JPH07100883B2 - Black polyester fiber and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a black polyester fiber and a method for producing the same.

(Prior Art) Since polyester fibers have excellent heat resistance and light resistance, they are widely used not only for clothing but also for industrial materials. Recently, raw polyester fibers have begun to be used for clothing, sundries and industrial applications, and research and development of colorants including pigments and dyes have been advanced.

The addition of a pigment to the polyester dyeing layer is described in, for example, Japanese Patent Publication No. 56-45505, and it is preferable to use a dispersant in order to improve the dispersibility of the pigment.
No. 742, JP-A-56-16546, JP-A-56-36541 and the like.

On the other hand, as a synthetic resin colorant, the following structural formula 1- (p-methylphenylamino) -4-hydroxyanthraquinone (CI60725) (edited by the Society of Synthetic Organic Chemistry, "Dye Handbook", 3rd edition (Sho 53-8-20) Maruzen, P86
1) and 1-phenylamino-4-hydroxyanthraquinone are known.

On the other hand, in order to obtain a black-colored synthetic fiber, it is necessary to blend a dye or pigment with carbon black.
-40619, Japanese Patent Publication No. 56-47204 and Japanese Patent Publication No. 58-304
No. 14 bulletin, etc.

(Problems to be Solved by the Invention) When a pigment is used as a colorant, it requires several times as much usage fee as a dye, and it is inferior in color developability and it is difficult to obtain a clear color.

Further, a resin molded product colored with the colorant represented by the above structural formula has a problem in bleeding resistance, and is particularly difficult to use for polyester fibers.

On the other hand, it is difficult to obtain a deep black color even if a pigment is added together with carbon black, and when the above dye is blended, the heat resistance is poor and the uniform coloring property is poor.

An object of the present invention is to provide a black polyester fiber having a clear black color and luster, and having excellent bleeding resistance with deepness and heat resistance and weather resistance, and another object is to provide such excellent properties. Another object of the present invention is to provide a method for industrially easily producing the black polyester fiber having the black polyester fiber.

(Means for Solving the Problems) The present invention has the general formula [I] (In the formula, X represents —CONH ₂ or —NHCOR, and R represents a hydrogen atom or an alkyl group.) A black polyester fiber containing a colorant and carbon black, According to the method of the present invention, when melt-spinning polyester, (In the formula, X represents —CONH ₂ or —NHCOR, and R represents a hydrogen atom or an alkyl group.) And carbon black are incorporated before spinning.

In the resin colorant represented by the above general formula [I] of the present invention, the alkyl group represented by R is a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group. , Hexyl group, heptyl group, octyl group, stearyl group and the like.

The colorant for resin represented by the above general formula [I] used in the present invention can be produced, for example, by the following method.

That is, the following structural formula [II] And quinizarin represented by the following structural formula [III] A mixture of leucoquinizarin represented by the following general formula [IV] It can be produced by reacting an amine represented by the formula (wherein X is the same as defined above) in the presence of boric acid in 95% ethanol water at a temperature of 70 to 80 ° C.

The black polyester fiber of the present invention is usually 0.002 to 1.5% by weight, preferably 0.005 to 1.2% by weight of the colorant in the polyester.
Add 5% by weight.

Carbon black is usually added to polyester in an amount of 0.005 to 3% by weight, preferably 0.01 to 2.5% by weight.

In the present invention, in addition to the above colorant and carbon black, azo-based, phthalocyanine-based, anthraquinone-based, dioxazine-based, perylene-perinone-based organic pigments and titanium oxide, iron oxide, ultramarine blue, carbon black and the like are generally used for polyester. Pigments, oil-soluble or disperse dyes such as azo-based, anthraquinone-based, perinone-based, and heterocyclic-based dyes, and these pigments and dyes may be used in combination.

At least 85% by weight of the polyester applied to the present invention is made of polyethylene terephthalate, and aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid as dicarboxylic acids other than terephthalic acid, oxalic acid, succinic acid, glutaric acid, and adipine. Acids, aliphatic dicarboxylic acids such as azelaic acid and sebacic acid, and glycols other than ethylene glycol such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, pentamethylene glycol, neopentyl glycol, hexamethylene One kind or two or more kinds of glycols and the like may be copolymerized, and polyethylene terephthalate is particularly preferable.

The colorant and carbon black applied to the present invention may be added to polyester at any stage before spinning, but it is preferable to rapidly knead before spinning. In this case, the colorant and carbon black are previously dispersed and mixed in the liquid aliphatic polyester.

The fat-immediate polyester is obtained by polycondensing an aliphatic dicarboxylic acid and an aliphatic glycol, for example, adipic acid, sebacic acid, azelaic acid, an aliphatic dicarboxylic acid such as glutaric acid, and ethylene glycol, propylene. Polycondensation reaction with glycols such as glycol, petylene glycol, pentyl glycol, hexyl glycol, neopentyl glycol and diethylene glycol.

In addition to these, the aliphatic polyester applicable to the present invention is preferably one in which at least one end is blocked with a monohydric alcohol, and examples of the monohydric alcohol include n-octyl alcohol, 2-ethylhexyl alcohol, and n-nonyl alcohol. , And aliphatic alcohols such as n-decyl alcohol.

The colorant and carbon black are usually used after being dispersed in an aliphatic polyester in an amount of about 1 to 35% by weight.

In order to add the dispersion liquid at the time of spinning, for example, the polyester introduced from the polymer introduction tube is provided with an association portion, and the dispersion liquid in which the colorant measured by the plunger pump or the gear pump is dispersed in the liquid aliphatic polyester is injected. .

The polymer flow path after the association part is, for example, in the order of the first kneading part-gear pump-second kneading part-spin beam (third kneading part) -spin pack, and the allowable pressure loss in the kneading part is made as large as possible before use. The number of known static kneading elements can be increased. Examples of the static kneading element include a static mixer (manufactured by Kenix Co., Ltd.), a ROSS-LSG mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an SM mixer (manufactured by Zulsar Co.), and a BKM mixer (manufactured by Zulsar Co.). The associating part, the first kneading part, and the gear pump can be incorporated into a wear plate for joining the gear pumps to improve the accuracy of measuring the additive and to make the apparatus compact.

Ordinary fluorescent whitening agents, matting agents, gloss imparting agents, foaming agents, antistatic agents, heat and light stabilizers, etc. may be added to the black polyester fiber of the present invention.

(Effects of the Invention) The colored polyester fiber of the present invention has a clear black color and gloss, and also has a depth and is excellent in bleeding resistance and heat and light resistance, and is suitable for clothing, sundries and industrial use. It is widely used, and the method of the present invention is industrially very easy, and can be easily produced by adding some equipment.

Example 1 The following structural formula was added to 60 parts by weight of an aliphatic polyester (acid value 1.0, viscosity 25 poise) composed of adipic acid and 1,3-butylene glycol. 15 parts by weight of dye, carbon black (Mitsubishi Carbon 10,
25 parts by weight of Mitsubishi Kasei Co., Ltd. was kneaded with a three-roll mill to obtain a black colorant.

5 parts by weight of the above liquid colorant was added to 100 parts by weight of polyethylene terephthalate having a number average molecular weight of 21,000, and a static mixer (manufactured by Konick) 18 elements, and a BKM mixer (manufactured by Zulsar) 4 for mixing and dispersing after addition. The element was used in the polymer channel.

The added polymer is passed through the pack and spun and stretched in the usual way for 3d.
A yarn having a single yarn fineness of was obtained. When the color of the yarn was measured with a Kurabo color measuring machine, Lab was 21.89 / 0.12 / -1.48, which was deep and was glossy black.

Example 2 In 60 parts by weight of an aliphatic polyester composed of adipic acid and diethylene glycol (acid value 0.8, viscosity at room temperature 75 poise), the following structural formula was added. 15 parts by weight of dye, carbon black (trade name Raven 42
25 parts by weight of Dense Columbia Carbon) was kneaded with a three-roll mill to obtain a black colorant.

5 parts by weight of the above colorant was added to 100 parts by weight of polyethylene terephthalate having a number average molecular weight of 20,000, rapid kneading was performed using a static kneading element as in Example 1, and spinning and drawing were performed by a usual method to obtain a single yarn fineness of 3d. Black thread was obtained.

When the color of the yarn was measured, it was Lab22.20 / 0.22 / -1.51 and the color was deep glossy black.

Example 3 Aliphatic polyester consisting of adipic acid, propylene glycol and 2-ethylhexyl alcohol (acid value of 0.
7, viscosity 80 poise) 50 parts by weight of the following structural formula 20 parts by weight of dye, carbon black (trade name Raven 42
0 Dense, made of Columbia Carbon) was kneaded with 3 rolls to obtain a blue colorant.

The colorant was added to polyester in an amount of 5.0 parts by weight in the same manner as in Example 1 to obtain a glossy black yarn having a single yarn fineness of 3d.

When a knit was made from the above-mentioned yarn and the wear resistance according to JIS method for clothing was checked and the fastness to washing by washing was checked.
It was excellent at 5th grade.

Comparative Example 1 To 75 parts by weight of an aliphatic polyester (acid value 1.0, viscosity 25 poise) consisting of adipic acid and 1,3-butylene glycol,
Twenty-five parts by weight of carbon black (Mitsubishi Carbon 10, manufactured by Mitsubishi Kasei) was kneaded with three rolls to obtain a black colorant.

5% of the above coloring agent was added in the same manner as in Example 1, and the single yarn fineness was 3d.
Got the thread. The measured color Lab is 23.34 / -0.03 / -1.20 and L
The value was high, and when compared with the yarn of Example 1, it was a black color with poor quality.

Comparative Example 2 75 parts by weight of an aliphatic polyester composed of adipic acid and diethylene glycol (acid value 0.8, viscosity at room temperature: 75 poise) was added to carbon black (trade name Raven 420 dense,
Twenty-five parts by weight of Colombia Carbon) was kneaded with three rolls to obtain a black colorant.

5% of the above coloring agent was added as in Example 2, and the single yarn fineness was 3d.
Got the thread. When the color was measured, Lab had a high L value of 24.29 / 0.09 / -1.54, and compared with the yarn of Example 2, it was a poor quality black.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-50-151955 (JP, A) JP-A-61-34053 (JP, A) JP-B 44-12850 (JP, B1) JP-B 47- 13385 (JP, B1) JP-B-45-0709 (JP, B1)

Claims (7)

[Claims] 1. A general formula [I] (In the formula, X represents —CONH ₂ or —NHCOR, and R represents a hydrogen atom or an alkyl group.) A black polyester fiber containing a colorant and carbon black. 2. The fiber according to claim 1, wherein the polyester is polyethylene terephthalate. 3. When melt-spinning polyester, the compound of general formula [I] (In the formula, X represents -CONH ₂ or -NHCOR and R represents a hydrogen atom or an alkyl group.) A black polyester fiber characterized by including carbon black before spinning and a colorant represented by the formula Manufacturing method. 4. The method according to claim 3, wherein the polyester is polyethylene terephthalate. 5. The method according to claim 3, wherein the colorant is dispersed and blended in an aliphatic polyester. 6. The method according to claim 5, wherein the fatty acid polyester has at least one end blocked with a monohydric alcohol. 7. The method according to claim 3, wherein the compounding is carried out by rapid kneading using a static kneading element.