JPH062990B2 - Liquid colorant for polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an undercoat colorant for polyester fibers.

Conventionally, a method of adding a pigment or a dye to a reaction system at the time of polyester polymerization reaction is well known as a method for coloring a saturated polyester undiluted solution such as polyethylene terephthalate.
Since it is 0 to 300 ° C.), what is practically used is limited to pigments having good heat resistance such as titanium dioxide, carbon black and extender pigments. Further, since the polymerization kettle is significantly contaminated, there are drawbacks such as the installation of a special kettle and the large labor cost required for cleaning the kettle.

The masterbatch method or the dry color method was adopted to improve the above-mentioned drawbacks, but the drawbacks in both directions are as follows.

1. When manufacturing a masterbatch, it is difficult to disperse the pigment in a high concentration.

2. When manufacturing a masterbatch, it is necessary to dry the resin before processing, crystallize the masterbatch after processing, and sometimes further dryness, which consumes a large amount of energy.

3. Further, during the production of the masterbatch, the thermal history of the polyester resin, which is the dispersion medium used, causes a decrease in the physical properties such as the tensile strength of the colored and spun fiber.

4. In the dry color method, there are problems in scattering of the colorant during premixing and dispersibility of the pigment or dye.

5. At the time of spinning, it is necessary to dry the masterbatch and the dry color, and it is necessary to install a dedicated drying facility or dry the mixture with the natural resin in a dryer.
For this reason, when changing colors, it is necessary to wash from the drying equipment to the spinning line, and it is difficult to handle frequent color changes.

A liquid colorant that is easy to handle and has little color change time during premixing, such as amino alcohols such as mono-, di-, or triethanolamine as a dispersion aid, and a secondary colorant such as ethylene glycol. A composition using a polyhydric alcohol as a dispersion medium is known. However, in the above composition, due to the high viscosity of the dihydric alcohols, the fluidity decreases as the pigment content increases, which means that the quantitative feedability by the automatic feeder at the time of blending the colorant is reduced. It appears as a fault of being bad. There is also a problem in practical use that the dispersibility of the colorant is not always good. In order to ameliorate the above-mentioned drawbacks or problems of the polyester fiber stock solution colorant, the inventors of the present invention have studied various liquid dispersants, and in JP-A-58-149311, disclosed a monobasic or polybasic organic acid. We have disclosed a liquid colorant containing a polyhydric ester having an acid component as a monohydric or polyhydric alcohol as an alcohol component as a vehicle component. The vehicle component consisting of this polyhydric ester has a low molecular weight, so that it exceeds 200 ° C. It was found that decomposition started and yarn breakage occurred depending on the spinning conditions of the polyester fiber. Therefore, the present invention has been accomplished by further studying the vehicle component of the liquid colorant. That is, the present invention comprises 100 parts by weight of a pigment or dye and 30 to 2000 parts by weight of a liquid polyester obtained by reacting a dibasic organic acid with a dihydric alcohol as a constituent.
It is a coloring agent for coloring a polyester fiber stock solution, which is more than 1500 poise and 10,000 poise or less at room temperature.

Examples of raw materials or dyes that can be used in the present invention include azo-based, phthalocyanine-based, anthraquinone-based, dioxazine-based, perylene-perinone-based organic pigments, and pigments commonly used in polyesters such as titanium oxide, iron oxide, ultramarine blue and carbon black. It is also possible to use oil-soluble or disperse dyes such as azo-based, anthraquinone-based, perinone-based, and heterocyclic-based dyes and these pigments and dyes in combination.

The liquid polyester in the present invention is one in which two or more organic acid components and two or more alcohol components are bonded via an ester bond, and the organic acid component or the alcohol component may be the same kind or different kinds. May be. As a preferred liquid polyester, the main constituent components are aliphatic or aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, glutaric acid, hydrogenated phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid and phthalic anhydride, And a dihydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, pentyl glycol, hexyl glycol, neopentyl glycol or diethylene glycol, which has been subjected to a polycondensation reaction. In addition to the above dicarboxylic acids or dihydric alcohols, carboxylic acid such as coconut oil fatty acid, soybean oil aliphatic, oleic acid and lauric acid, trivalent carboxylic acid such as trimellitic acid and pyromellitic acid, Alcohol components such as n-octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-decyl alcohol and other monohydric alcohols, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, sorbitol and other polyhydric alcohols. Alcohol can be used as appropriate.

In order to obtain good measurement accuracy when using a liquid colorant,
It is preferable that it exhibits fluidity at room temperature or heat retention, and particularly if it has a viscosity higher than 10,000 poise at room temperature, it impairs the measurement accuracy and is not preferable for practical use.

Further, although the liquid polyester of the present invention has a relatively high boiling point, it may cause a foaming phenomenon due to vaporization of the polyester depending on the conditions during spinning and drawing, which may cause yarn breakage, In this case, especially 200 ℃
A liquid polyester having a vapor pressure of 10 mmHg or less is selected. Specifically, it may be synthesized with the liquid polyester and then purified by distillation under reduced pressure or by removing unreacted substances and low boiling point reactants under reduced pressure.

The colorant for coloring the polyester fiber stock solution of the present invention can be produced by an ordinary disperser such as a triple roll mill, a ball mill, a sand mill, an attritor, or a kneader, or a combination thereof.

In addition to the pigment or dye, the liquid colorant of the present invention may contain additives such as an antistatic agent, an ultraviolet absorber and an antioxidant depending on the purpose.

The liquid polyester of the present invention does not decompose and change even at the spinning temperature of the polyester resin (270 ° C. or higher) and has a low viscosity, so that the pigment or dye is, for example, 25% by weight of carbon black, 35% by weight of organic pigment and 35% by weight of inorganic pigment. Even if the content is 70% by weight at room temperature or heat retention (15
It has the preferable properties of exhibiting fluidity at 0 ° C. or lower) and good compatibility with polyester resin. Therefore, the polyester fiber stock solution coloring / dissolving agent of the present invention has (1) good dispersibility and enables high-concentration coloring.

(2) It is easy to bite into the screw during spinning and there is no phenomenon such as yarn breakage.

(3) Good quantitative supply when the colorant is blended.

(4) There is almost no deterioration in the physical properties of the fiber.

There is a feature called.

Next, examples will be described.

Example 1 A reaction vessel equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, a temperature control device, a partial condenser, etc. was charged with 452 parts of adipic acid and 348 parts of 1,3-butylene glycol, while flowing nitrogen gas. The reaction temperature was gradually raised to 240 ° C. and the reaction was continued until the acid value was 10. Next, remove the partial condenser from the reaction vessel, and
Vacuum distillation was performed at 0 mmHg for 1 hour to obtain a liquid polyester having an oxidation of 2.5 and a viscosity of 20 poise.

65 parts by weight of the above liquid polyester, 12 parts by weight of anthraquinone yellow (product name: Filerester Yellow 2648A, manufactured by Cibaigi), 16 parts by weight of perylene red (product name: Pyrogen Red-3911HD, manufactured by BASF), carbon black (Mitsubishi Carbon MCF-88, Mitsubishi) 7 parts by weight of Kasei Co., Ltd. was kneaded with a three-roll mill to obtain a brown liquid colorant of 6000 poise.

Polyester resin (trade name RE-500, manufactured by Toyobo) 1
5 parts by weight of this coloring agent was added to 00 parts by weight, and after spinning with a spinning tester (manufactured by Fuji Filter) to a yarn thickness of 10 denier, it was drawn 3.3 times at 100 ° C. to obtain a 3 denier yarn. Obtained. Tensile strength (dry / wet) by observing visually the presence or absence of yarn breakage during spinning and drawing at a yarn thickness of 3 denier and the dispersibility of the pigment or dye in the obtained colored fiber
Was measured. The results are shown in Table 1.

Example 2 Commercially available phthalate polyester (trade name Polycizer P
-29, manufactured by Dainippon Ink Co., Ltd., 67.2 parts by weight, anthraquinone dye (trade name: Kayaset Blue A-CR, manufactured by Nippon Kayaku) 26.2 parts by weight, penolin pigment (trade name: Kayaset Red E-BG). (Manufactured by Nippon Kayaku Co., Ltd.) was kneaded with 3 rolls to obtain a 7200 poise liquid colorant.

5 parts by weight of this colorant was added to 100 parts by weight of the polyester resin used in Example 1, and the same operation and measurement as in Example 1 were performed. The results are shown in Table 1.

As is clear from Table 1, the polyester fiber using the colorant of the present invention has good dispersibility, no coarse colored particles of 3 μm or more are observed, and spinning, drawability and physical properties are hardly deteriorated. The results are shown.

Comparative Example 1 85 parts by weight of ethylene glycol was kneaded with 15 parts by weight of the carbon black used in Example 1 using an attritor,
A liquid colorant of 1000 poise was obtained.

When 4 parts by weight of this colorant was added to the polyester resin used in Example 1 and the same operation and measurement as in Example 1 were carried out, this colored fiber was found to have colored particles of 3 μm or more, and the dispersibility of the pigment was It was bad. Also, yarn breakage occurred during spinning and drawing.

Comparative Example 2 70 parts by weight of ethylene glycol and 30 parts by weight of phthalocyanine blue used in Example 1 were kneaded with an attritor to obtain a liquid colorant of 8000 poise.

When 3 parts by weight of this colorant was added to the polyester resin used in Example 1 and the same operation and measurement as in Example 1 were carried out, this colored fiber showed colored particles of 3 μm or more, and the dispersibility of the pigment was It was bad. In addition, yarn breakage occurred during spinning and drawing.

Comparative Example 3 A liquid colorant having a vehicle component of dipentaerythritol saturated fatty acid ester in place of the liquid polyester resin of Example 1 was obtained. A polyester fiber was produced in the same manner as in Example 1 using this liquid colorant.
Thread breakage occurred during drawing.

Claims (4)

[Claims] 1. A pigment or dye comprising 100 parts by weight and 30 to 2000 parts by weight of a liquid polyester obtained by reacting a dibasic organic acid with a dihydric alcohol as a constituent, and the composition exceeds 1,500 poises and 10,000 at room temperature. A liquid colorant for a polyester fiber base, which is a liquid of poise or less. 2. The liquid colorant for a polyester fiber base material according to claim 1, wherein the dibasic organic acid is an aliphatic dicarboxylic acid. 3. The liquid colorant for a polyester fiber base material according to claim 1, wherein the dibasic organic acid is an aromatic dicarboxylic acid. 4. The liquid colorant for a polyester fiber base material according to claim 1, wherein the liquid polyester has a vapor pressure at 200 ° C. of 10 mmHg or less.