JP5912669B2 - Cationic dye-dyeable flame retardant polyester fiber and its fiber products - Google Patents

Description

  The present invention relates to a cationic dyeable flame retardant polyester fiber having cationic dye dyeability and flame retardancy.

  Polyester fibers typified by polyethylene terephthalate fibers are widely used in clothing and industrial applications because of their excellent heat resistance, chemical resistance and mechanical properties. However, since polyester fibers have a strong fiber structure, dyeing usually has to be performed under high temperature and high pressure, which is problematic in terms of energy cost.

  Conventionally, in order to improve the dyeability of polyester fibers, many methods for improving the dyeability by modifying the polyester polymer have been proposed. For example, a metal sulfonate group-containing acid component such as 5-sodiumsulfoisophthalic acid has been proposed. A method of imparting dyeability with a cationic dye by copolymerizing with polyester is known (Patent Document 1). Also, in addition to metal sulfonate group-containing acid components such as 5-sodium sulfoisophthalic acid, an acid component such as adipic acid is copolymerized with polyester to provide dyeability that can be dyed at normal pressure with disperse dyes and cationic dyes. The method of doing is also known (patent document 2).

On the other hand, there is a demand for flame resistance to textile products such as curtains (including shower curtains and lace curtains), bedding, wall cloths, inkjet cloths and carpets, and polyester fibers used in these textile products are also required. Of course, flame retardancy is required. Particularly in the field of these textile products, in addition to flame retardancy, in order to make the dyed product vivid, dyeing properties that can be dyed at normal pressure with disperse dyes and cationic dyes are also required for polyester fibers. Polyester fibers obtained by copolymerizing a sulfonate group-containing acid component or the like have a problem that they are easily irritated and have limited applications.

  In addition, flame retardant and cationic dyes can be used using a polyester polymer obtained by copolymerizing a metal sulfonate-containing compound in an amount of 0.5 to 5 mol% and a phosphorus flame retardant with a content of 5000 to 15000 ppm based on phosphorus atoms. It is known to use a dyeable polyester fiber (Patent Document 3). However, this flame retardant cationic dye dyeable polyester fiber can be dyed with a cationic dye, but is insufficient in terms of atmospheric pressure dyeability.

Japanese Patent Publication No.34-10497 JP-A-8-269820 Japanese Patent Laid-Open No. 2005-273043

  The present invention has been made by further study and improvement in view of the state of modification of conventional polyester polymers. The object of the present invention is to achieve excellent dyeability and excellent difficulty for cationic dyes at normal pressure. A cationic dye-dyeable flame-retardant polyester fiber having flame retardancy is provided, and another object of the present invention is to provide a textile product using the cationic dye-dyeable flame-retardant polyester fiber.

The gist of the first invention of the present invention is that a polyester whose main repeating unit is ethylene terephthalate, an alkali metal salt of sulfoisophthalic acid, an aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and a phosphorus-based flame retardant are the following conditions (a ), (B), and (c), a cationic dye-dyeable flame retardant polyester fiber composed of a copolyester resin copolymerized.
(A) 0.8 ≦ S ≦ 3.0
(B) 3.0 ≦ A ≦ 10.0
(C) 3000 ≦ P ≦ 10000
(Wherein S is the copolymerization amount (mol%) of the alkali metal salt of sulfoisophthalic acid, A is the copolymerization amount (mol%) of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and P is the phosphorus-based difficulty. (Shows the amount of copolymerization (ppm) based on the phosphorus atom of the flame retardant)
The gist of the second invention of the present invention resides in a fiber product using the cationic dye-dyeable flame retardant polyester fiber.

  The cationic dye-dyeable flame retardant polyester fiber of the present invention has a cation formed by copolymerization of an alkali metal salt of sulfoisophthalic acid and an aliphatic dicarboxylic acid having 4 to 10 carbon atoms in a polymer of the resin having the constitution. It exhibits excellent dyeability for dyes and exhibits good dyeability when dyed at normal pressure. Further, the cationic dye-dyeable flame retardant polyester fiber of the present invention exhibits excellent flame retardancy that contains a phosphorus flame retardant in the polymer and is difficult to spread. Furthermore, in the production of the cationic dye-dyeable flame retardant polyester fiber of the present invention, the fiber property and workability can be obtained without fusion in the spinning process and the yarn making process, and the cationic dye-dyeable flame retardant polyester can be obtained. Fiber is widely used as a textile product.

Hereinafter, embodiments of the present invention will be described in detail.
<Copolymerized polyester resin>
In the present invention, the copolyester resin constituting the cationic dye-dyeable flame retardant polyester fiber is a polyester whose main repeating unit is ethylene terephthalate, and an alkali metal salt of sulfoisophthalic acid is 0.8 to 3.0 mol%. The polyester resin is a copolymerized polyester resin having a content of 3.0 to 10.0 mol% of an aliphatic dicarboxylic acid having 4 to 10 carbon atoms and a phosphorus flame retardant content of 3000 to 10000 ppm based on a phosphorus atom.

<Alkali metal salt of sulfoisophthalic acid>
The alkali metal salt of sulfoisophthalic acid in the copolymerized polyester resin provides a dyeing seat for the cationic dye to obtain a dyeing property by the cationic dye, and the copolymerization amount is 0.8 to 3.0 mol. %, Preferably 1.5 to 2.5 mol%. If the copolymerization amount of the alkali metal salt of sulfoisophthalic acid is less than 0.8 mol%, not only the dyeing seat of the cationic dye is insufficient, but the dyeing amount is reduced, and the sharpness peculiar to the cationic dye is also poor. . When the copolymerization amount of the alkali metal salt of sulfoisophthalic acid exceeds 3.0 mol%, the melt viscosity of the polymer is increased during the polymerization, and only a low-viscosity polymer is obtained. As a result, spinning is performed. The fiber has a reduced fiber strength.

  Examples of the alkali metal salt of sulfoisophthalic acid include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5-rubidium sulfoisophthalic acid, and 5-cesium sulfoisophthalic acid. Particularly preferred is 5-sodium sulfoisophthalic acid. Moreover, you may use together alkaline earth metal salts, such as magnesium and calcium, with the alkali metal salt of sulfo isophthalic acid as needed.

<C4-C10 aliphatic dicarboxylic acid>
The aliphatic dicarboxylic acid having 4 to 10 carbon atoms in the copolyester resin gives an appropriate disorder to the amorphous structure of the fiber, facilitates the ingress of the dye, and contributes to the improvement of the dyeability. Is required to be 3.0 to 10.0 mol%, preferably 4.0 to 7.0 mol%. When the copolymerization amount of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms is less than 3.0 mol%, the dyeability in atmospheric dyeing is lowered. Moreover, when the copolymerization amount of aliphatic dicarboxylic acid having 4 to 10 carbon atoms exceeds 10.0 mol%, the glass transition temperature and melting point of the polymer are lowered, and mechanical properties and friction fastness required for fibers or fiber products are reduced. Insufficient heat resistance.

  Examples of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and these may be used alone or in combination. A particularly preferred aliphatic dicarboxylic acid in the present invention is adipic acid.

<Phosphorus flame retardant>
In addition, the copolymerized polyester resin is copolymerized so that a non-halogen-based phosphorus flame retardant that reduces the burden on the environment and imparts flame retardancy is contained in an amount of 3000 to 10,000 ppm based on phosphorus atoms. It is necessary to If the phosphorus atom content of the phosphorus flame retardant in the polymer is less than 3000 ppm, effective flame retardancy cannot be obtained, and if it exceeds 10,000 ppm, the flame retardancy is excellent, but not only the production cost is increased. In addition, it becomes difficult to stably produce the polymer and the fiber.

  In the present invention, as a particularly preferable phosphorus-based flame retardant, a phosphorus compound represented by the following general formula (1) can be mentioned, and when combined with the metal sulfonate isophthalic acid and the aliphatic dicarboxylic acid, a durable flame retardant Sex can be obtained.

(In the formula, R ₁ is a hydrogen atom or a C1-C8 hydroxyalkyl group)

<Physical properties of copolymer polyester resin>
The copolymer polyester resin constituting the cationic dye-dyeable flame retardant polyester fiber of the present invention preferably has a glass transition temperature of 60 to 70 ° C and a melting point of 215 to 240 ° C. When the glass transition temperature is 60 to 70 ° C. and the melting point is 215 to 240 ° C., the dyeability in atmospheric dyeing is good, and the mechanical properties, fastness, heat resistance, and the like necessary for a fiber product are good.

<Manufacture of copolyester resin>
The copolyester resin in the present invention can be produced, for example, as follows.
That is, terephthalic acid and ethylene glycol are directly esterified or terephthalic acid dimethyl ester and ethylene glycol are transesterified to synthesize oligomers of bishydroxylethyl terephthalate and its low polymer, and then into the reaction system. After adding a predetermined amount of an alkali metal salt of sulfoisophthalic acid, an aliphatic dicarboxylic acid having 4 to 10 carbon atoms and a phosphorus flame retardant as copolymerization components, a polycondensation reaction is started.

  Addition of alkali metal salt of sulfoisophthalic acid, aliphatic dicarboxylic acid having 4 to 10 carbon atoms and phosphorus-based flame retardant may be performed by dispersing in ethylene glycol, or added as an ethylene glycol solution as an ethylene glycol ester. May be.

  The polycondensation reaction is performed using a polycondensation catalyst such as antimony trioxide and germanium dioxide until the intrinsic viscosity of the polymer produced at a high temperature under reduced pressure becomes 0.55 to 0.65. In addition, at any stage of the polymerization, other copolymer components may be added and copolymerized as necessary, or additives such as antioxidants, fluorescent agents, matting agents, and light resistance improvers may be added. May be. After completion of the polycondensation reaction, the taken copolymer resin is pelleted and dried.

<Manufacture of cationic dye dyeable flame retardant polyester fiber>
When making a fiber using a copolyester resin, it is melt-spun at a temperature higher than the melting point of the copolyester resin and stretched by the same melt spinning method as that for producing a normal polyester fiber. Yarn processing such as false twisting is applied to obtain a fiber in a form suitable for obtaining a fiber product. There is no restriction | limiting in particular about the fiber cross-sectional shape at the time of making a fiber, a fineness, etc.

<Fiber products using cationic dyeable flame retardant polyester fiber>
The cationic dye-dyeable flame retardant polyester fiber of the present invention can be used for textile products such as curtains, bedding, carpets and wall cloths. In making a textile product, the cationic dye dyeable flame retardant polyester fiber of the present invention may be used alone, or in combination with other fibers within a range that does not impair the dyeability and flame retardancy by the cationic dye, Glossy feeling, cool feeling, sharp feeling, wet feeling and the like can be imparted.

  Hereinafter, the present invention will be specifically described by way of examples. The measurement items in the examples were based on the following method.

<Phosphorus atom (P) content>
Quantification was carried out by fluorescent X-ray method using a lightning X-ray spectrometer model 3270 manufactured by Rigaku Corporation.

<Flame retardance>
It was measured by JIS L1091 D method (45 degree coil method).
In the method D, a sample specimen is prepared so as to be 100 mm and 1 g, and the number of times of flame contact until the specimen becomes 10 mm is measured. The number of times of measurement is 5 times, and in each measurement, if the number of flame contact until reaching 10 mm is all 3 times or more, it is acceptable (O), and the number of flame contact is 2 even in one of the five test specimens. If it is less than or equal to the number of times, it will be rejected (x).

<Intrinsic viscosity [η]>
0.25 g of copolyester resin was pulverized, dissolved in 50 ml of a mixed solvent of phenol / tetrachloroethane (50/50), and temperature-controlled at 25 ° C. (manufactured by Sun Electronics Co., Ltd., AVL-4 type) Measured with The calculation formula is as follows.
[Η] = {(1 + 1.04ηsp) 1/2 −1} /0.26

<Glass transition temperature (Tg) and melting point>
The Tg (° C.) and the melting point (° C.) of the copolyester resin were measured using a DSC220 manufactured by Seiko Denshi Kogyo Co., Ltd. at a temperature rising rate of 10 ° C./min.

<Cationic dye dyeability>
Dye bath with cationic dye (AIZEN CATHILON MARINE BLUE GPLH manufactured by Hodogaya Chemical Co., Ltd.) at a concentration of 1.5% owf (for fiber mass) and dyeing under normal pressure at a temperature of 98 ° C. for 60 minutes. Judging by the property, it was evaluated in four stages of ◎, ○, Δ, and × from superior to inferior.

Example 1
(1) A slurry having a molar ratio of terephthalic acid (hereinafter abbreviated as TPA) and ethylene glycol (hereinafter abbreviated as EG) to 1/1. An esterification reaction was performed. As a result, a polyester oligomer having a reaction rate of 95% was obtained. Subsequently, the obtained polyester oligomer was transferred to a polycondensation reaction can.
(2) An EG dispersion of adipic acid (hereinafter abbreviated as AD) is added to the polycondensation reaction vessel so that the AD concentration in the polymer is 5 mol%, and R in the chemical formula (1) is added. _When the phosphorus flame retardant _{1 in} which ₁ is a hydroxyethyl (CH ₂ CH ₂ OH) group is used as an EG solution adjusted to a concentration of 60% by mass, the content of phosphorus atoms (P) in the resulting polymer is 6000 ppm. Was added as follows.
(3) Triethyl phosphate is added to the polycondensation reaction can as a color tone adjusting agent, and an EG solution of EG ester of 5-sodiumsulfoisophthalic acid (hereinafter abbreviated as DMS) is further added to the DMS concentration in the polymer. It added so that it might become 1.75 mol%.
(4) Further, antimony trioxide was added to the polycondensation reaction can as a polycondensation catalyst, and polycondensation was performed under reduced pressure to obtain a copolymer polyester resin. The obtained copolyester resin was used as a chip and dried by a conventional method. Table 1 shows the characteristic values of the resin.
(5) Next, using the obtained polyester polyester resin pellets as a raw material and using a spinning device in which a spinneret of a 36-hole circular spinning hole was installed, a spinning temperature of 260 ° C., a spinning speed of 2000 m / The resulting undrawn yarn was drawn at a drawing speed of 600 m / min, a drawing temperature of 78 ° C., a heat setting temperature of 145 ° C., and a maximum drawing ratio of 0.73 times to obtain a polyester fiber of 84 dtex / 36 filaments. Obtained.
(6) A knitted fabric was prepared from the obtained polyester fiber with a 20-gauge cylinder knitting machine, and a flame test was performed to measure flame retardancy. Further, the dyeability of the obtained knitted fabric was evaluated, and the results are shown in Table 1.

(Examples 2-5 and Comparative Examples 1-3)
In Example 1, a copolymer polyester resin was obtained in the same manner as in Example 1 except that the addition amounts of DMS, AD and phosphorus flame retardant (as P) were changed as shown in Table 1. A polyester fiber was obtained by melt spinning using the obtained copolyester resin. A knitted fabric was prepared from the obtained fibers, the flame retardancy was measured, and the dyeability of the cationic dye was evaluated. The results are shown in Table 1.

  The cationic dye-dyeable flame retardant polyester fiber of the present invention is a textile product such as a curtain, bedding, carpet, wall cloth, etc., which can exhibit the sharpness and leveling excellent dyeing property and flame retardancy with the cationic dye. If it is a field where dyeability and flame retardancy are required, it is also useful for clothing.

Claims (4)

Polyester whose main repeating unit is ethylene terephthalate, alkali metal salt of sulfoisophthalic acid, aliphatic dicarboxylic acid having 4 to 10 carbon atoms and phosphorus flame retardant satisfy the following conditions (a), (b) and (c) A cationic dye-dyeable flame retardant polyester fiber composed of a copolyester resin which is a resin having a melting point of 215 to 240 ° C.
(A) 0.8 ≦ S ≦ 3.0
(B) 3.0 ≦ A ≦ 10.0
(C) 3000 ≦ P ≦ 10000
(Wherein S is the copolymerization amount (mol%) of the alkali metal salt of sulfoisophthalic acid, A is the copolymerization amount (mol%) of the aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and P is the phosphorus-based difficulty. (Shows the amount of copolymerization (ppm) based on the phosphorus atom of the flame retardant) The cationic dye-dyeable flame retardant polyester fiber according to claim 1, wherein the phosphorus flame retardant is a phosphorus compound represented by the following chemical formula (1).
(In the formula, R ₁ is a hydrogen atom or a C1-C8 hydroxyalkyl group) The cationic dyeable dyeable flame retardant polyester fiber according to claim 1 or 2, wherein the copolyester resin is a resin having a glass transition temperature of 60 to 70 ° C. A fiber product using the cationic dye-dyeable flame retardant polyester fiber according to any one of claims 1 to 3.