JPS6342915A - Black-colored polyester fiber and its production - Google Patents

Abstract

PURPOSE:To obtain the title fiber having not only bright black, gloss, with depth as well but also high bleeding, heat and light resistances by adding a specific colorant and carbon black before spinning at the time of melt-spinning polyester. CONSTITUTION:When a polyester, preferably polyethylene terephthalate is melt- spun, a colorant of formula I [X is -CONH2, -NHCOR (R is H, alkyl)] and carbon black are added to the polyester, preferably in amounts of 0.005-1.25wt% and 0.01-2.5wt%, respectively. The colorant of formula I is prepared by, e.g., reaction of a mixture of quinizarin of formula II with leucoquinizarin of formula III with an amine of formula IV in the presence of boric acid in 95% ethanol-water at 70-80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a black polyester fiber and a method for producing the same.

(Prior Art) Polyester & 111 fibers have excellent heat resistance and light resistance, so they are widely used not only for clothing but also for industrial materials. Recently, spun-dyed polyester fibers have been used for clothing,
Research and development is progressing on colorants, including pigments and dyes, which have begun to be used in miscellaneous goods and industrial applications.

The addition of pigments to the doped polyester is described in, for example, Japanese Patent Publication No. 56-45505, and the use of dispersants to improve the dispersibility of pigments is described in Japanese Patent Application Laid-open No. 55-152742, Japanese Patent Publication No. 56-16546
JP-A-56-86541, etc.

On the other hand, a synthetic lid fat-enveloping colorant is 1-(p-methylphenylamino)-4-hydroxyanthraquinone (C, 1,60725), which is represented by the following structural formula: Third printing (August 20, 1982)
) Maruzen, P861) and 1-phenylamino-4-hydroxyanthraquinone are known.

On the other hand, in order to obtain synthetic fibers colored black, a dye or pigment was blended with carbon black.
It is described in Japanese Patent Publication No. 5-40619, Japanese Patent Publication No. 56-47204, Japanese Patent Publication No. 58-80414, etc.

(Problems to be Solved by the Invention) When a pigment is used as a coloring agent, not only does it require several times the amount used compared to one dye, but it also has poor coloring properties, making it difficult to obtain clear colors. Furthermore, the resin molded product represented by the above structural formula and colored with a colorant has a problem in bleed resistance, and is particularly difficult to use for polyester fibers.

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

The object of the present invention is to provide a black polyester fiber that has a clear black color and gloss, has a deep color, has excellent bleed resistance, and has heat and weather resistance.Another object of the present invention is to provide a black polyester fiber that has such excellent properties. The object of the present invention is to provide a method for industrially easily manufacturing black polyester fiber having a black polyester fiber having a black color.

(Means for Solving the Problems) The present invention provides a colored compound represented by the general formula [I] OH (wherein, X represents t-CONH2 or -NHCOR, and R represents a hydrogen atom or an alkyl group). The method of the present invention relates to a black polyester fiber made by blending an agent and carbon black, and the method of the present invention is based on the general formula [I] OOH (wherein, X 1.t-CONH2?: 1 .t −N
In HCOR, R represents a hydrogen atom or an alkyl group. ) and carbon black are blended together before spinning.

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

The resin colorant represented by the general formula [1] used in the present invention can be produced, for example, by the following method.

That is, a mixture of quinizarin represented by the following +g formula ■1 0H and leucoquinizarin represented by the following purchasing formula HOH, and amines represented by the following general formula (wherein, X is the same as defined above). 70-80 in 95% ethanol water in the presence of boric acid.
It can be produced by reacting at a temperature of 1.5°C.

The black polyester fiber of the present invention contains the colorant in the polyester in an amount of usually 0.002 to 1.5% by weight, preferably 0.
．． 005 to 1.25% by weight.

Carbon black is usually contained in polyester from 0.005 to
It is blended in an amount of 8% by weight, preferably 0.01 to 2.5% by weight.

In addition to the colorant and carbon black, the present invention also includes organic pigments such as azo, phthalocyanine, anthraquinone, dioxazine, and perylene/perinone, as well as titanium oxide, iron oxide, ultramarine, and carbon black, which are commonly used in polyester. Pigments, oil-soluble or dispersed dyes such as azo, anthraquinone, perinone, and heterocyclic dyes, and combinations of these pigments and dyes can be used.

The polyester applied in the present invention is at least 85% by weight
is made of polyethylene terephthalate, and dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid, oxalic acid, conoholic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. Aliphatic dicarboxylic acids, and glycols other than ethylene glycol such as diethylene glycol, triethylene glycol, polyethylene glycol,
Propylene glycol, polypropylene glycol, tetramethylene glycol, pentamethylene glycol,
One or more types of neopentyl glycol, hexamethylene glycol, etc. may be copolymerized, but polyethylene terephthalate is particularly preferred.

The colorant and carbon black applied to the present invention may be added to the polyester at any stage before spinning, but it is preferable to rapidly knead the polyester before spinning.

In this case, the colorant and carbon black are dispersed in advance in liquid aliphatic polyester and blended.

Aliphatic polyesters are obtained by condensation polymerization of aliphatic dicarboxylic acids and aliphatic glycols, such as aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and glutaric acid, and ethylene glycol and propylene. It is the result of a polycondensation reaction with glycols such as glycol, butylene glycol, pentyl glycol, hexyl glycol, neopentyl glycol, and diethylene glycol.

In addition to these aliphatic polyesters, the aliphatic polyester applicable to the present invention is preferably one in which at least 10,000 ends are blocked with m alcohols, and examples of the -hydric alcohol include n-octyl alcohol, 2-ethylhexyl alcohol, n-nonyl Examples include aliphatic alcohols such as alcohol and n-decyl alcohol.

The colorant and carbon black are usually dispersed in an aliphatic polyester in an amount of about 1 to 85% by weight.

To add a dispersion liquid during spinning, for example, a meeting part is provided in the polyester of the round polymer introduction tube, and a dispersion liquid in which a measured amount of colorant is dispersed in liquid aliphatic polyester using a plunger pump or gear pump is added. inject.

The polymer flow path after the meeting part is arranged in the order of, for example, the first kneading part, the gap pump, the second kneading part, the spin beam (third kneading part), and the spinning 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. Static mixer (manufactured by Koenix Co., Ltd.), RO3S-LSG mixer (manufactured by Tokushu Kikako Co., Ltd.), and 8M mixer (manufactured by Sulther Co., Ltd.) are used as static kneading elements.
, BKM mixer (manufactured by Zurther), etc. The meeting section, the first kneading section, and the gear pump can be incorporated into a wear plate for connecting the gear pump, thereby increasing the accuracy of measuring the additive and making the device more compact.

1 black polyester fiber of the present invention, a conventional fluorescent brightener;
Matting agents, brightening agents, blowing agents, controllability agents, heat and light stabilizers, etc. may be added.

(Effect of the invention) The colored polyester m-fiber of the present invention has a clear black color and luster, has depth, has excellent bleed resistance, and has heat and light resistance, and can be used for clothing, miscellaneous goods, and industrial purposes. Moreover, the method of the present invention is industrially very easy and can be easily manufactured by adding some equipment (41).

Example 1 Aliphatic polyester consisting of adipic acid and 1,3-butylene glycol (acid value 1.0, viscosity 25 voids) 60
15 parts by weight of a dye with the following structural formula, carbon black (Mitsubishi Carbon 1)
0, manufactured by Mitsubishi Kasei) were mixed in three rolls,
A black colorant was obtained.

5 parts by weight of the above liquid colorant was added to 100 parts by weight of polyethylene terephthalate with a number average molecular weight of 21,000, and after addition, a static mixer was used to mix and disperse.
18 elements (manufactured by K-EX Corporation) and 4 elements of a BKM mixer (manufactured by Zurther Corporation) were used in the polymer flow path.

The added polymer is passed through a pack and spun and stretched in the usual manner.8
A yarn with a single yarn fineness of d was obtained. When the color of the yarn was measured using a Kurabo color measuring machine, the Lab value was 21.8910, 12/-1,
It had a floor length of 48 and was a glossy black color.

Example 2 Aliphatic polyester consisting of adipic acid and diethylene glycol (acid value 0.8, viscosity at room temperature 75 voids) 6
15 parts by weight of a dye having the following structural formula and 25 parts by weight of carbon black (trade name Sieben 420 Dense, manufactured by Columbia Carbon) were kneaded into the zero-fold nail part using eight rolls to obtain a black colorant.

5 parts by weight of L coloring agent was added to 100 parts by weight of polyethylene terephthalate having a number average molecular weight of 20,000, and rapid kneading was performed using a static kneading element in the same manner as in Example 1.
Spinning and drawing was carried out using a conventional method to obtain a black yarn with a single fiber fineness of 8d.

When the color of the yarn was measured, L a b 22.20 / 0.2
2/-1.51, and the color was glossy black.

Example 8 Aliphatic polyester consisting of adipic acid, propylene glycol and 2-ethylhexyl alcohol (acid value 0.
7. Viscosity: 80 poise) Add 20 parts by weight of the dye of the following structural formula to the 50-layer claw part, and add 3 parts of carbon black (trade name Sieben 420 Dense, manufactured by Columbia Carbon) to the 80-layer claw part.
The mixture was kneaded using a main roll to obtain a blue colorant.

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

A knit was made from the yarn described above and tested for friction, weather resistance and washing fastness according to JIS method for clothing use.4
Excellent at grade 5.

Comparative Example 1 8 bottles of 25 parts by weight of carbon black (Mitsubishi Carbon 10, manufactured by Mitsubishi Kasei) were added to 75 parts by weight of aliphatic polyester (acid value 1.0, viscosity 25 voids) consisting of adipic acid and 1,3 butylene glycol. The mixture was kneaded with a roll to obtain a black colorant.

and coloring agent were added at 5% as in Example 1, and the single yarn fineness was 8.
A yarn of d was obtained. When I measured the color, Lab was 28.84/-0,
The L value was high at 03/-1.20 (compared to the yarn of Example 1, the black color was poor in quality).

Comparative Example 2 Aliphatic polyester consisting of adipic acid and diethylene glycol (acid value 0.8, viscosity at room temperature 75 poise) 7
5 parts by weight, carbon black (trade name: Shihen 420)
Dense (manufactured by Columbia Carbon)) was kneaded with 8 rolls to obtain a black colorant.

5% of the above coloring agent was added as in Example 2, and the single yarn fineness was 3.
A yarn of d was obtained. Color measured) M L a b is 24.29
The L value was high at 10.09/-1.54 (compared to the yarn of Example 2, the black color was poor in quality).

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Tachihide Dosoku -,,,,! , Town 1+
7. ,:,,4

Claims (7)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the formula, X represents -CONH_2 or -NHCOR, and R represents a hydrogen atom or an alkyl group.) A black polyester fiber prepared by blending a colorant represented by the following with carbon black. (2) The fiber according to claim 1, wherein the polyester is polyethylene terephthalate. (3) When melt-spinning polyester, the general formula [
I 〕 ▲There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・〔 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 blending a coloring agent represented by the following with carbon black before spinning. Production 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 into an aliphatic polyester. (6) Claim 5 in which the fatty acid polyester has at least one end blocked with a monohydric alcohol.
The method described in section. (7) The method according to claim 3, wherein the blending is carried out by rapid kneading using a static kneading element.