JPS6045689A - Liquid colorant for polyester 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 raw materials of polyester fibers.

Conventionally, this is the method for coloring saturated polyesters such as polyethylene terephthalate with a stock solution.

A well-known method is to add pigments or dyes to the reaction system during the polyester polymerization reaction, but since the reaction system is at a high temperature (240 to 300°C) in this method, titanium dioxide, titanium dioxide, It is limited to pigments with good heat resistance such as carbon black and extender pigments.

In addition, since the double polymerization kettle is significantly contaminated, there are drawbacks such as the need to install a dedicated kettle and a great deal of labor and expense for cleaning the kettle.

In order to improve the above-mentioned drawbacks, a masterbatch method or a dry color method has been adopted, but both methods have the following drawbacks.

1. When producing master punches, it is difficult to disperse pigments at high concentrations.

2. When manufacturing master bunches, the resin is dried before processing and the master bunch is crystallized after processing.

Further, sometimes additional drying is required, which consumes a large amount of energy.

3. Furthermore, during the production of the master bunch, the physical properties such as the tensile strength of the two-colored spun and drawn fibers occur due to the thermal history of the polyester resin used as the dispersion medium.

4. The dry color method has problems with the scattering of colorants during premixing and the dispersibility of pigments or dyes.

5. During spinning, it is necessary to dry the masterbatch and dry color, and it is necessary to provide dedicated drying equipment or to dry the mixture with natural resin in a dryer.

Therefore, when changing five colors, it is necessary to clean everything from the drying equipment to the spinning line, making it difficult to handle frequent color changes.

Liquid colorants are easy to handle, have no premix contamination, and short color change times.3 Due to the presence of mono-, di-, or triethanolamines, their fluidity decreases as pigment content increases. 5. This results in a disadvantage that the automatic feeder is not capable of quantitatively feeding the colorant when blending it. Further, there was also a practical problem that the dispersibility of the two colorants was not necessarily good.

In order to improve the drawbacks or problems of the above-mentioned colorants for coloring polyester fiber stock solution, the present inventors investigated various liquid dispersants, and as shown in Japanese Patent Application No. 57-28199, - Although esters containing a base or polybasic organic acid as the acid component and a monohydric or polyhydric alcohol as the alcohol component have been disclosed, the present invention was achieved through continued investigation. That is, the present invention.

100 parts by weight of pigment or dye and 30 parts of liquid polyester
~2000 parts by weight, 1'0.000 at room temperature
This is a coloring agent for coloring polyester fiber stock solution, which is characterized by having a voidage or less.

Pigments 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 for polyester, such as titanium oxide, iron 2 ultramarine, and carbon blank. It is also possible to use oil-soluble or dispersed dyes such as azo, anthraquinone, perinone, and heterocyclic dyes, and to use 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 ester bonds, and the organic acid components or alcohol components may be of the same type or different types. You can. Preferred liquid polyesters include 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; It is the result of a polycondensation reaction between dihydric alcohol such as ethylene glycol, propylene glycol, butylene gelylcol, pentyl glycol, hexyl glycol, neopentyl glycol, and diethylene glycol. In addition to the above dicarboxylic acids or dihydric alcohols, acid components include coconut oil fatty acids, soybean oil fatty acids, monohydric carboxylic acids such as oleic acid and lauric acid, and trimellitic acid.

Trihydric carboxylic acids such as pyromellitic acid, monohydric alcohols such as n-octyl alcohol, inoctyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol + n7yl alcohol, trimethylolpropane, glycerin, pentaerythritol, Polyhydric alcohols such as dipentaerythritol and sorbitol can be used as appropriate.

In order to obtain good measurement accuracy when using liquid colorants,
It is preferable that it exhibits fluidity at room temperature or when kept warm, and in particular, if it has a viscosity higher than 10,000 voids at room temperature, it will impede measurement accuracy and is not preferred in practice.

Therefore, the viscosity of the liquid polyester is preferably 200 voids or less, preferably 100 voids or less at room temperature. Especially when the viscosity at room temperature is 200 boids or more,
Pigments or dyes may have poor dispersibility.

Furthermore, although the liquid polyester of the present invention has a relatively high boiling point, depending on the conditions during spinning and drawing, the polyester may vaporize and cause foaming, which may cause yarn breakage. In such cases, especially at 200℃
A liquid polyester having a vapor pressure of less than l Q mmHg is selected. Specifically, after synthesis with liquid polyester, it may be purified by distillation under reduced pressure, or low boiling point reactants may be removed together with unreacted substances under reduced pressure.

The coloring agent for coloring a polyester fiber stock solution of the present invention can be produced using a conventional dispersing machine such as a three-roll mill, a ball mill, a sand mill, an attritor, a kneader, or a combination thereof.

In addition to pigments or dyes, the liquid colorant of the present invention may contain additives such as antistatic agents, ultraviolet absorbers, and antioxidants, depending on the purpose.

The liquid polytomoe stell of the present invention does not decompose or deteriorate even at the spinning temperature of polyester resin (270°C or higher), and because of its low viscosity, it contains pigments or dyes of 25% by weight for carbon blanks, 35% by weight for organic pigments, etc. For inorganic pigments, even if the content is 70% by weight, at room temperature or when kept warm (1
It has the desirable properties of exhibiting fluidity at temperatures below 50° C. and good compatibility with polyester resins. For this reason, the coloring agent for coloring polyester fiber stock solution according to the present invention is as follows.

1) Good dispersibility and high density coloring possible.

2) Good penetration into the screw during spinning and no phenomena such as thread breakage.

3) Good quantitative supply ability when blending colorants.

4) tI! There is almost no deterioration in the physical properties of LMk.

It has this feature.

Next, an example will be described.

Example 1 452 parts of adipic acid and 348 parts of 1,3-butylene glycol were charged into a reaction vessel equipped with a temperature needle, a stirrer, a nitrogen gas inlet tube, a temperature control device, a partial condenser, etc., and the reaction temperature was adjusted while flowing nitrogen gas. The temperature was gradually raised to 240°C, and the reaction was continued until the acid value reached 10. Next, remove the partial condenser from the reaction vessel.

Distillation was carried out under reduced pressure for 1 hour using 11 g of 50-60 mm, and the acid value was 2.5. A liquid polyester having a viscosity of 20 voids was obtained.

74 parts by weight of the above liquid polyester, 2.5 parts by weight of Macocyanine Blue (trade name Lionor Blue FG-7330, manufactured by Toyo Ink), carbon blank (trade name Sieben 4.20 dens).

(manufactured by Columbia Carbon) was kneaded in an attritor to obtain a liquid colorant with 1300 voids (measured at 25° C. using a B-type precision needle; the same applies to the following examples).

3 parts by weight of this colorant was added to a polyester resin (trade name: RE-500 manufactured by Toyobo Co., Ltd., Toyobo Co., Ltd.), and the mixture was spun to a yarn thickness of 10 denier using a spinning tester (Fuji Filter iii!l).

The yarn was drawn 3.3 times at 100° C. to obtain a 3-denier yarn.

The presence or absence of yarn breakage during spinning and drawing at a yarn thickness of 3 denier and the dispersibility of pigments or dyes in the resulting colored fibers were observed under a microscope, and the tensile strength (dry and wet) was measured. The results are shown in Table 1.

Example 2 65 parts by weight of the liquid polyester produced in Example 1, Anthraquinone Yellow (trade name: Fillester Yellow 2)
648A, Ciba Geigy N) 12 parts by weight, Perylene Red (trade name: Paliogen Resod -3911HD, BA
(manufactured by SF) and 7 parts by weight of carbon black (Mitsubishi Carbon MCF-88, manufactured by Mitsubishi Kasei) were kneaded using three rolls to obtain a brown liquid colorant with 6000 voids.

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

Example 3 423 parts of adipic acid, n
- 302 parts of bentanediol, 7 parts of diethylene glycol
Using 5 parts as a raw material, a liquid polyester having an acid value of 1.5° and a viscosity of 60 voids was obtained.

81.2 parts by weight of the above liquid polyester, 17.5 parts by weight of anthraquinone dye (Estophil Yellow S-50-L, Sandoz '15), anthraquinone dye (Estophil Blue 5-RLS).

Sandoz Co., Ltd.) 0.6 parts by weight and carbon blank (Mitsubishi Carbon 10, manufactured by Mitsubishi Kasei) 0.7 parts by weight were dispersed in a sand mill using glass beads to obtain an olive coloring agent with 480 voids.

Polyester resin 1o used in Example 1.

3.8 parts by weight of this colorant was added to the parts by weight, and the same operations and measurements as in Example 1 were performed. The results are shown in Table 1.

Example 4 97.5 parts by weight of commercially available adipic acid polyester (trade name: Adeka Sizer PN-150, manufactured by Adeka Argus),
52.5 parts by weight of titanium oxide (trade name: Fuji Titanium TA-6001, manufactured by Fuji Titanium) was milled using a magnetic ball mill.
A white colorant with 50 voids was obtained.

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

Example 5 Commercially available phthalic acid polyester (trade name Polycizer P)
-29. (manufactured by Dainippon Ink) 67.2 parts by weight, anthraquinone dye (trade name Kayaset Blue A-CR, Nippon Kayaku Layer) 26.2 parts by weight.

Perinone pigment (product name: Kayaseno Trend E-BG,
Nippon Kayaku i1i! 6.6 parts by weight were kneaded using three rolls to obtain a 7200 voids liquid colorant.

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

As is clear from Table 1, the polyester fibers using the colorants of the present invention had good dispersibility, and no coarse colored particles of 3 μm or more were observed.

Good results were shown with almost no deterioration in spinning, drawability, and physical properties.

Comparative Example 1 15 parts by weight of the carbon black used in Example 1 was mixed with 85 parts by weight of ethylene glycol using an attritor,
A liquid coloring agent of too boys was obtained.

When 4 parts by weight of this coloring agent was added to the polyester resin used in Example 1 and the same operations and measurements as in Example 1 were performed, this colored fiber had a 3 mez p J? Colored particles 1 and h were observed, and the dispersibility of the pigment was poor. Furthermore, thread breakage occurred during spinning and drawing.

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

When 3 parts by weight of this colorant was added to the polyester resin used in Example 1 and the same operations and measurements as in Example 1 were performed, colored particles of 3 μm or more were observed in this colored fiber, indicating that the dispersibility of the pigment was poor. It was defective. Furthermore, yarn breakage occurred during spinning and drawing.

Table 1

Claims (1)

[Claims] 1. Consisting of 100 parts by weight of pigment or dye and 30 to 2,000 parts by weight of liquid polyester, to, ooo at room temperature.
A liquid coloring agent for polyester fiber base material, which is characterized by being a liquid with a liquid content of less than a void. 2. The liquid coloring agent for polyester fiber base material according to claim 1, wherein the constituent components of the liquid polyester are mainly obtained by reacting a dibasic organic acid and a dihydric alcohol. 3. The liquid coloring agent for polyester fiber base material according to claim 2, wherein the dibasic organic acid is an aliphatic dicarboxylic acid. 4. The colorant paste for polyester fiber base material according to claim 2, wherein the dibasic organic acid is an aromatic dicarboxylic acid. 5. Liquid polyester vapor rM O at 200°C
The liquid coloring agent for polyester fiber base material according to claims 1 to 4, which is a liquid polyester having a weight of 11 g or less.