JPH04300977A - Liquid colorinig agent for molded acrylic resin - Google Patents

Abstract

PURPOSE:To provide a liquid coloring agent having an excellent coloring property on the coloring of a raw material solution used for producing acrylic fibers, not affecting the spinning property of the raw material solution and not causing the aggregation of the pigment during the storage thereof. CONSTITUTION:A liquid coloring agent for molded acrylic resins comprises 100 pts.wt. of polyoxyethylene.polyoxypropylene block copolymer preferably having a number-average mol.wt. of 1000-8000 and 0.5-150 pts.wt. of a pigment.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to a liquid colorant for molded acrylic resins. More specifically, the present invention relates to a liquid coloring agent for coloring acrylic fibers spun from a dimethylcarbamyl solution of an acrylic resin.

0002

[Prior art] Acrylic fibers have excellent dyeing clarity, light resistance,
In terms of bulkiness, it has superior properties not found in polyamide and polyester fibers, which are general-purpose clothing fibers, so it is widely used for clothing and interior decoration such as curtains and mats. However, in applications such as curtains and parasols that require light resistance, those colored using basic dyes, disperse dyes, and acid dyes have the disadvantage of poor light resistance. In order to improve the above-mentioned drawbacks, a method is known in which a pigment solution containing an acrylonitrile polymer or a surface-treated pigment is dispersed in a solvent, filtered, and then added to the dope (for example, JP-A-61 -6701
Publication No. 4). However, although pigments added to the spinning stock solution can be spun without coarse particles immediately after dispersion, depending on the type of pigment, they aggregate and settle within a few hours or days, and the aggregates clog the filter of the spinning nozzle, causing pressure This causes problems during spinning, such as the inability to spin and yarn breakage.

In order to improve pigment dispersion stability in acrylonitrile polymer solutions and solvents, ball mills, sand mills,
Attempts have been made to use media dispersion methods such as attritor, mechanical dispersion methods such as three-roll dispersion, and methods using additives such as activators, pigment surface treatment agents, and liquid resins, but the above drawbacks have not been resolved.

OBJECTS OF THE INVENTION The present invention provides a liquid coloring agent that has excellent coloring properties when coloring acrylic fibers with a stock solution and does not adversely affect spinnability. The present invention also provides a liquid colorant that is free from pigment agglomeration during storage.

0004

[Means for Solving the Problems] That is, the present invention provides polyoxyethylene with a number average molecular weight of 1000 to 8000.
This is a liquid coloring agent for molded acrylic resin, consisting of 100 parts by weight of a polyoxypropylene block polymer and 0.5 to 150 parts by weight of a pigment.

The number average molecular weight of the polyoxyethylene/polyoxypropylene block polymer which is the liquid dispersion medium of the present invention is 1000 to 8000, preferably 100.
0 to 5,000, and if the molecular weight is too large, the viscosity will become high even in liquid form, which is not preferable.

Pigments of the present invention include, for example, inorganic pigments such as titanium oxide white, carbon black, and transparent red iron oxide, and organic pigments such as azo, condensed azo, perylene, anthraquinone, isoindolinone, and phthalocyanine. , oil-soluble dyes such as perinone-based, anthraquinone-based, and quinophthalone-based dyes, and disperse dyes. Further, extender pigments such as barium sulfate, silica, talc, kaolin, and clay can also be used. In addition to the above pigments, dyes may be used in combination.

[0007] The liquid colorant of the present invention contains 0.5 to 150 parts by weight of the pigment per 100 parts by weight of the liquid dispersion medium, and if the amount of pigment exceeds 150 parts by weight, the viscosity of the liquid colorant increases. As a result, the supply performance by the quantitative feeder deteriorates, which is not preferable. In order to obtain the liquid colorant of the present invention, a predetermined amount of pigment and a liquid dispersion medium are blended and mixed using a mixer such as a homo mixer or a disper mill, and then kneaded using a general kneader such as a 3-roll or sand mill. to disperse the pigment. The viscosity of the obtained liquid colorant is preferably 10 to 300 poise at 25°C (BM type rotational viscosity, rotor No. 4, 20 rpm). The liquid colorant of the present invention can be used for acrylic fibers spun from a dimethylcarbamyl solution of an acrylic resin. The amount of liquid colorant added is 0.00 parts per 100 parts of solid content of the acrylic resin.
1 to 15 parts by weight is preferred. Examples will be explained below. All parts and percentages in the examples are based on weight.

[0008]

[Example 1] 40 parts of Fine Ferri Red-35 (transparent red iron oxide manufactured by Sakai Chemical Co., Ltd.) and 60 parts of Pluronic L-64 (polyoxyethylene/polyoxypropylene block polymer manufactured by Asahi Denka, molecular weight = 2000) were placed in a disper mill. After mixing and stirring, use three rolls (rotation speed 350 rpm).
m) by two passes to obtain a liquid colorant of 58 poise/25°C. 2.0 parts of this liquid colorant was dissolved in 100 parts of an acrylonitrile polymer solution (solid content 20%, DMF solvent 80%) using a volumetric metering feeder, and stretched in two stages using a wet spinning machine. Acrylic fibers of 1.5 denier were obtained. The results of the short fibers obtained are shown in Table 1.
The fiber yarn had good clarity and color development, and could be used satisfactorily for clothing and interior decoration. In the table, the colorimetric values L*, a*, b* are "KUR" manufactured by Kurashiki Boseki Co., Ltd.
CI
Measured under the conditions of E1970, D light source, and 1 g of fiber. Level dyeability, spinnability and stretchability were evaluated on a four-level scale (◎: extremely good, ○: good, △: fair, ×: poor).

[0009]

[Example 2] Pluronic L-64 to Pluronic L-64
A liquid coloring agent having a viscosity of 95 poise/25° C. was obtained in the same manner as in Example 1 except that 84 (molecular weight = 3000) was used in place of 6. Acrylic nitrile polymer solution (solid content 20%, DM
0.7 part of this liquid colorant was dissolved in 100 parts of F solvent (80%) using a volumetric quantitative feeder, and drawn in two stages using a wet spinning machine to obtain a 1.5 denier acrylic fiber. Table 1 shows the results of the short fibers obtained.

0010

[Example 3] A liquid colorant having a viscosity of 133 voids/25° C. was obtained in the same manner as in Example 1 using 20 parts of Mitsubishi Carbon MA-100 (manufactured by Mitsubishi Kasei Corporation) and 480 parts of Pluronic L-6. Acrylonitrile polymer solution (solid content 20%)
10 parts of this liquid colorant were dissolved in 90 parts of DMF solvent (80%) using a volumetric metering feeder, and drawn in two stages using a wet spinning machine to obtain acrylic fibers of 1.5 denier. Table 1 shows the results of the short fibers obtained.

[0011]

[Comparative Example 1] D containing 5% acrylonitrile polymer
Mitsubishi Carbon MA-100 10 in 90 parts of MF solution
After stirring in a dissolver for 10 minutes, the mixture was passed through a 15-liter horizontal sand mill three times to obtain a liquid colorant with coarse particles of 25 μm or less and a viscosity of 2.8 poise/25° C. Immediately after filtering this liquid colorant with a 5μ cartridge filter, 10 parts of this liquid colorant was added and dissolved in 100 parts of the acrylonitrile solution used in Example 1 using a quantitative feeder, and the same procedure as in Example 1 was carried out. This was spun to obtain 1.5 denier acrylic fiber. Table 1 shows the results of the short fibers obtained.

0012

[Comparative Example 2] The colored liquid after filtration obtained in Comparative Example 1 was left at room temperature for one day and night, and an attempt was made to spin it under the same conditions as Comparative Example 1. The nozzle pressure increased and spinning became impossible. After thoroughly stirring this liquid colorant with a dissolver, spinning was attempted again, but the result was the same.

Table 1 Pigment content L*
a* b* Level dyeing property Spinnability Stretchability Example 1 0.80
42.10 24.66 9.18
◎ ○ ○Example 2 0.
80 40.96 24.98
7.89 ◎ ○ ○Example 3 2.0 13.98 0
．． 11 -0.06 ◎ ◎
◎Comparative example 1 1.0 16.
88 -0.09 -0.48 ◎
○ △Comparative example 2 1.0
── ── ── ○
× ×

[0014]

[Effects of the Invention] The liquid colorant for molded acrylic resin of the present invention uses a liquid dispersion medium with excellent pigment dispersibility, so it has excellent pigment dispersibility and dispersion stability. Therefore, it can be used as a coloring agent for base material, especially added to a dimethylcarbamyl-based solution of an acrylic resin, and a resin molded article with excellent coloring power can be obtained. Furthermore, when used as a coloring agent for acrylic fibers, it is possible to produce acrylic fibers with excellent appearance without adversely affecting spinnability, drawability, etc.

Claims (1)

[Claims] 1. A liquid coloring agent for molded acrylic resin, comprising 100 parts by weight of a polyoxyethylene/polyoxypropylene block polymer having a number average molecular weight of 1,000 to 8,000 and 0.5 to 150 parts by weight of a pigment.