JPH0559319A - Liquid coloring agent for mass-coloring of condensation polymer - Google Patents

Abstract

PURPOSE:To obtain the subject coloring agent having excellent compatibility with condensation polymers and high heat-resistance and able to be smoothly and uniformly supplied to an extruder without causing the lowering of the physical properties of the colored polymer by using a specific aromatic condensed phosphoric acid ester as a vehicle. CONSTITUTION:The objective coloring agent is produced by compounding (A) an aromatic condensed phosphoric acid ester of formula (n is 1-20) with (B) a pigment and/or dye and adjusting the viscosity to <=10,000 poise at ordinary temperature. The component A is usually a mixture of the compounds of formula having different n values. The viscosity of the component A is preferably <=1,000 poise. The condensation polymer to be used in combination with the coloring agent is preferably polyamide or polyester.

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 condensation polymer base stock, and more particularly to a liquid colorant using an aromatic condensed phosphoric acid ester as a dispersion medium for dyes and pigments.

[0002]

BACKGROUND OF THE INVENTION Condensation polymers such as polyamides and polyesters are known for their excellent physical and chemical properties,
It is widely used in various industrial fields such as monofilaments, molded products, and films. Conventionally, various techniques have been known as a method for coloring an undiluted solution of a condensation polymer having a polar bond and having a relatively high melting point. For example, a method of adding a pigment or dye during the polymerization reaction of the condensation polymer, a masterbatch method in which the pigment or dye is dispersed in the condensation polymer at a high concentration, and a dry color in which the pigment or dye is dispersed and processed with metallic soap or wax. The method is well known. In the method of adding a pigment or a dye during the polymerization reaction of the above polyamide or the like, since the reaction is at a high temperature and for a long time, it is almost impossible to use a dye or an organic pigment having poor heat resistance. , It is limited to very limited pigments such as oxide type inorganic pigments and carbon black, and because the reaction kettle is colored and contaminated, it takes a long time to wash the kettle when changing colors unless a special reaction kettle is installed. It was disadvantageous in that it was expensive and expensive. Further, according to the masterbatch method, due to heat history in the kneading of pigments or dyes and the drying process of the masterbatch, deterioration of yarn physical properties such as tensile strength of polyamide fibers obtained by melt spinning or agglomeration occurs. There is a defect. Furthermore, the dry coloring method in which a pigment or dye processed into a powder form with a dispersion aid is directly blended with polyamide pellets, etc., the pigment or dye is a fine powder, which causes severe scattering and a problem of workplace pollution. It was not preferable because the cleaning of the mixer was extremely troublesome. In place of the above method, recently, a liquid colorant prepared by kneading a pigment or dye with a liquid vehicle at room temperature is also used. In this method, a colorant is quantitatively supplied to a molten polyamide by using a gear pump or a plunger pump (for example, JP-A-63-9271).
No. 7). However, condensation polymers such as polyamide are extremely polar resins and have poor compatibility with ordinary vehicles for liquid colorants, and if the vehicle has poor heat resistance, for example, yarn breakage or white smoke may occur during spinning. Trouble may occur, or so-called fish eyes may occur on the molded product. At present, no satisfactory liquid colorants have been developed which are able to circumvent these problems.

[0003]

In order to solve the above-mentioned drawbacks, the present invention adopts a liquid vehicle which has good compatibility with a highly polar condensation polymer and has good heat resistance at a temperature above its melting point. It is an object of the present invention to provide an original liquid colorant which can be smoothly and uniformly supplied into an extruder without causing deterioration of physical properties of the colored polymer.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted various studies on vehicles, which are dispersion media for liquid colorants, in consideration of heat resistance, compatibility, dispersibility of pigment dyes, and viscosity. As a result, a liquid colorant using a non-halogenated aromatic condensed phosphoric ester selected from among aromatic phosphoric acid esters already used as a flame retardant for a polymer,
The inventors have found that they have good compatibility with condensation polymers such as polyamides and polyesters and have sufficient physical properties to withstand spinning at high temperatures and various molding processes, and have completed the present invention. That is, the present invention has the general formula

[0005]

[Chemical 2]

A condensation characterized in that the aromatic condensed phosphoric acid ester represented by the formula (n is an integer from 1 to 20) is mixed with a pigment and / or a dye, and the viscosity at room temperature is 10,000 poise or less. The present invention provides a liquid colorant for base polymer base materials. Hereinafter, the present invention will be described in detail.

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

The aromatic condensed phosphoric acid ester used in the present invention has a structure represented by the general formula (1), and the benzene nucleus in this formula is not limited to an unsubstituted one, and for example, has 1 to 1 carbon atoms. Those substituted with one or more alkyl groups of 8 can also be preferably used as the aromatic condensed phosphoric acid ester of the present invention. The numerical value of n in the formula is appropriately selected depending on the pigment or dye to be mixed, and in general, by appropriately selecting n, the liquid colorant for undercoating can be supplied by a gear pump or a plunger pump. Adjust to a proper viscosity of 10,000 poise or less at a suitable room temperature. When n is 20 or more, the viscosity becomes too high to be used. Further, when n is 0, it does not correspond to a condensed ester, and this is inferior in heat resistance and cannot be used.

The aromatic condensed phosphoric acid ester used in the present invention is difficult to produce with a single n, and can usually be used as a mixture of aromatic phosphoric acid ester compounds in which n is different. .. Therefore, some n may be mixed to some extent, but even if some n is mixed to some extent, if the average degree of polymerization is 0.5 or more and n is 0.5 or more, the viscosity may be adjusted appropriately. Can be preferably used in the present invention.

The aromatic condensed phosphoric acid ester used in the present invention has been conventionally used as a flame retardant for a condensation polymer, and has already been blended as a flame retardant in a condensation polymer, but as a vehicle for a colorant. Not used. When used as a flame retardant and as a vehicle for a colorant, the order of addition with a color pigment or the like is different, and the amount of the present invention used is generally small. However, if the amount of the vehicle used is appropriately increased, it is possible to impart flame retardancy as well as coloring the condensation polymer.

The condensation-type polymer in which the colorant of the present invention is used is a thermoplastic polymer which is polymerized by a condensation reaction and is applied to, for example, polyamide, polyester, polyurethane, polycarbonate, etc., and is particularly suitable for polyamide and polyester. ing. Mineral oil, vegetable oil, liquid polybutene and the like can be further added to the above-mentioned aromatic condensed phosphoric acid ester used in the present invention.

Since the liquid colorant of the present invention is continuously supplied by an automatic weighing machine or the like at the time of use, it preferably exhibits fluidity at room temperature or heat retention.
Must be 000 poise or less. Therefore, the viscosity of the aromatic condensed phosphoric acid ester must be 10,000 poise or less, but the aromatic condensed phosphoric acid ester used in the present invention has an extremely high viscosity even if the pigment is blended at about 30% by weight. Since it does not rise to 1, the porosity of 2,000 poise or less, preferably 1,000 poise or less at room temperature can be particularly preferably used. When a liquid polyester disclosed in JP-A-60-45689 is used as a pigment dispersion medium, one having a poise of 200 poise or less at room temperature must be used. However, the aromatic condensed phosphoric acid ester used in the present invention In the case of, it is possible to use up to a viscosity as high as 2,000 poise.

The production of the liquid colorant for the condensation polymer base material of the present invention is carried out by blending a pigment or a dye with the aromatic condensed phosphoric acid ester, and then blending the blend with a three-roll mill, ball mill, sand mill, attritor, kneader or the like. It is manufactured by kneading with a kneader. In addition to the above components, a dispersant, an antistatic agent, an ultraviolet absorber, an antioxidant, an inorganic filler, etc. can be added to the liquid colorant of the present invention, if necessary.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 As a vehicle, an aromatic condensed phosphoric acid ester of n = 1 in formula (1) (CR-733S, trade name manufactured by Daihachi Chemical Industry Co., Ltd., specific gravity 1.31, viscosity 600 centipoise, average degree of polymerization n) = 0.6), and 60 parts by weight of perylene red (CI. Name Pig. Red-178) 4
Disperse 0 parts by weight with three rolls, 900 poise (BS type rotational viscometer rotor speed 10 rpm, 25 ° C)
And the liquid colorant of the same) was obtained. Then, nylon 6 (solution viscosity η with concentrated H ₂ SO _4
The above colorant was pressed into the molten polymer ( _rel = 2.67) from the melt spinning head using a gear pump so that the pigment content was 0.8%, and kneaded and dispersed with 40 elements of a static mixer (Kenix). After measuring the temperature 26
Spinning was carried out at 5 ° C. and cold drawing was carried out to obtain a single denier 3 denier yarn. The discharge state during spinning was extremely good, there were no troubles such as lump yarn, yarn breakage, and white smoke generation, and no yarn breakage occurred during drawing. No bleeding of the vehicle was observed around the nozzle of the spinneret or on the surface of the obtained yarn.

Example 2 As a vehicle, n = 2 aromatic condensed phosphoric acid ester (CR-735, trade name manufactured by Daihachi Chemical Industry Co., Ltd., specific gravity 1.33, viscosity 4000 centipoise, average degree of polymerization n)
= 1.6) 70 parts by weight of cyanine blue (CI.Na.
me Pig. 30 parts by weight of Blue-15) was treated in the same manner as in Example 1 to obtain a liquid colorant of 1250 poise. Then, in Example 1 so that the pigment content becomes 1.0%.
Spinning and drawing were carried out in the same manner as in 1. to obtain a yarn of 3 denier single yarn. As in Example 1, the ejection state during spinning was extremely good, no yarn breakage or white smoke was observed during spinning / drawing, and no vehicle was found around the spinneret nozzle or on the surface of the obtained yarn. No bleed was seen.

Comparative Example 1 The same treatment as in Example 1 was carried out with 70 parts by weight of commercially available adipic acid polyester (trade name ADEKA CIZER PN-400, manufactured by Asahi Denka Co., Ltd.) and 30 parts by weight of cyanine blue (same as Example 2). Then, a liquid colorant having 1800 poise was obtained. When the above colorant was used to carry out spinning and drawing in the same manner as in Example 1, the discharge state during spinning was unstable, and many Kobu yarns and yarn breakages occurred, causing white smoke from the spinneret. did. In addition, yarn breakage frequently occurred during drawing, and vehicle bleeding was observed around the spinneret nozzle and on the surface of the obtained yarn.

Example 3 75 parts by weight of the vehicle used in Example 1 and 25 parts by weight of cyanine green (CI.NamePig.Green-7) were dispersed in an attritor to obtain a liquid pigment of 100 poise. It was The above liquid colorant has a pigment content of 0.4%.
So that it can be directly transported from the tube pump to the hopper hole of the injection molding machine, automatically weighed and continuously fed with nylon 6
A colored molded plate (same as in Example 1) was obtained. The obtained molded plate had good color dispersion and showed excellent transparency. No bleeding of the vehicle was observed on the surface of the molded plate.

Example 4 Polyethylene terephthalate (inherent viscosity 0.65 in a 1: 1 weight ratio of phenol to tetrachloroethane at 25 ° C. in a mixed solvent at 25 ° C.) was used in place of nylon 6 of Example 1.
Was spun at a temperature of 290 ° C. and stretched 4 times at 115 ° C. to obtain a yarn of 3 denier single yarn. Similar to Example 1,
The discharge state during spinning is extremely good,
There were no problems such as yarn breakage or white smoke, and no yarn breakage occurred during stretching. No bleeding of the vehicle was observed around the nozzle of the spinneret or on the surface of the obtained yarn.

Example 5 70 parts by weight of the vehicle used in Example 2 and anthraquinone yellow (CI. Name Pig. Yellow-1)
47) 30 parts by weight was treated in the same manner as in Example 1, and 8
A liquid colorant of 50 poise was obtained. Using the above colorant and polyethylene terephthalate (same as in Example 4), spinning and drawing were carried out in the same manner as in Example 4 so that the pigment content was 1.0% to obtain a single denier 3 denier yarn. It was The discharge condition during spinning was extremely good, there were no problems such as lump yarn, yarn breakage, and white smoke, and no yarn breakage occurred during drawing. Also, no vehicle bleed was seen.

Comparative Example 2 Commercially available adipic acid polyester (same as Comparative Example 1) 7
0 parts by weight, anthraquinone type yellow (same as Example 5)
30 parts by weight was treated in the same manner as in Example 1 and 1100
A poise liquid colorant was obtained. Spinning / stretching was performed using the above colorant in the same manner as in Example 5, but the discharge state during spinning was unstable, and yarn breakage occurred several times during spinning / stretching. In addition, vehicle bleed was seen around the nozzle of the die.

[0021]

INDUSTRIAL APPLICABILITY The liquid colorant for use in the condensation polymer base of the present invention uses an aromatic condensed phosphoric acid ester as a dispersion medium for dyes and pigments, and is stable even at a high temperature of 300 ° C. No troubles such as yarn breakage occur during high temperature color spinning. Further, the dispersion medium used in the liquid colorant of the present invention has good compatibility with polyamide or polyester and therefore does not bleed on the surface of polyamide or polyester. Furthermore, the above-mentioned dispersion medium has excellent flow characteristics and can be uniformly mixed with the melt-condensation polymer to achieve uniform coloring. Further, by increasing the amount of the aromatic condensed phosphoric acid ester, it is possible to impart appropriate flame retardancy.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08G 69/00 NRB 9286-4J

Claims (5)

[Claims] 1. A general formula: A condensed polymer raw material characterized in that an aromatic condensed phosphoric acid ester represented by the formula (n is a number from 1 to 20) is mixed with a pigment and / or a dye, and the viscosity at room temperature is 10,000 poise or less. Wearable liquid colorant. 2. The condensation polymer base liquid colorant according to claim 1, which comprises 100 parts by weight of a pigment and / or dye and 20 to 2000 parts by weight of an aromatic condensed phosphoric acid ester. 3. The liquid colorant for the condensation polymer base material according to claim 1, wherein the condensation polymer is polyamide. 4. The liquid colorant for the condensation polymer base material according to claim 1, wherein the condensation polymer is polyester. 5. A liquid colorant for a condensation polymer base material according to claim 1, which comprises 100 parts by weight of a dye or pigment and 20 to 2,000 parts by weight of an aromatic condensed phosphoric acid ester.