JPH06313096A - Material for coloring polyester resin in high concentration and coloring composition using the same and used for polyester fiber - Google Patents

Abstract

PURPOSE:To prepare a master batch containing a pigment in a high concentration, improving the processability of a polyester into fibers and the deterioration resi-stance of the polyester, and giving the fibers wide in uses. CONSTITUTION:This material for coloring a polyester resin in a high concentration comprises (a) 30-80 pts.wt. of a pigment, (b) 5-70 pts.wt. of a saturated copolyester having a number-average mol.wt. of 2000-20000 and a melting point of 80-135 deg.C, (c) 3-10 pts.wt. of the neutralized product of a carboxylic acid- containing polyolefin wax, and (d) 5-20 pts.wt. of the partially saponified product of montanic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coloring composition for a saturated polyester resin. More specifically, the present invention relates to a high-concentration solid colorant (hereinafter referred to as a masterbatch) used when a polyester fiber is subjected to undiluted processing.

[0002]

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 clothing such as suits, blouses and socks, automobile mats, tire cords, industrial material curtains such as fishnets, rugs, and interiors such as nonwoven fabrics. However, polyesters are generally less dyeable than natural fibers, acrylics, nylons, etc., and have low fastness. Therefore, a method for obtaining clear colored fibers without impairing the physical properties of polyesters has been desired.

Conventionally, a method of coloring a polyester during a reaction step is known, but it is difficult to change the color. Therefore, another method is to add and mix a coloring composition during melt spinning of a polyester resin. Has been used. The coloring composition includes a powdery dry color in which a pigment and a dispersant are mixed, a liquid color or a paste color in which the pigment is dispersed in a liquid dispersant at room temperature, and the pigment is dispersed at a high concentration in a solid resin at room temperature. There is a masterbatch in the form of pellets, flakes or beads.
Each of these coloring compositions has advantages and disadvantages, and they are used for applications that make use of their respective characteristics, but among them, masterbatch pellets are desired from the viewpoint of easy handling and work environment conservation during use. And several have been proposed.

For example, there has been a method of dispersing a pigment in a polyester dissolved in a solvent, but this method has difficulty in removing the solvent, and a carrier in which a glycol and a specific dispersant are combined has been proposed. The physical properties of the colored fiber deteriorated due to the fact that the carrier used has high hygroscopicity, and the amount of the carrier added together with the pigment increases due to the low pigment acceptance amount. Especially in industrial material applications where high physical properties are required, the physical properties are remarkably deteriorated and this problem cannot be solved. Further, the use of polypropylene or the like as another carrier has been considered, but these have poor compatibility with the polyester resin and a phenomenon such as impairing spinning workability occurs or a predetermined concentration and saturation cannot be obtained. However, there is a drawback that the commercial value of the fiber is reduced. In order to improve these drawbacks, JP-A-51-1
A low melting point copolyester as seen in Japanese Patent No. 36725 has been proposed.

This coloring composition has good compatibility with the polymer to be colored and has made great progress in the physical properties of the fiber. However, in terms of pigment dispersibility and environmental protection for carrying out a pigment dispersion treatment in a solvent system.・ The process was not yet satisfactory.

[0006]

DISCLOSURE OF THE INVENTION The present invention has improved these drawbacks, is easy in the manufacturing process of a coloring composition, and has a small deterioration in physical properties of fibers requiring high physical properties even at a high pigment concentration, and has a stock solution processability. The present invention provides a solid colored composition (masterbatch pellets) that does not impair the above.

[0007]

The first invention is (a) a dye of 30 to 80 parts by weight, and (b) a number average molecular weight of 2,000 to.
5 to 70 parts by weight of a saturated copolyester having a melt flow rate of 250 to 500 g / 10 min, a neutralization product of a carboxylic acid-containing polyolefin wax, 3 to 10 parts by weight, (d) It is a highly concentrated polyester resin colored product comprising 5 to 20 parts by weight of a partially saponified montanic acid. The second invention is (A) 5 to 80 parts by weight of the polyester resin high-concentration colored product 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.
It is a colored composition for polyester fibers, which comprises ˜95 parts by weight.

The (a) dye in the present invention may be any one as long as it does not significantly change or decompose even when treated at the melting point of polyester for several minutes, and examples thereof include inorganic pigments and organic pigments. For example, as the inorganic pigment, titanium dioxide,
Ultramarine, iron oxide, chromium oxide, cadmium sulfide, carbon black, etc. Organic pigments include anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, dioxazine-based, quinophthalone-based, perylene-based and perinone-based You can Also, a mixture of these may be used.

The blending amount of the dye is 30 to 80 parts by weight, preferably 40 to 70 parts by weight. When the blending amount of the dye is less than 30 parts by weight, sufficient coloring is performed without impairing the performance of the polyester fiber. If it is more than 80 parts by weight, the fluidity becomes small and the production of the masterbatch becomes difficult. The (b) saturated copolyester of the present invention is a saturated polyester formed by the copolycondensation of a dicarboxylic acid component and a diol component, and as the dicarboxylic acid,
Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid,
Aliphatic dicarboxylic acids such as adipic acid and sebacic acid,
Ethylene glycol rule, 1.4-
Butanediol, diethylene glycol, neopentyl glycol, etc. are used and copolycondensed by various combinations of these and changes in the blending amount.

The number average molecular weight of the saturated copolyester of the present invention is 2000 to 20000, preferably 8000.
˜15,000. When it is less than 8,000, it becomes a factor that causes deterioration of the physical properties of the fiber, and when it is more than 15,000, it is difficult to knead the meat because the melt viscosity is high and the dispersibility of the pigment becomes a problem. For kneading with pigment, Banbury mixer, pressure kneader, extruder,
A suitable method is to disperse the pigment while heating it to a temperature not lower than the melting point of the copolyester using a known kneading machine having a heating device such as a two-roll or three-roll roll. Above all, in order to uniformly disperse the pigment evenly, it is most preferable to use a heating three-roll, because it is easy to use. Also, in use, although it is limited to the melting point and melt viscosity of the copolyester,
Melting point is 80-135 ℃, Melt flow rate (MFR)
250-500 g / 10 min, preferably melting point 100-1
It is 20 degreeC and MFR300-400g / 10min. If the melting point is less than 80 ° C and the MFR is more than 500, pelletization during masterbatch production becomes difficult, and MFR250
If it is less than the melting point of more than 135 ° C., the melt viscosity is high during kneading and it is difficult to knead, and there is a problem in the dispersibility of the pigment. The amount of the saturated copolyester blended is 5 to 70 parts by weight. When the amount is more than 70 parts by weight, the softening point of the saturated copolyester is low and the melt viscosity is small, so that the workability during the production of the masterbatch is deteriorated and the performance of the fiber may be impaired.

In the present invention, (c) a neutralized product of a carboxylic acid-containing polyolefin wax means that all or part of the carboxylic acid of the carboxylic acid-containing polyolefin wax is a metal such as sodium, calcium, aluminum, magnesium or zinc. It is a cation, an ammonium ion or an 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, and paraffin wax. (Meth) acrylic acid, maleic acid,
Those grafted with α, β-unsaturated carboxylic acids such as fumaric acid and itaconic acid, or their anhydrides, random or block copolymers of ethylene or propylene with the above α, β-unsaturated carboxylic acids, etc. , Its molecular weight range is 500 to 15,000. Those neutralized with ammonium ions or alkylammonium ions generate ammonia gas or amine gas at high temperature, which may cause environmental pollution or mold corrosion, so use those neutralized with metal cations from the viewpoint of thermal stability. Is preferred. The content 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 it exceeds 10 parts by weight, the effect of increasing the addition amount is not obtained and the cost becomes high, 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 one which is neutralized with calcium and has a small amount of pigment dispersibility. The partially saponified montanic acid used in the present invention has a melting point of 70 to 1
The temperature is 10 ° C, preferably 80 to 105 ° C. Furthermore, it is preferable that polyethylene terephthalate does not undergo significant alteration or decomposition even if it is treated with the melting point of polyethylene terephthalate for several minutes.
600 acid value about 10 ~ 13mgKOH / g, saponification value about 1
40-150 mg KOH / g is the heating loss of 300 ℃ 3-
It can be suitably used at 5%. The compounding amount of the partially saponified montanic acid is 5 to 20 parts by weight, preferably 5 to 10 parts by weight. When the amount is more than 20 parts by weight, the workability at the time of producing the masterbatch is impaired due to the effect of external lubricity, and there is no effect on the pigment dispersion. Above this, the effect of increasing the addition amount is not preferable.

The number average molecular weight (B) of the present invention is 20,000.
The polyethylene terephthalate having a molecular weight of up to 30,000 is not particularly limited, and may be a copolyester that meets the required performance by mixing with other glycols or carboxylic acids as long as the effects of the present invention are not impaired. When the number average molecular weight of polyethylene terephthalate is less than 20,000, the workability in processing the raw liquid of polyester fibers is impaired,
When it exceeds 30,000, the fluidity of the masterbatch becomes low and the distributability at the time of dilution becomes poor. The compounding amount of polyethylene terephthalate is 20 to 95 parts by weight. When the amount is less than 20 parts by weight, the cohesive force is small and it becomes brittle, so that workability during masterbatch production is poor.

The coloring composition of the present invention may contain, if necessary, stabilizers such as antioxidants, ultraviolet absorbers, flame retardants, surfactants, antistatic agents, etc. within a range that does not impair the effects of the present invention. You may add additives, such as. The coloring composition of the present invention,
(B) After kneading the components excluding polyethylene terephthalate having a number average molecular weight of 20,000 to 30,000 with a kneader, a two-roll mill, a three-roll mill, or the like, (B) a polyester having a number average molecular weight of 20,000 to 30,000. In addition, it can be obtained by pelletizing with a single-screw or twin-screw extruder.

[0015]

EXAMPLES The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. Example 1 (a) β-type copper phthalocyanine blue “Lionol blue FG7330” (manufactured by Toyo Ink Mfg. Co., Ltd.) 50 parts (b) Copolyester “Vylon GM900” (molecular weight about 20,000, melting point 115 ° C., Toyobo ( Co., Ltd.) 35 parts (c) Neutralized product of carboxylic acid-containing polyolefin wax "AC polyethylene 285A" (molecular weight about 3000, neutralization rate 50%, Allied Chemical Co., Ltd.) 5 parts (d) Montane acid partial ken Compound "LuwaxOP" (number average molecular weight of about 1600, oxidation value of about 13 mgKOH / g, saponification value of about 150 mgKOH / g, manufactured by BASF) 10 parts (a) to (d) are mixed and mixed by heating with a three-roll mill. After that, an intermediate product was obtained by cooling and grinding. 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 60 parts of the above intermediate are mixed and processed with a single-screw extruder, and pelletized without trouble during work. A high pigment concentration masterbatch was obtained.

100 parts of polyethylene terephthalate "Unipet RT543" was mixed with 3 parts of the obtained masterbatch pellets, spun by a vertical test spinning machine (Fuji Filter Spinning Tester), and drawn 4 times.
A heat treatment was performed at 0 ° C. to obtain a 3.00 denier blue fiber with no variation in fineness. There was no trouble during spinning and drawing, and the intrinsic viscosity [η] of the masterbatch-free polyethylene terephthalate was 0.672 dl / g, whereas the [η] of the obtained fiber was 0.655 dl / g and the intrinsic viscosity retention rate was 97. It was 5%. Example 2 3 parts of the masterbatch pellets obtained in Example 1 were mixed with polyethylene terephthalate "Unipet RT580" 10
0 parts were blended, spun by a vertical test spinning machine (Fuji Filter Spinning Tester), drawn 4 times, and then heat-treated at 140 ° C. to obtain a 3.00 denier blue fiber with no variation in fineness. . There was no trouble during spinning or drawing, and the intrinsic viscosity [η] of the masterbatch-free polyethylene terephthalate was 1.021 dl / g, whereas the [η] of the obtained fiber was 0.964 dl / g.
It was 4.4%.

Comparative Example 1 (a) β-type phthalocyanine blue "Lionol blue FG7330" 50 parts (b) Copolyester "Vylon GM400" (molecular weight 25,000, melting point 143 ° C, Toyobo Co., Ltd.) 35 parts (c) Neutralized product of carboxylic acid-containing polyolefin wax "AC polyethylene 285A" 5 parts (d) Partially saponified montanic acid "Luwax OP" 10 parts (a) to (d) are mixed and heated with a three-roll mill. An intermediate product was obtained by cooling and pulverizing. 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 masterbatch having a high pigment concentration without any trouble during the operation.

3 parts of the obtained masterbatch pellet was used as polyethylene terephthalate "Unipet RT543" 1
When 100 parts were blended and spinning was tried in the same manner as in Example 1, an increase in reduced pressure was recognized due to poor dispersion of the pigment, and yarn breakage occurred. Comparative Example 2 (a) 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 montanic acid “Luwax OP” 20 parts (a) to (c) were mixed, heated and mixed with a three-roll mill, and then cooled and pulverized to obtain an intermediate. After mixing 50 parts of the obtained intermediate product and 50 parts of "Unipet RT543", an attempt was made to process with a single-screw extruder, but the target master pellet could not be obtained.

Comparative Example 3 (a) β type phthalocyanine blue "Lionol Blue FG7330" 50 parts (b) Copolyester "Vylon GM900" 35 parts (c) Polyethylene wax "Sun Wax 131P" (molecular weight about 3500, melting point 108) C., manufactured by Sanyo Chemical Industry Co., Ltd. 5 parts (d) Partially saponified montanic acid “Luwax OP” 10 parts (a) to (d) are mixed and mixed by heating with a three-roll mill, followed by cooling and grinding. And got the 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 masterbatch having a high pigment concentration without any trouble during the operation.

3 parts of the obtained masterbatch pellets were added to polyethylene terephthalate "Unipet RT543" 1
It was mixed with 100 parts and spun in the same manner as in Example 1. The intrinsic viscosity [η] of the masterbatch-free polyethylene terephthalate was 0.872 dl / g, whereas the [η] of the obtained fiber was 0.550 dl / g, and the intrinsic viscosity retention rate was 8
It was 1.8%. Comparative Example 4 (a) β-Phthalocyanine Blue "Lionol Blue FG7330" 50 parts (b) Copolyester "Vylon GM900" 40 parts (c) Neutralized product of carboxylic acid-containing polyolefin wax "AC polyethylene 285A" 10 parts ( After mixing a) to (c) and heating and mixing with a three-roll mill, an intermediate product was obtained by cooling and grinding. After mixing 60 parts of the obtained intermediate and 40 parts of "Unipet RT543", the mixture was processed with a single-screw extruder to obtain pellet-like high pigment concentration matter batches without any trouble during the operation.

3 parts of the obtained masterbatch pellet was added to polyethylene terephthalate "Unipet RT543" 1
When 100 parts were blended and spinning was tried in the same manner as in Example 1, an increase in reduced pressure was recognized due to poor dispersion of the pigment, and yarn breakage occurred.

[0022]

Industrial Applicability According to the present invention, since the pigment is highly loaded and the dispersibility and the color developability are good, a relatively small amount of polyethylene terephthalate, which is the resin to be colored, may be mixed, so that the physical properties are deteriorated. Also few. Further, since this masterbatch has a pellet shape, it is easy to handle, is extremely useful in a wide range of fiber applications, and has an extremely high industrial value in terms of cost and quality.

Claims (2)

[Claims] 1. A dye 30 to 80 parts by weight, (b) a number average molecular weight of 2000 to 20000, 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) a neutralized product of a carboxylic acid-containing polyolefin wax, 3 to 10 parts by weight, and (d) a partially saponified product of montanic acid 5 ~ 20 parts by weight,
A highly concentrated colored product of a polyester resin. 2. (A) 5 to 80 parts by weight of the highly concentrated polyester resin coloring matter according to claim 1, (B) a number average molecular weight of 20.
A coloring composition for polyester fiber, which comprises 20 to 95 parts by weight of polyethylene terephthalate having a melting point of 2,000 to 30,000 and a melting point of 250 to 260 ° C.