JPH04281013A - Liquid colorant for spun-dyed polyamide - Google Patents

Abstract

PURPOSE:To obtain a liquid colorant for spun-dyed polyamide, having excellent compatibility with polyamide, dispersibility with dyes and pigments and physical properties sufficiently standing high-temperature spinning and various kinds of moldings and processing. CONSTITUTION:A modified alpha-olefinic oligomer is mixed with dye or pigment and is made to have <=10,000 poise viscosity at normal temperature to give the objective liquid colorant for spun-dyed polyimide.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid colorant for use in polyamide raw materials, and more particularly to a liquid colorant using a modified α-olefin oligomer as a dispersion medium for dyes and pigments.

0002

BACKGROUND OF THE INVENTION Due to its excellent physical and chemical properties, polyamide is widely used in various industrial fields such as fibers, monofilaments, molded products, and films. Conventionally, various techniques are known as methods for coloring polyamide with a stock solution. For example, well-known methods include adding pigments or dyes during the polyamide polymerization reaction, masterbatch methods in which pigments or dyes are dispersed in polyamide resin at high concentrations, and dry color methods in which pigments or dyes are dispersed with metallic soap, wax, etc. ing.

0003

[Problems to be Solved by the Invention] In the above method of adding pigments or dyes during the polyamide polymerization reaction, the reaction is at high temperatures and takes a long time, so most dyes and organic pigments that have poor heat resistance cannot be used. The use of pigments such as oxide-based inorganic pigments and carbon black is limited, and the reaction vessel is colored and contaminated, so unless a dedicated reaction vessel is installed, cleaning the vessel when changing colors is required. The disadvantages were that it required a lot of time and effort, and it was expensive. Furthermore, in the masterbatch method, due to the heat history during the kneading of pigments or dyes and the drying process of the masterbatch, there are defects such as a decrease in yarn physical properties such as tensile strength of polyamide fiber obtained by melt spinning, or the occurrence of agglomerates. There is. Furthermore, in the dry coloring method, in which pigments or dyes processed into powder using a dispersing agent are directly blended into polyamide pellets, etc., the pigments and dyes are finely powdered, which causes them to scatter and contaminate the workplace, causing problems when changing colors. It took a lot of time to clean the mixer, which was not desirable. In place of the above-mentioned method, liquid colorants have recently been used in which pigments and dyes are kneaded in a liquid vehicle at room temperature. This method uses a gear pump, plunger pump, etc. to supply a fixed amount of coloring agent to polyamide in a molten state (for example, JP-A-63-9
(No. 2717) However, polyamide is an extremely polar resin and has poor compatibility with the liquid colorant vehicle, and if the vehicle has poor heat resistance, problems such as yarn breakage and white smoke generation occur during spinning. At present, a satisfactory liquid colorant that can sufficiently avoid these problems has not been developed. In view of the above, the present inventors have conducted various studies on vehicles that are dispersion media for liquid colorants, and have found that a liquid colorant that uses a modified α-olefin oligomer as a dispersion medium for pigments or dyes is compatible with polyamide. The present invention was completed based on the finding that it has good solubility and has physical properties that can sufficiently withstand spinning at high temperatures and various molding processes.

0004

[Means for Solving the Problems] That is, the present invention blends a dye or a pigment into a modified α-olefin oligomer,
This is a liquid coloring agent for polyamide base material, which is characterized by having a viscosity of 10,000 poise or less at room temperature. The present invention will be explained in detail below.

Examples of the pigments or dyes used in the present invention include azo pigments, anthraquinone pigments, perylene, perinone pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, phthalocyanine pigments, pyrocholine pigments, and fluorobin pigments. organic pigments such as pigments, yellow lead, cobalt blue, red iron, titanium dioxide,
Examples include inorganic pigments such as ultramarine, carbon black, and zinc oxide, azo dyes, anthraquinone dyes, perylene, and perinone dyes. The above pigments or dyes may be used alone or in combination of two or more. It is also possible to use pigments and dyes in combination.

Next, the modified α-olefin oligomer used in the present invention is an α-olefin oligomer grafted with a carbonyl group-containing monomer or an ethylene/α-olefin cooligomer. α− above
The olefin oligomer is composed of α-olefin having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and has a number average molecular weight of about 300 to 2,000, preferably 6
00 to 2,000, and the kinematic viscosity at 100°C is 3
It is 0 to 300 cSt.

The above ethylene/α-olefin cooligomer has an ethylene content of 30 to 80% by weight and an α-olefin content of 3 to 12 carbon atoms of 70 to 20% by weight.
and the number average molecular weight is 500 to 9,000, 100°C
The kinematic viscosity at is 50 to 48,000 cSt. The modified α-olefin oligomer used in the present invention is the above-mentioned α-olefin oligomer or ethylene α-olefin oligomer.
- 0.2 to 50% by weight of carbonyl group-containing monomer based on the olefin cooligomer, preferably 0.2 to 30% by weight
% by weight grafted.

Examples of the carbonyl group-containing monomers include monobasic acids such as acrylic acid, methacrylic acid, and oleic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. dibasic acids, acid anhydrides such as maleic acid, itaconic acid, and 5-norbornene-2,3-dicarboxylic acid, and esters, half esters, amides, and imides thereof. Among the above carbonyl group-containing monomers, maleic acid and maleic anhydride are particularly preferably used.

In the present invention, the above modified α-olefin oligomers or modified ethylene/α-olefin co-oligomers may be used alone or in combination. The graft reaction is usually carried out by adding a carbonyl group-containing monomer to an α-olefin oligomer or an ethylene/α-olefin co-oligomer in the presence of a radical initiator.

Mineral oil, vegetable oil, liquid polybutene, etc. can be further added to the modified α-olefin oligomer used in the present invention. Since the liquid colorant of the present invention is continuously supplied using an automatic measuring machine or the like during use, it is preferable that the colorant exhibits fluidity at room temperature or when kept warm, and for this purpose, it must be 10,000 poise or less at room temperature. . Therefore, the viscosity of the modified α-olefin oligomer must be 10,000 poise or less, but the modified α-olefin oligomer used in the present invention has an extremely high viscosity even when 30% by weight of pigment is added. 2,000 poise or less, preferably 1,000 poise at room temperature.
Poise or less is used.

[0011] As a dispersion medium for pigments, JP-A-60-456
When using the liquid polyester disclosed in Publication No. 89 etc., it is necessary to use a polyester of 200 poise or less at room temperature, but in the case of the modified α-olefin oligomer used in the present invention, it can be used up to about 2,000 poise. It is possible. The production of the liquid colorant for polyamide base use of the present invention involves blending a pigment or dye with a modified α-olefin oligomer,
It is manufactured by kneading the compound using a conventional kneading machine such as a three-roll mill, ball mill, sand mill, attritor, or kneader. In addition to the above-mentioned components, the liquid colorant of the present invention may contain a dispersant, an antistatic agent, an ultraviolet absorber, an antioxidant, an inorganic filler, and the like, if necessary.

0012

[Examples] The present invention will be specifically explained below with reference to Examples. Example 1 Ethylene/propylene cooligomer 1 (ethylene composition 5
3 mol%, number average molecular weight Mn 2,200, Q value 1.85
) was heated at 160° C. under a nitrogen atmosphere, and while stirring, 6.25 parts by weight of maleic anhydride as a modifier and 1.25 parts by weight of ditertiary butyl peroxide as an initiator were added from another nozzle. parts by weight were added dropwise over 5 hours. Next, unreacted maleic anhydride and decomposed products of ditertiary peroxide were removed under vacuum at 180°C, and the resultant mixture had a Mn of 2,450 and an acid value of 27 mgKOH/
g, 120 poise maleic acid-modified ethylene at 25°C/
A propylene co-oligomer was obtained. 70 parts by weight of the above maleic acid-modified ethylene/propylene co-oligomer, perylene red (CI.Name Pig.Red-1)
78) Disperse 30 parts by weight using three rolls to obtain 8
00 poise (B8 type viscometer, rotor rotation speed 10 rpm)
, measured at 25° C. (same in the following examples) was obtained. Next, nylon 6 (solution viscosity ηr due to concentrated H2SO4
Using a gear pump, the above colorant was press-injected into the molten polymer of el=2.67) from the melt spinning head so that the pigment content was 0.8%, and the mixture was kneaded and dispersed using a static mixer (manufactured by Koenix Co., Ltd.) with 40 elements. After measuring the temperature 2
The yarn was spun at 65°C and cold drawn to obtain a single yarn of 3 denier. There were no problems such as yarn breakage or generation of white smoke during spinning, and no yarn breakage occurred during drawing. Furthermore, no vehicle bleeding was observed on the surface of the obtained yarn.

Comparative Example 1 70 parts by weight of commercially available adipic acid polyester (trade name: Adekasizer PN-400, manufactured by Asahi Denka) and 30 parts by weight of perylene red (same as in Example 1) were treated in the same manner as in Example 1. A liquid colorant of 1,700 poise was obtained. Using the above colorant, spinning and
When drawing was performed, thread breakage occurred frequently during spinning, and white smoke was generated from the spinneret. In addition, yarn breakage occurred frequently during stretching, and vehicle bleeding was observed on the surface of the obtained yarn.

Example 2 Ethylene/propylene co-oligomer 2 (ethylene composition 4
9 mol%, Mn 1,240, Q value 1.74) in the same manner as in Example 1 except that 100 parts by weight of Mn1.
, 310, an acid value of 29 mgKOH/g, and a maleic acid-modified ethylene/propylene co-oligomer of 35 poise at 25°C was obtained. 75 parts by weight of the above maleic acid-modified ethylene/propylene co-oligomer, furnace carbon black (primary particle diameter 30 mμ, DBP oil absorption 113 ml/10
0g) 25 parts by weight was dispersed using three rolls, and 1
, 600 poise liquid colorant was obtained. Next, the same operation as in Example 1 was carried out so that the pigment content was 1.5%, and a single yarn of 3 denier was obtained. As in Example 1, no yarn breakage during spinning and drawing, no white smoke generation during spinning, and no vehicle bleed onto the yarn surface was observed. Further, the state of carbon dispersion in the yarn was also good.

Comparative Example 2 75 parts by weight of the vehicle used in Comparative Example 1 and 25 parts by weight of carbon black (same as in Example 2) were treated in the same manner as in Example 2. The resulting colored mixture has no fluidity;
Viscosity measurements were not possible. Next, using the above-mentioned colored mixture, spinning and drawing were attempted in the same manner as in Example 2, but since there was no fluidity, the gear pump could not supply a constant amount, resulting in frequent uneven coloring and yarn breakage. , satisfactory spinning could not be performed.

Example 3 80 parts by weight of the maleic acid-modified ethylene/propylene cooligomer obtained in Example 2, 15 parts by weight of rutile titanium oxide (primary particle size 0.3 μm), and cyanine blue (CI.N).
ame Pig. B1-15) 5 parts by weight was subjected to a dispersion treatment using an attritor to obtain a 120 poise liquid colorant. The above liquid colorant is directly transported from a metering pump to the hopper hole of the injection molding machine so that the titanium oxide content is 0.45% and the cyanine blue content is 0.15%. A colored molded plate was obtained. The obtained molded plate had good color dispersion, and no vehicle bleeding was observed on the surface of the molded plate.

[0017]

Effects of the Invention The liquid coloring agent for polyamide raw materials of the present invention uses a modified α-olefin oligomer as a dispersion medium for dyes and pigments, so it is stable even at high temperatures of 300°C, and is suitable for high-temperature coloring and spinning of polyamide. No problems such as thread breakage occur. Further, the above-mentioned dispersion medium used in the liquid colorant of the present invention has good compatibility with polyamide, so that it does not bleed onto the surface of polyamide. Furthermore, the above-mentioned dispersion medium has excellent fluidity properties and is particularly effective as a dispersion medium for carbon black.

Claims (5)

[Claims] 1. A liquid coloring agent for polyamide raw materials, which is characterized in that a dye or pigment is blended with a modified α-olefin oligomer, and the viscosity at room temperature is 10,000 poise or less. 2. The liquid coloring agent according to claim 1, wherein the modified α-olefin oligomer is an α-olefin oligomer or an ethylene/α-olefin cooligomer grafted with a carbonyl group-containing monomer. Claim 3: The modified α-olefin oligomer contains 0.2 to 5 carbonyl group-containing monomers to the α-olefin oligomer or ethylene/α-olefin cooligomer.
2. The liquid colorant according to claim 1, which is grafted in an amount of 0% by weight. 4. The modified α-olefin oligomer according to claim 2, wherein the carbonyl group-containing monomer is maleic acid or maleic anhydride. 5. The liquid coloring agent according to claim 1, comprising 100 parts by weight of a dye or pigment and 20 to 2,000 parts by weight of a modified α-olefin oligomer.