JP3077448B2 - Highly concentrated colored polyester resin and colored composition for polyester fiber using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coloring composition for saturated polyester resins. More specifically, the present invention relates to a high-concentration solid colorant (hereinafter, referred to as a masterbatch) used when processing a polyester fiber in a stock solution.

[0002]

2. Description of the Related Art Aromatic polyesters represented by polyethylene terephthalate have excellent and well-balanced properties such as heat resistance, weather resistance, texture, and bulkiness.
It is used in a wide range of fields such as suits such as suits, blouses and socks, automobile mats, tire cords, industrial materials such as fish nets, curtains, rugs, and non-woven fabrics. However, polyesters are generally less dyeable and have lower fastness than natural fibers, acrylics, nylons, and the like. Therefore, a method of obtaining clear colored fibers without impairing the physical properties of the polyesters has been desired.

Conventionally, a method of coloring during the polyester reaction step is known, but since it is difficult to change the color, another method is to add and mix a coloring composition during melt spinning of a polyester resin. Has been used. Coloring compositions include powdery dry color in which a pigment and a dispersant are mixed, liquid color or paste color in which a pigment is dispersed in a liquid at room temperature, and a high concentration of pigment dispersed in a resin at room temperature. There is a masterbatch formed into pellets, flakes, or beads by being formed.
Each of these coloring compositions has advantages and disadvantages, and is used for applications that take advantage of the characteristics of each.Among these, master batch pellets are desired in terms of ease of handling and preservation of the working environment during use. And some have been proposed.

For example, there has been a method of dispersing a pigment in a polyester dissolved in a solvent. However, this method has difficulty in removing the solvent, and a carrier comprising a glycol and a specific dispersant has been proposed. The physical properties of the colored fibers were reduced due to the effect of the carrier used, such as high hygroscopicity, and the low amount of the pigment received, which increased the amount of the carrier added together with the pigment. In particular, in the case of industrial materials that require high physical properties, remarkable deterioration in physical properties was observed, and this problem could not be solved. In addition, the use of polypropylene or the like as another carrier was considered, but these have poor compatibility with the polyester resin, and phenomena such as impairing the spinning workability occur or the predetermined density or saturation cannot be obtained. There is a drawback that the commercial value of the fiber is reduced. In order to improve these drawbacks, Japanese Patent Laid-Open No.
A low melting point copolyester as disclosed in JP-A-36725 has been proposed.

[0005] This coloring composition has good progress in the physical properties of the fiber because of its good compatibility with the polymer to be colored, but it has a problem in terms of pigment dispersibility and work environment preservation for performing pigment dispersing treatment in a solvent system.・ The process was not enough.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves these drawbacks, is easy in the production process of the coloring composition, has a small decrease in the physical properties of fibers that require high physical properties even at a high pigment concentration, The present invention provides a solid colored composition (master batch pellet) that does not impair the solid color composition.

[0007]

Means for Solving the Problems The first invention comprises (a) 30 to 80 parts by weight of a dye, and (b) a number average molecular weight of 2000 to 2000.
20000, melting point of 80 to 135 ° C, melt flow rate of 250 to 500 g / 10 min, 5 to 70 parts by weight of a saturated copolymerized polyester, (c) 3 to 10 parts by weight of a neutralized carboxylic acid-containing polyolefin wax, (d) A highly concentrated colored polyester resin comprising 5 to 20 parts by weight of a partially saponified montanic acid. The second invention comprises (A) 5 to 80 parts by weight of a high-concentration colored product of the polyester resin of the first invention,
(B) polyethylene terephthalate 20 having a number average molecular weight of 20,000 to 30,000 and a melting point of 250 to 260 ° C.
~ 95 parts by weight of a coloring composition for polyester fibers.

The dye (a) in the present invention is not particularly limited as long as it does not significantly deteriorate or decompose even when treated at the melting point of the polyester for several minutes, and examples thereof include inorganic pigments and organic pigments. For example, as inorganic pigments, titanium dioxide,
Examples of organic pigments such as ultramarine, iron oxide, chromium oxide, cadmium sulfide, and carbon black include anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxazine, quinophthalone, perylene, and perinone. Can be. Further, a mixture thereof may be used.

The amount of the pigment is from 30 to 80 parts by weight, preferably from 40 to 70 parts by weight. If the amount of the pigment is less than 30 parts by weight, sufficient coloring can be performed without impairing the performance of the polyester fiber. When the amount is more than 80 parts by weight, the fluidity becomes small and the production of a master batch becomes difficult. The (b) saturated copolyester of the present invention is a saturated polyester formed by co-condensation polymerization of a dicarboxylic acid component and a diol component.
Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid,
Aliphatic dicarboxylic acids such as adipic acid and sebacic acid;
As the diol component, ethylene glycol rule, 1.4-
Copolycondensation is carried out by using butanediol, diethylene glycol, neopentyl glycol, etc., and by changing these various combinations and amounts.

The saturated copolymer polyester of the present invention has a number average molecular weight of 2,000 to 20,000, preferably 8,000.
１５15000. If it is less than 8,000, it may cause a decrease in the physical properties of the fiber, and if it is more than 15,000, the melt viscosity is high, so that it is difficult to grind, and thus there is a problem in the dispersibility of the pigment. For kneading with pigment, use a Banbury mixer, pressure kneader, extruder,
A method of dispersing the pigment while heating it to a temperature equal to or higher than the melting point of the copolymerized polyester using a known kneader having a heating device such as a two-roller or a three-roller is preferable. Among them, the use of a heated three rolls is most preferable in order to uniformly and uniformly disperse the pigment. In use, it is limited by the melting point and melt viscosity of the copolyester,
Melting point 80-135 ° C, melt flow rate (MFR)
250-500 g / 10 min, preferably 100-1
20 ° C., MFR 300 to 400 g / 10 min. If the melting point is lower than 80 ° C. and the MFR is higher than 500, pelletization during the production of the master batch becomes difficult, and the MFR 250
If the melting point is lower than 135 ° C., it is difficult to knead the meat, for example, because the melt viscosity is high during kneading, and there is a problem in the dispersibility of the pigment. The amount of the saturated copolymerized polyester is 5 to 70 parts by weight. If the amount is more than 70 parts by weight, the softening point of the saturated copolyester is low and the melt viscosity is low, so that the workability during the production of the master batch is inferior and the performance of the fiber may be impaired.

The neutralized product of (c) the carboxylic acid-containing polyolefin wax in the present invention means that all or a part of the carboxylic acid of the carboxylic acid-containing polyolefin wax is a metal such as sodium, calcium, aluminum, magnesium, zinc or the like. Those neutralized with a cation, ammonium ion or alkylammonium ion, or a mixture thereof. Polyolefin wax containing carboxylic acid is obtained by oxidative modification of polyolefin wax such as polyethylene wax, polypropylene wax, paraffin wax, etc. (meth) acrylic acid, maleic acid,
Grafted with an α, β-unsaturated carboxylic acid such as fumaric acid, itaconic acid or its anhydride, or a random or block copolymer of ethylene or propylene with the above α, β-unsaturated carboxylic acid; And its molecular weight range is from 500 to 15,000. Products neutralized with ammonium ions or alkylammonium ions generate ammonia gas or amine gas at high temperatures, which may cause environmental pollution and mold corrosion. Use products neutralized with metal cations from the viewpoint of thermal stability. Is preferred. The compounding amount of the neutralized carboxylic acid-containing polyolefin wax is 3 to 10 parts by weight. Within this range, a colored composition having good pigment dispersibility and color developability can be obtained. If the amount exceeds 10 parts by weight, the effect of increasing the amount of addition is not obtained and the cost increases, which is not preferable.

The (d) partially saponified montanic acid of the present invention is obtained by esterifying an oxide of montan wax with a higher alcohol and partially saponifying it with a metal oxide. The metal cation of the metal oxide is generally neutralized with calcium and has a pigment dispersing ability in a small amount. The melting point of the partially saponified montanic acid used in the present invention is 70 to 1
The temperature is 10 ° C, preferably 80 to 105 ° C. Further, it is preferable that the polyethylene terephthalate does not remarkably deteriorate or decompose even if treated for several minutes at the melting point of polyethylene terephthalate.
600 acid value about 10-13 mgKOH / g, saponification value about 1
40-150mgKOH / g is 300- ℃ loss on heating 3 ~
It can be suitably used at 5%. The amount of the partially saponified montanic acid is 5 to 20 parts by weight, preferably 5 to 10 parts by weight. If the amount is more than 20 parts by weight, the workability during the production of the masterbatch is impaired due to the effect of external lubrication, and there is no effect on the pigment dispersion.

The number average molecular weight (B) of the present invention is 20,000.
The polyethylene terephthalate of up to 30,000 is not particularly limited, and may be a copolymerized polyester which has the required performance by mixing other glycols or carboxylic acids within a range that does not impair the effects of the present invention. If the number average molecular weight of the polyethylene terephthalate is less than 20,000, the workability of processing the polyester fiber in a stock solution will be impaired,
If it exceeds 30,000, the fluidity of the masterbatch will be low, and the distribution at the time of dilution will be poor. The blending amount of polyethylene terephthalate is 20 to 95 parts by weight. If the amount is less than 20 parts by weight, the cohesive force is small and the material becomes brittle, so that the workability during the production of the master batch is poor.

The coloring composition of the present invention may contain, if necessary, stabilizers such as antioxidants and ultraviolet absorbers, flame retardants, surfactants, and antistatic agents as long as the effects of the present invention are not impaired. May be added. The coloring composition of the present invention is
(B) After kneading the components excluding polyethylene terephthalate having a number average molecular weight of 20,000 to 30,000 using a kneader such as a kneader, a two-roller, or a three-roll, (B) a polyester having a number-average molecular weight of 20,000 to 30,000 is further added. In addition, it is obtained by pelletizing with a single-screw or twin-screw extruder.

[0015]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”. Example 1 (a) 50 parts of β-type copper phthalocyanine blue “Lionol Blue FG7330” (manufactured by Toyo Ink Mfg. Co., Ltd.) (b) copolymerized polyester “Vylon GM900” (molecular weight: about 20,000, melting point: 115 ° C., Toyobo Co., Ltd.) (C) Neutralized product of carboxylic acid-containing polyolefin wax "AC polyethylene 285A" (molecular weight: about 3000, neutralization ratio: 50%, manufactured by Allied Chemical Co.) 5 parts (d) Partial montanic acid "LuwaxOP" (number-average molecular weight: about 1600, oxidation value: about 13 mgKOH / g, saponification value: about 150 mgKOH / g, manufactured by BASF) 10 parts (a) to (d) are mixed and heated and mixed with a three-roll mill After that, an intermediate was obtained by cooling and pulverization. Number average molecular weight about 250
00 polyethylene terephthalate “Unipet RT5
43 ”(melting point: 255 ° C., intrinsic viscosity: 0.72, manufactured by Nippon Unipet Co., Ltd.) and 40 parts of the above intermediate were blended, processed by a single screw extruder, and pelletized without any trouble during operation. A master batch having a high pigment concentration was obtained.

To 100 parts of polyethylene terephthalate "Unipet RT543", 3 parts of the obtained masterbatch pellets were blended and spun by a vertical type test spinning machine (Fuji Filter spinning tester).
Heat treatment was carried out at 0 ° C. to obtain 3.00 denier blue fibers having no fineness variation. There was no trouble in spinning and drawing, and the intrinsic viscosity [η] of the polyethylene terephthalate without the master batch was 0.672 dl / g, whereas the obtained fiber had an intrinsic viscosity of 0.655 dl / g and an intrinsic viscosity retention of 97. 5%. Example 2 3 parts of the master batch pellets obtained in Example 1 were mixed with polyethylene terephthalate “Unipet RT580” 10
0 parts, spinning with a vertical type test spinning machine (Fuji Filter spinning tester), 4 times drawing and heat treatment at 140 ° C to obtain 3.00 denier blue fiber without fineness variation. . There was no trouble during spinning and drawing, and the intrinsic viscosity [η] of the obtained fiber was 0.964 dl / g, whereas the intrinsic viscosity [η] of polyethylene terephthalate without the master batch was 1.021 dl / g.
It was 4.4%.

Comparative Example 1 (a) 50 parts of β-type phthalocyanine blue “Lionol Blue FG7330” (b) 35 parts of copolymerized polyester “Vylon GM400” (molecular weight 25,000, melting point 143 ° C., manufactured by Toyobo Co., Ltd.) (c) 5 parts of neutralized carboxylic acid-containing polyolefin wax "AC polyethylene 285A" (d) Partially saponified product of montanic acid "Luwax OP" 10 parts After mixing (a) to (d) and heating and mixing with three rolls Then, an intermediate was obtained by cooling and pulverization. After mixing 60 parts of the obtained intermediate and 40 parts of “Unipet RT543”, the mixture was processed by a single screw extruder to obtain a pellet-shaped master batch having a high pigment concentration without any trouble during operation.

3 parts of the obtained master batch pellets were mixed with polyethylene terephthalate “Unipet RT543” 1
In the same manner as in Example 1, spinning was attempted. However, an increase in reduced pressure due to poor dispersion of the pigment was observed, and thread breakage occurred. Comparative Example 2 (a) 50 parts of β-type phthalocyanine blue “Lionol Blue FG7330” 50 parts (b) Neutralized product of carboxylic acid-containing polyolefin wax “AC polyethylene 285A” 30 parts (c) Partially saponified product of montanic acid “Luwax OP” After mixing 20 parts of (a) to (c) and mixing by heating with a three-roll mill, an intermediate was obtained by cooling and pulverizing. After mixing 50 parts of the obtained intermediate and 50 parts of “Unipet RT543”, processing was attempted with a single screw extruder, but the desired master pellet could not be obtained.

Comparative Example 3 (a) 50 parts of β-type phthalocyanine blue “Lionol Blue FG7330” (b) 35 parts of copolymerized polyester “Vylon GM900” (c) Polyethylene wax “Sunwax 131P” (molecular weight: about 3500, melting point: 108) 5 ° C., manufactured by Sanyo Chemical Industries, Ltd. 5 parts (d) 10 parts of partially saponified montanic acid “Luwax OP” (a) to (d) were mixed, heated and mixed with three rolls, and then cooled and pulverized. To give an intermediate. After mixing 60 parts of the obtained intermediate and 40 parts of “Unipet RT543”, the mixture was processed by a single screw extruder to obtain a pellet-shaped master batch having a high pigment concentration without any trouble during operation.

3 parts of the obtained master batch pellets were mixed with polyethylene terephthalate “Unipet RT543” 1
In the same manner as in Example 1, spinning was carried out. While the intrinsic viscosity [η] of the polyethylene terephthalate without the master batch was 0.872 dl / g, the obtained fiber had an [η] of 0.550 dl / g and an intrinsic viscosity retention of 8
1.8%. Comparative Example 4 (a) 50 parts of β-type phthalocyanine blue “Lionol Blue FG7330” (b) 40 parts of copolymerized polyester “Vylon GM900” (c) 10 parts of neutralized carboxylic acid-containing polyolefin wax “AC polyethylene 285A” 10 parts ( After a) to (c) were mixed and heated and mixed with three rolls, an intermediate was obtained by cooling and pulverization. After mixing 60 parts of the obtained intermediate and 40 parts of “Unipet RT543”, the mixture was processed by a single screw extruder to obtain a pellet-shaped matter batch having a high pigment concentration without any trouble during operation.

3 parts of the obtained master batch pellets were mixed with polyethylene terephthalate “Unipet RT543” 1
In the same manner as in Example 1, spinning was attempted. However, an increase in reduced pressure due to poor dispersion of the pigment was observed, and thread breakage occurred.

[0022]

According to the present invention, the pigment is highly filled, the dispersibility and the color development are good, and the amount of the pigment to be mixed into polyethylene terephthalate, which is a resin to be colored, can be relatively small. Also less. Further, since the masterbatch is in the form of pellets, it is easy to handle, is extremely useful in a wide range of fiber applications, and has extremely high industrial value in terms of cost and quality.

Claims (2)

(57) [Claims] (1) 30 to 80 parts by weight of a dye, (b) a number average molecular weight of 2,000 to 20,000, and a melting point of 80 to 135.
5 to 70 parts by weight of a saturated copolymerized polyester having a melt flow rate of 250 to 500 g / 10 min, (c) 3 to 10 parts by weight of a neutralized carboxylic acid-containing polyolefin wax, and (d) partially saponified montanic acid 5 ~ 20 parts by weight,
Highly colored polyester resin. (A) 5 to 80 parts by weight of a high-concentration colored product of the polyester resin according to claim 1, and (B) a number average molecular weight of 20.
A colored composition for polyester fibers comprising 20 to 95 parts by weight of polyethylene terephthalate having a melting point of 250 to 260 ° C and a melting point of 000 to 30,000.