol propane.
In particular, when a trifunctional one such as glycerin, trimethanol propane or trimellitic acid is used as an alcohol component or an acid component, a carboxyl group-containing polyester excellent in thermal stability can be obtained, and a polyamide using the polyester as a dispersion medium. The use of carboxyl group-containing polyester obtained by using these trifunctional ones together is preferable because the number of yarn breakages decreases.

If the molecular weight of the polyester is less than 500, there is a problem in thermal stability, and the polyester tends to decompose in the molten resin. On the other hand, if it exceeds 3500, the viscosity is too high and there is no fluidity, making it difficult to quantitatively supply the additive composition by a pump. The acid value of the polyester is 10 (K
OHmg / g) or more, preferably in the range of 40 to 150. On the other hand, the hydroxyl value is 10 (KOHmg / g) or less. In the case of the liquid polyester which is a conventional dispersion medium, the acid values are all less than 10, which is a great difference from the liquid carboxyl group-containing polyester of the present invention.

The additive composition of the present invention is a liquid carboxyl group-containing polyester 30 to 50 with respect to 100 parts by weight of the additive comprising the dye and pigment and / or the modifier.
It consists of 00 parts by weight. Within this range, the dispersion uniformity and function of the additive can be maintained, and the physical properties of the polyamide resin are not significantly changed.

[0012]

The carboxyl group-containing polyester used as the dispersion medium in the additive composition of the present invention has an appropriate affinity for the polyamide resin because the carboxyl group has an appropriate compatibility, so that the compatibility with the polyamide resin is improved and the oil in the polyamide is improved. The size of the diameter of the polyester dispersed in the form of drops is
It is remarkably smaller than the polyester having no carboxyl group. Due to this action, it is considered that the additive composition is uniformly dispersed in the polyamide, and that the strength of the polyamide-based resin is evenly obtained.

[0013]

EXAMPLES The present invention will be described below with reference to examples. All parts and% in the examples and comparative examples are parts by weight and% by weight.

Comparative Example 1 (Experiment A: No Pigment) A liquid polyester polyol having a molecular weight of 2000 (acid value: 1 or less) synthesized from adipic acid and diethylene glycol was used, and this polyol was melt-spun onto nylon 6 in a molten state. It was pressed in from the head, mixed, spun into filaments at 300 m / min, and further stretched 4 times to obtain 10 denier nylon 6 stretched yarn. A-1 is a spun yarn containing 2% of the polyol, and A-2 is a spun yarn containing 6% of the polyol.

(Experiment B: With Pigment) In Experiment B, a colorant comprising the polyester polyol (acid value: 1 or less) and a pigment was used, which was added to Nylon 6 and the same as in Experiment A. The yarn was manufactured. That is, a pigment was used as a pigment, 20 parts of this pigment was added to 80 parts of the polyol, and the mixture was kneaded to prepare an undercoat colorant. This colorant was used in Experiment A
In the same manner as in (1), adding to nylon 6 in a molten state, a dyed yarn having a pigment concentration of 0.5% (B-1: containing 2% of polyol),
A spun-dyed yarn (B-2: containing 6% of polyol) having a pigment concentration of 1.5% was obtained by spinning and drawing.

Example 1 (Experiment A) A liquid carboxyl group-containing polyester 1 having a molecular weight of 2000 (acid value: 110, hydroxyl value: 0.5 or less) synthesized from adipic acid and diethylene glycol was used. Experiment A (no pigment) was carried out by adding Nylon 6 in the molten state in the same manner as in. A-3 is a dyed yarn containing 2% of the polyester, and A-4 is 6
% Of the contained yarn.

(Experiment B) Twenty parts of the pigment was added to the liquid carboxyl group-containing polyester 1 (acid value: 110, hydroxyl value:
0.5 or less) 80 parts and kneaded to prepare a colorant for undercoating. This colorant was added to Nylon 6 in a molten state in the same manner as in Experiment A, and the dyed yarn (B
-3: containing 2% of polyester) and a spun-dyed yarn with a pigment concentration of 1.5% (B-4: containing 6% of polyester) were obtained by spinning and drawing.

Example 2 (Experiment B) Liquid carboxyl group-containing polyester 2 (molecular weight: 2000, acid value: 65, synthesized by adding trimethanolpropane to adipic acid and diethylene glycol)
80 parts of hydroxyl value: 3 or less) and 20 parts of Rouge were kneaded to prepare a colorant for undercoating. This colorant was added to Nylon 6 in a molten state in the same manner as in Experiment A of Example 1, and a dyed yarn having a pigment concentration of 0.5% (B-5: containing 2% of polyester).
Then, a spun-dyed yarn (B-6: containing 6% of polyester) having a pigment concentration of 1.5% was spun and drawn.

In the above experiments A and B, the number of yarn breakages, the yarn strength, and the average diameter of the dispersion medium dispersed in the nylon resin in the form of oil droplets (image analysis device "Japan Avionics.
A-II "is used. However, it is measured by removing fine particles by image processing. Table 1 shows the measurement results of the above. In addition,
When the pigment was added, the contrast of the image was not obtained, so the average diameter of the dispersion medium was not calculated.

[0020]

[Table 1]

As is clear from Table 1, in Experiment A, the average diameter of the dispersion medium in the nylon resin is more than doubled in the Examples, and the number of yarn breakages during spinning is reduced. The same can be said for Experiment B in which the pigment is added. When a trifunctional raw material was added to the molecule as in Example 2, no fiber breakage occurred even when the dispersion medium was added to the resin at a high concentration.

[0022]

The additive-containing composition of the present invention, which is a polyamide resin in a molten state, uses a liquid carboxyl group-containing polyester as a dispersion medium for additives such as dyes and pigments and modifiers. Since the compatibility of polyamide is improved and the yarn-forming property is excellent, the polyamide-dyed yarn can be stably produced.

Claims (5)

[Claims] 1. An additive for blending a polyamide resin undiluted solution, comprising an additive (A) consisting of a dye / pigment and / or a modifier, and a liquid carboxyl group-containing polyester (B). Containing composition. 2. The additive-containing composition according to claim 1, wherein the liquid carboxyl group-containing polyester (B) has a molecular weight of 500 to 3,500. 3. A carboxyl group-containing polyester (B)
The acid value of is 10 (KOHmg / g) or more.
The additive-containing composition described. 4. The additive-containing composition according to claim 2, wherein the carboxyl group-containing polyester is a polyester obtained by using triol and / or tricarboxylic acid as a part of raw material components during the polyester synthesis. 5. A liquid carboxyl group-containing polyester (B) 30 to 500 relative to 100 parts by weight of the additive (A).
The additive-containing composition according to claim 1, which is mixed at a ratio of 0 part by weight.