KR101166487B1 - Dyeable polyolefin resin composition with improved dyeability and dye fastness property, dyeable polyolefin fiber, and dyeable polyolefin fabric - Google Patents

Abstract

The present invention relates to a saltable polyolefin-based composite resin composition, and more particularly, to a salt-containing polyolefin-based composite resin composition comprising a specific polyester mixed with a polyolefin, a saltable polyolefin-based composite fiber prepared therefrom, and saltable It relates to a polyolefin-based composite fabric.
Since the salt-containing polyolefin-based composite resin composition according to the present invention has sufficient spinning property, it is possible to smoothly prepare the salt-containing polyolefin-based composite fiber by melt spinning, and the salt-containing polyolefin prepared from the prepared salt-containing polyolefin-based composite fiber. Based composite fabrics have excellent dyeability and color fastness. In addition, the salt-containing polyolefin-based composite fiber prepared from the salt-containing polyolefin-based composite resin composition has water repellency (hydrophobicity) which is an inherent property of the polyolefin fiber when a specific polyester has a range of content.

Description

Dyeable polyolefin resin composition with improved dyeability and dye fastness property, dyeable polyolefin fiber, and dyeable polyolefin-based composite resin composition with improved dyeability and color fastness dyeable polyolefin fabric}

The present invention relates to a salt-containing polyolefin-based composite resin composition, a salt-containing polyolefin-based composite fiber, and a salt-containing polyolefin-based composite fabric prepared therefrom. An improved saltable polyolefin based composite resin composition, a salted polyolefin based composite fiber prepared therefrom, and a salted polyolefin based composite fabric.

Since the Zigler-Natta catalyst made it possible to manufacture highly crystalline polyolefin polymers, especially polypropylene (PP) polymers in 1957, polyolefin fibers, especially PP fibers, began to be developed due to its strength, light weight, and thermal insulation. It was first commercialized by Meraklon, Italy. Contrary to the initial expectations that polyolefin fibers, especially PP fibers, would be as good as nylon or PET fibers, they are still used primarily for carpets and non-clothing nonwovens, and their demand is extremely limited. There is no method of dyeing polyolefin fibers, especially PP fibers. Recently, due to the light weight, heat retention, water repellency, and fast drying properties of polyolefin fibers, in particular, PP fibers, PP fibers have been gradually used for expensive sports and leisure apparel. Commercialization is not yet done.

Currently, a method of imparting color to polyolefin fibers, particularly PP fibers, is not dyeing after fabrication, but an original yarn that gives a color by adding a pigment of a desired color in a spinning process during fiber production. To produce. However, this method is very difficult to apply polyolefin fibers, especially PP fibers, to high value-added apparel products because they are difficult to produce the desired design and various colors, and it is difficult to produce the product immediately in response to the market demand. have.

Efforts to solve such dyeing properties of polyolefin fibers, in particular PP fibers, have been steadily progressed since the 1960s, and several patents have been issued for dyeing polyolefin fibers, especially PP fibers, both domestically and internationally. In particular, research on PP fiber dyeability has been published at several universities in the United States and China. This is a method of reacting or blending polyolefins, especially organic or inorganic materials that can provide dye-sites to PP fibers, on the PP backbone. However, these technologies are still considered to require technical supplementation for commercial scale-up, and there is little mention on whether polyolefin fibers, in particular, PP fibers, such as light weight, water repellency, and heat retention, are in need of technical review. Seems to be. Therefore, commercially available chlorinated polyolefin fibers, especially PP fibers, have not been on the market, which means that most products by techniques known to be developed so far can be used commercially in terms of dyeing and color fastness. It is believed that this is due to the fact that it is impossible to commercialize due to the fact that the production cost is too high or the manufacturing cost is so high.

The reason why polyolefin fibers, especially PP fibers are not dyed is as follows. Firstly, polyolefin fibers, especially PP fibers, have a non-polar paraffin structure, so that there is no dyeing site and the dye cannot stay inside. Secondly, polyolefin fibers, especially PP fibers, are hydrophobic and incapable of water penetration. Therefore, water based dyes cannot easily penetrate into polyolefin fibers, especially PP fibers.

The present invention is derived to solve the conventional problems, one object of the present invention is to facilitate the production of fibers by melt spinning, and excellent dyeability to the general disperse dye or acid dye of the fabric prepared from the fiber In addition, the present invention provides a salt-containing polyolefin-based composite resin composition in which a fabric prepared from the fibers has excellent fastnesses (daylight fastness, washing fastness, friction fastness, etc.). It is also an object of the present invention that the polyolefin fibers, preferably produced by melt spinning, have inherent properties (water repellency, fast drying, lightness, etc.), in particular water repellency (hydrophobic) and physical properties, while at the same time excellent spinning, dyeing and fastness properties It is to provide a salt-containing polyolefin-based composite resin composition to have.

It is another object of the present invention to provide a saltable polyolefin-based composite fiber prepared from the salt-containing polyolefin-based composite resin composition having the above characteristics, and a saltable polyolefin-based composite fabric prepared from the salted polyolefin-based composite fiber. Is in.

In order to solve one object of the present invention, the present invention is 70 to 90% by weight of one or more polyolefin (polyolefin) and polybutylene tere selected from the group consisting of polyethylene, polypropylene, polyisobutylene and copolymers thereof It provides a salt-containing polyolefin-based composite resin composition comprising 10 to 30% by weight of at least one polyester selected from phthalate (polybutylene terephthalate), or polytrimethylene terephthalate (polytrimethylene terephthalate). In this case, the polyolefin is preferably polypropylene, and specifically, the content of polypropylene in the saltable polyolefin-based composite resin composition is 75 to 85% by weight, and more preferably 15 to 25% by weight of polyester.

In addition, in order to solve the object of the present invention, the present invention is 65 to 95% by weight of one or more polyolefins selected from the group consisting of polyethylene, polypropylene, polyisobutylene and copolymers thereof and ethylene glycol A composition comprising 5 to 35% by weight of modified copolymer polyester in which a part of (ethylene glycol) is replaced with another diol, wherein the modified copolymer polyester is based on 100 moles of the first monomer based on the monomer before condensation polymerization. 60 to 95 moles of dimers and 5 to 40 moles of third monomers, the molar sum of the second monomers and the third monomers compared to 100 moles of the first monomer is 100 moles, and the first monomer is terephthalic acid, dimethyl tere At least one dicarboxylic acid selected from phthalate (dimethyl terephthalate), diethyl terephthalate, and isophthalic acid, or Consisting of esters of dicarboxylic acids, the second monomer being ethylene glycol, the third monomer being diethylene glycol, cyclohexane dimethanol, and neopentyl glycol It provides a salt-containing polyolefin-based composite resin composition comprising at least one diol selected from the group consisting of. In this case, the polyolefin is preferably polypropylene, specifically, the content of polypropylene in the saltable polyolefin-based composite resin composition is 70 to 90% by weight, more preferably 10 to 30% by weight of the modified copolyester. Preferably, the modified co-polyester in the saltable polyolefin-based composite resin composition is more preferably composed of 60 to 90 mol of the second monomer and 10 to 40 mol of the third monomer relative to 100 mol of the first monomer on the basis of the monomer before the condensation polymerization.

In order to solve the other object of the present invention, the present invention provides a saltable polyolefin-based composite fiber prepared by melt spinning the above-described salt-containing polyolefin resin composition. At this time, the fibers are characterized in that the short fibers or long fibers.

In order to solve the other object of the present invention, the present invention provides a salt-containing polyolefin-based composite fabric prepared from the above-described salt-containing polyolefin-based composite fibers. In this case, the fabric is characterized in that the woven fabric, knitted fabric, or nonwoven fabric. In addition, the chlorinated polyolefin-based composite fabric according to the present invention may be a film in the form, the fabric of the film form can be produced by extrusion molding (extrusion molding) method using the chlorinated polyolefin-based resin composition as a raw material. Can be.

Since the salt-containing polyolefin-based composite resin composition according to the present invention has sufficient spinning property, it is possible to smoothly prepare the salt-containing polyolefin-based composite fiber by melt spinning, and the salt-containing polyolefin prepared from the prepared salt-containing polyolefin-based composite fiber. Based composite fabrics have excellent dyeability and color fastness. In addition, the salt-containing polyolefin-based composite fiber prepared from the salt-containing polyolefin-based composite resin composition has water repellency (hydrophobicity) which is an inherent property of the polyolefin fiber when a specific polyester has a range of content.

1 is a glycol modified polyethylene terephthalate (Glycol Modified Polyethylene Terephthalate, PETG) in which a part of ethylene glycol is replaced with cyclohexane dimethanol in the modified copolyester constituting the saltable polyolefin-based composite resin composition according to the present invention. ) Shows the chemical structure.

In the present invention, the salt-containing polyolefin-based composite resin composition, the salt-containing polyolefin-based composite fiber, and the salt-containing polyolefin-based composite fabric include polyolefin and polyester, and the polyolefin content is at least 60% by weight, preferably 65% by weight. More preferably, it means 70 weight% or more.

One aspect of the present invention relates to a saltable polyolefin-based composite resin composition.

The saltable polyolefin-based composite resin composition according to the present invention includes, for example, 70 to 90% by weight of one or more polyolefins selected from the group consisting of polyethylene, polypropylene, polyisobutylene, and copolymers thereof, and polybutylene. 10 to 30% by weight of one or more polyesters selected from terephthalate (polybutylene terephthalate (PBT), or polytrimethylene terephthalate (PTT).

When the content of the polyester in the saltable polyolefin-based composite resin composition is less than 10% by weight, the dyeability of the fabric prepared from the fiber prepared by melt spinning the salt-soluble polyolefin-based composite resin composition is significantly decreased, and dyeing such as sunlight fastness or washing fastness The fastness characteristics are also poor and cannot be used as a commercial product. In addition, when the content of the polyester in the saltable polyolefin-based composite resin composition is more than 30% by weight, the radioactivity is very poor, the production of fibers by melt spinning is virtually impossible. Specifically, the content of polyolefin, in particular polypropylene, in the saltable polyolefin-based composite resin composition is preferably 75 to 85% by weight, and the content of polyester is 15 to 25% by weight. It has a K / S value of 3.0 or more, excellent dyeing fastness characteristics such as sunlight fastness or washing fastness. Therefore, a fiber can be manufactured smoothly by fusion spinning. In addition, the polyolefin in the saltable polyolefin-based composite resin composition is preferably characterized in that the polypropylene. Polypropylene has the highest strength and water repellency compared to other olefins, and at the same time has the lowest dyeability, so its use and commercial value are the highest when it gives excellent dyeability to polypropylene fibers. In addition, the polyester in the salt-containing polyolefin-based composite resin composition is characterized in that the polybutylene terephthalate (polybutylene terephthalate). Polybutylene terephthalate is usually condensation polymerization of terephthalic acid (TPA) or dimethyl terephthalate (DMT) with 1,4-butanediol (1,4-butanediol, BD). Polytrimethylene terephthalate prepared by condensation polymerization of terephthalic acid or dimethyl terephthalate with 1,3-propanediol (PD) when mixed with polyolefin Compared with), it gives somewhat higher spinning properties and is more advantageous in terms of fiber strength and K / S value of fabric.

In addition, the salt-containing polyolefin-based composite resin composition according to the present invention is 65 to 95% by weight of one or more polyolefin (polyolefin) and ethylene selected from the group consisting of polyethylene, polypropylene, polyisobutylene and copolymers thereof as another example A composition comprising 5 to 35% by weight of modified copolymer polyester in which a part of ethylene glycol (EG) is replaced with another diol, wherein the modified copolymer polyester comprises a first monomer 100 based on monomers prior to condensation polymerization. The molar sum of the second monomer 60 to 95 moles and the third monomer 5 to 40 moles relative to the mole, the molar sum of the second monomer and the third monomer compared to 100 moles of the first monomer is 100 moles, the first monomer is terephthalic acid (terephthalic acid, TPA), dimethyl terephthalate (DMT), diethyl terephthalate (DET), and at least one selected from isophthalic acid (IPA) Consisting of an ester of dicarboxylic acid or dicarboxylic acid, the second monomer is ethylene glycol, and the third monomer is diethylene glycol (DEG), cyclohexane dimethanol (CHDM) ), And neopentyl glycol (Neopentyl glycol, NPG) is characterized by consisting of one or more diols selected from the group consisting of. The modified copolyester constituting the saltable polyolefin-based composite resin composition according to the present invention is a part of the ethylene glycol used as a monomer of conventional polyethylene terephthalate (PET), or polyethylene isophthalate (other) Substituted with diols to give rheological and thermal properties similar to or compatible with polyolefins, commercially available glycol modified polyethylene terephthalate (PETG). 1 is a glycol modified polyethylene terephthalate (Glycol Modified Polyethylene Terephthalate, PETG) in which a part of ethylene glycol is replaced with cyclohexane dimethanol in the modified copolyester constituting the saltable polyolefin-based composite resin composition according to the present invention. ) Shows the chemical structure.

When the content of the modified copolyester in the saltable polyolefin composite resin composition is less than 5% by weight, the dyeing property of the fabric prepared from the fiber prepared by melt spinning the salted polyolefin composite resin composition is remarkably inferior to daylight fastness or washing fastness. The fastness of dyeing is also poor and cannot be used as a commercial product. In addition, when the content of the modified copolymerized polyester in the saltable polyolefin-based composite resin composition exceeds 35% by weight, the spinning property is very poor, which makes the production of fibers by melt spinning virtually impossible. Specifically, the content of polyolefin, in particular polypropylene, in the saltable polyolefin-based composite resin composition is preferably 70 to 90% by weight, and the content of polyester is 10 to 30% by weight. It has a K / S value of 3.0 or more, excellent dyeing fastness characteristics such as sunlight fastness or washing fastness. Therefore, a fiber can be manufactured smoothly by fusion spinning. In addition, the polyolefin in the saltable polyolefin-based composite resin composition is preferably characterized in that the polypropylene. Polypropylene has the highest strength and water repellency compared to other olefins, and at the same time has the lowest dyeability, so its use and commercial value are the highest when it gives excellent dyeability to polypropylene fibers. In addition, in the saltable polyolefin-based composite resin composition, a group consisting of diethylene glycol, cyclohexane dimethanol, and neopentyl glycol, which constitute the third monomer constituting the modified copolymerized polyester, is The at least one diol selected from is selected from the first monomers terephthalic acid, dimethyl terephthalate, dimethyl terephthalate, diethyl terephthalate, and isophthalic acid. It consists of 5-40 moles of 100 moles of carboxylic acid (dicarboxylic acid) or dicarboxylic acid (dicarboxylic acid). If the content of the third monomer is 5 moles or less of 100 moles of the first monomer, the modified copolymerized polyester is different from the polyolefin. It is difficult to knead during melting because it has properties and thermal properties The content of the modified copolyester required to give the dyeing and dyeing fastness to the composite resin composition is relatively increased, in which case the radioactive and hydrophobic (hydrophobic) of the fiber becomes very poor, and thus the salt-containing polyolefin-based composite resin The composition becomes difficult to use for commercial use. In addition, when the content of the third monomer exceeds 40 moles compared to 100 moles of the first monomer, the adhesion of the salt-containing polyolefin-based composite resin composition is increased, so that the fibers stick together with each other during solidification by cooling after melt spinning, thereby providing a substantially uniform quality. The production of the fibers is not smooth and consequently inferior in economics, resulting in a problem that the strength of the fibers produced by the amorphous increase of the modified copolyester falls below an appropriate level. Considering the overall aspects such as radioactivity, dyeability, dyeing fastness, water repellency (hydrophobicity), quality reliability, and economics, the modified copolyester in the saltable polyolefin-based composite resin composition is compared with 100 moles of the first monomer based on monomers before condensation polymerization. It is preferable that it consists of 60-90 mol of 2nd monomers and 10-40 mol of 3rd monomers. In addition, the third monomer constituting the modified copolymerized polyester in the saltable polyolefin-based composite resin composition is a group consisting of diethylene glycol, cyclohexane dimethanol, and neopentyl glycol. If it is at least one selected from, but not significantly limited, it is preferably characterized in that the neopentyl glycol (Neopentyl glycol). Modified copolymer with the same properties as using neopentyl glycol as tertiary monomer, even with smaller moles of diethylene glycol or cyclohexane dimethanol as tertiary monomer Polyester can be prepared.

Another aspect of the present invention relates to the use of the above-described chlorinated polyolefin-based composite resin composition, and relates to fibers and fabrics.

The saltable polyolefin-based composite resin composition according to the present invention may be prepared into the salt-containing polyolefin-based composite fiber by conventional melt spinning. In this case, the salt-containing polyolefin-based composite fiber may be used as a raw material of the fabric, and is made of short fibers or long fibers, depending on the type of fabric.

The chlorinated polyolefin-based composite fibers, in particular long fibers, according to the present invention can be made into woven or knitted fabrics by conventional weaving or knitting machines. In addition, the chlorinated polyolefin-based composite fibers, in particular short fibers, according to the present invention can be produced into a nonwoven fabric by a conventional nonwoven fabric manufacturing method, for example, thermal bond, spunlace, spunbond, needle punching process, and the like.

In addition, the salt-containing polyolefin composite resin composition according to the present invention may be used to prepare a fabric in the form of a film, wherein the fabric in the form of a film is a method such as extrusion molding using the salt-containing polyolefin-based resin composition as a raw material. It can be prepared through.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only intended to illustrate the present invention more clearly, and do not limit the protection scope of the present invention.

1. Description of Analysis Method

(1) Melt Flow Index (MFI): Measured according to ASTM D1238, load conditions of 230 ° C. and 2.16 kg were used.

(2) Intrinsic viscosity (IV): measured according to KS M ISO 1628-1.

(3) Radioactivity: The frequency of occurrence of partial or total toe trimming was observed for 1 hour continuous melt spinning, and radioactivity was evaluated using 6 scales. The six measures used are as follows.

0 points: No radiation

1 point: more than 1 time

2 points: Not more than 1 time in total

3 points: 3 times of partial trimming

4 points: 3 times of partial trimming

5 points: No abnormality

(4) Fiber strength and elongation: It was measured according to KS K ISO 5079.

(5) Sinking time (hydrophobicity evaluation): Measured according to ERT (EDANA RECOMMENDED TEST METHODS) 10.3-99. When the fiber is placed in a metal net on the surface of the water, the metal net is below the surface within about 15 seconds. It is considered hydrophilic if it sinks into.

(6) K / S value of the fabric: The bath ratio, which is the weight ratio of the dye solution to the fabric, is 1:30 (that is, 30 parts by weight of the dye solution is used based on 100 parts by weight of fabric) and 30 minutes at 130 ° C. Dyeing made a dyed fabric. At this time, the dye solution was composed of 1 part by weight of the dye (disperse dye material, SYNOLON Blue AK product of Kyungin Corporation) and 29 parts by weight of water, and the additive contained 0.25 g / l of dispersant and 0.25 g / l of pH adjuster.

The spectrophotometer (X-Rite, Model SP-B8, USA) was used to measure the surface reflectance at the maximum absorption wavelength of the dyed fabric, and the K / S value was calculated according to the Kubelka-Munk equation below. The larger the / S value, the higher the dyeing concentration, i.e., the better the dyeability.

* K / S = (1-R) ² ÷ (2R) (K: extinction coefficient, S: scattering coefficient, R: reflectance)

(7) Daylight fastness of fabric: It was measured according to KS K ISO 105-B02. The larger the value, the better the daylight fastness.

(8) Wash fastness of fabric: measured according to KS K ISO 105 C06, the larger the value, the better the wash fastness.

2. Caustic Polyolefin  Composite resin composition, Caustic Polyolefin  Composite fiber, end Salt Polyolefin  Manufacture of Composite Fabrics

Example 1.

A salt polyolefin composite resin composition was prepared by melting and mixing 90 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 min and a melting point of about 165 ° C. and 10 parts by weight of polybutylene terephthalate (PBT). Melt-spinning the prepared salt-containing polyolefin composite resin composition by extrusion through a spinneret (spinning temperature: 270 ℃, spinning speed: 1,800 m / min), by supplying cooling air of 16 ℃ to the extruded unstretched yarn ( Feed rate: 2 m / sec). The unstretched yarn solidified by cooling was stretched at a draw ratio of 3.5 times, and then treated with a hydrophobic emulsion for polypropylene fibers (amount of 0.5% by weight based on the weight of the fiber) to prepare fibers having 2 deniers of fineness. Fabrics in the form of knitted fabrics were prepared from the fabrics using a knitting machine.

Example 2.

Except for preparing a salt-containing polyolefin composite resin composition by melting and mixing 85 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 minutes and a melting point of about 165 ° C. and 15 parts by weight of polybutylene terephthalate (PBT). The rest was carried out under the same conditions as in Example 1.

Example 3.

Except for preparing a salt-containing polyolefin composite resin composition by melting and mixing 75 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 minutes and a melting point of about 165 ° C. and 25 parts by weight of polybutylene terephthalate (PBT). The rest was carried out under the same conditions as in Example 1.

Example 4.

Except that the salt flow index was 17 g / 10 min and melt mixed at 70 parts by weight of homopolypropylene having a melting point of about 165 ° C. and 30 parts by weight of polybutylene terephthalate (PBT) to prepare a saltable polyolefin composite resin composition. The rest was carried out under the same conditions as in Example 1.

Comparative Example 1

The rest was performed under the same conditions as in Example 1 except that only homopolypropylene having a melt flow index of 17 g / 10 minutes and a melting point of about 165 ° C. was used instead of the saltable polyolefin composite resin composition.

Comparative Example 2

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight homopolypropylene and 15 parts by weight of polyethylene terephthalate (PET) melt mixed to prepare a salt-containing polyolefin composite resin composition It carried out under the same conditions as in Example 1.

Comparative Example 3

Except that the melt flow index was 17 g / 10 minutes and melt mixed at 85 parts by weight of homopolypropylene with a melting point of about 165 ° C. and 15 parts by weight of polyethylene naphthalate (PEN) to prepare a saltable polyolefin composite resin composition. It carried out under the same conditions as in Example 1.

Comparative Example 4

Except that the salt flow index was 17 g / 10 minutes and melt mixed at 95 parts by weight of homopolypropylene having a melting point of about 165 ℃ and 5 parts by weight of polybutylene terephthalate (PBT) to prepare a saltable polyolefin composite resin composition The rest was carried out under the same conditions as in Example 1.

Comparative Example 5

Except for preparing a salt-containing polyolefin composite resin composition by melting and mixing 65 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 minutes and a melting point of about 165 ° C. and 35 parts by weight of polybutylene terephthalate (PBT). The rest was carried out under the same conditions as in Example 1.

Example 5.

Except that the salt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight of homopolypropylene and 15 parts by weight of polytrimethylene terephthalate (PTT) was melt mixed to prepare a saltable polyolefin composite resin composition The rest was carried out under the same conditions as in Example 1.

Example 6.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 95 parts by weight of homopolypropylene and 5 parts by weight of modified copolymerized polyester # 1 was melt-mixed to prepare a salt-containing polyolefin composite resin composition, except for the It was carried out under the same conditions as 1.

Example 7.

Except that the salt flow index of 17 g / 10 minutes and the melting point of about 165 ℃ 90 parts by weight of homopolypropylene and 10 parts by weight of modified copolymerized polyester # 1 was melt mixed to prepare a salt-containing polyolefin composite resin composition except for It was carried out under the same conditions as 1.

Example 8.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight of homopolypropylene and 15 parts by weight of modified copolymerized polyester # 1 was melt-mixed to prepare a salt-containing polyolefin composite resin composition is an example It was carried out under the same conditions as 1.

Example 9.

Except that 70 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 min and a melting point of about 165 ° C. and 30 parts by weight of modified copolymerized polyester # 1 were melt mixed to prepare a salt-containing polyolefin composite resin composition. It was carried out under the same conditions as 1.

Example 10.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 65 parts by weight of homopolypropylene and 35 parts by weight of modified copolymerized polyester # 1 was melt-mixed to prepare a salt-containing polyolefin composite resin composition, except for the It was carried out under the same conditions as 1.

Comparative Example 6.

Except that 97 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 minutes and a melting point of about 165 ° C. and 3 parts by weight of modified copolymerized polyester # 1 were melt mixed to prepare a saltable polyolefin composite resin composition, except for the following. It was carried out under the same conditions as 1.

Comparative Example 7.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 60 parts by weight of homopolypropylene and 40 parts by weight of modified copolymerized polyester # 1 was melt-mixed to prepare a salt-containing polyolefin composite resin composition is an example It was carried out under the same conditions as 1.

Example 11.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight of homopolypropylene and 15 parts by weight of modified copolymerized polyester # 2 was melt-mixed to prepare a salt-containing polyolefin composite resin composition, the rest of the examples It was carried out under the same conditions as 1.

Example 12.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 95 parts by weight of homopolypropylene and 5 parts by weight of modified copolymerized polyester # 3 was melt mixed to prepare a salt-soluble polyolefin composite resin composition is It was carried out under the same conditions as 1.

Example 13.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight of homo polypropylene and 15 parts by weight of modified copolymerized polyester # 3 was melt mixed to prepare a salt-containing polyolefin composite resin composition is an example It was carried out under the same conditions as 1.

Example 14.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 65 parts by weight of homo polypropylene and 35 parts by weight of modified copolymerized polyester # 3 was melt-mixed to prepare a salt-containing polyolefin composite resin composition except for It was carried out under the same conditions as 1.

Comparative Example 8.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 97 parts by weight of homopolypropylene and 3 parts by weight of modified copolymerized polyester # 3 was melt-mixed to prepare a salt-containing polyolefin composite resin composition except for It was carried out under the same conditions as 1.

Comparative Example 9.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 60 parts by weight of homopolypropylene and 40 parts by weight of modified copolymerized polyester # 3 was melt-mixed to prepare a salt-containing polyolefin composite resin composition is an example It was carried out under the same conditions as 1.

Comparative Example 10.

A salty polyolefin composite resin composition was prepared by melt mixing 85 parts by weight of homopolypropylene having a melt flow index of 17 g / 10 min and a melting point of about 165 ° C. and 15 parts by weight of modified copolymerized polyester # 6. Melt-spinning the prepared salt-containing polyolefin composite resin composition by extrusion through a spinneret (spinning temperature: 270 ℃, spinning speed: 1,800 m / min), by supplying cooling air of 16 ℃ to the extruded unstretched yarn ( Feed rate: 2 m / sec). At this time, the phenomenon of sticking to each other between the fibers during the solidification by cooling after melt spinning, it was not smooth to produce a fiber of substantially uniform quality. After drawing the non-stretched solidified by some non-stick cooling at a draw ratio of 3.5 times, it is treated with a hydrophobic emulsion for polypropylene fibers (amount of 0.5% by weight based on the weight of the fiber) to prepare fibers having a fineness of 2 denier. Prepared. It was 3.3 g / de as a result which measured the strength of the fiber.

The modified co-polyester # 6 used in Comparative Example 10 has 50 moles of ethylene glycol and cyclohexane dimethanol (1,6) compared to 100 moles of terephthalic acid or dimethyl terephthalate on the basis of monomer components before condensation polymerization. -cyclohexane dimethanol) 50 moles. If more than 40 moles of a specific diol replacing a part of ethylene glycol in the modified copolyester, the modified copolyester shows high adhesiveness in the molten state, and thus the fibers stick together in the solidification step by cooling after melt spinning. do. In addition, it is believed that if the specific diols replacing a part of ethylene glycol in the modified copolyester exceeds 40 moles, the amorphousness of the modified copolyester is increased, resulting in a significant drop in the strength of the final fiber.

Example 15.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight of homopolypropylene and 15 parts by weight of modified copolymerized polyester # 4 was melt-mixed to prepare a salt-containing polyolefin composite resin composition except for It was carried out under the same conditions as 1.

Example 16.

Except that the melt flow index of 17 g / 10 minutes and melting point of about 165 ℃ 85 parts by weight of homopolypropylene and 15 parts by weight of modified copolymerized polyester # 5 was melt-mixed to prepare a salt-containing polyolefin composite resin composition except for It was carried out under the same conditions as 1.

Table 1 below shows PET, PBT, PTT, PEN, modified copolymer polyester # 1 (hereinafter referred to as pore pole # 1) to modified copolymer polyester # 5 (hereinafter referred to as pore pole) used in Examples 1 to 16 and Comparative Examples 1 to 9. # 5) shows the monomer component and content ratio (based on 100 moles of TPA or DMT) and their physical property values.

division PET PBT PTT PEN Opening pole # 1 Opening pole # 2 Opening pole # 3 Opening Pole # 4 Opening pole # 5 The number of moles in the monomer component and polyester TPA or DMT 100 100 100 100 100 100 100 100 NDC 100 EG 100 100 95 75 60 75 75 BD 100 PD 100 CHDM 5 25 40 DEG 25 NPG 25 Properties MFI (g / 10 minutes) Not measurable Not measurable Not measurable Not measurable 3.5 3.9 4.5 3.8 17.1 IV (㎗ / g) 0.85 0.80 1.02 0.80 0.79 0.73 0.69 0.74 0.62 Melting point (캜) 265 225 228 255 - - - - -

In Table 1, PEN means polyethylene naphthalate, and NDC means naphthalene dicarboxylic acid of the following chemical structural formula.

As shown in Table 1, the modified copolyesters in which a part of ethylene glycol, a monomer of PET, is replaced with diethylene glycol, cyclohexane dimethanol, or neopentyl glycol It can be seen that the thermal and thermal properties have changed to be in close or identical proximity with the physical properties of the polypropylene.

Table 2 shows the radioactivity, strength, elongation, hydrophobicity (immersion time), dyeing property (K / S value), color fastness (daylight fastness and washing fastness) of the fibers and fabrics prepared in Examples 1 to 16 and Comparative Examples 1 to 9. It is shown.

division Radioactive Fiber properties Fabric properties Strength (g / de) Shinto (%) Immersion time (hr) K / S value Daylight Fastness (Grade) Wash fastness (grade) Example 1 4 4.13 75 24 or more 2.6 3 4 Example 2 4 3.95 82 24 or more 3.3 4 4 Example 3 3 3.59 96 20 hours 3.5 4 5 Example 4 2 3.41 104 10 hours 3.6 4 5 Comparative Example 1 5 4.5 60 24 or more 0 - - Comparative Example 2 0 (non-manufacturing) - - - - - - Comparative Example 3 0 (non-manufacturing) - - - - - - Comparative Example 4 5 4.31 67 24 or more 1.7 One 2 Comparative Example 5 0 (non-manufacturing) - - - - - - Example 5 3 3.85 105 24 or more 3.1 4 4 Example 6 5 4.46 64 24 or more 2.7 3 3 Example 7 5 4.43 68 24 or more 3.1 4 4 Example 8 4 4.39 71 24 or more 3.4 4 4 Example 9 4 4.28 82 24 or more 3.8 5 5 Example 10 3 4.24 86 20 4.1 5 5 Comparative Example 6 5 4.48 63 24 or more 1.8 2 2 Comparative Example 7 0 (non-manufacturing) - - - - - - Example 11 5 4.35 74 Example 12 5 4.43 66 24 or more 3.2 4 4 Example 13 5 4.31 78 24 or more 3.6 4 5 Example 14 3 3.56 102 10 5.4 5 5 Comparative Example 8 5 4.46 64 24 or more 2.2 3 3 Comparative Example 9 0 (non-manufacturing) - - - - - - Example 15 5 4.36 73 24 or more Example 16 5 4.41 64 24 or more 3.8 5 5

As shown in Table 2, a modified copolymer of polypropylene is obtained by replacing a part of ethylene glycol, which is a monomer of PET, with diethylene glycol, cyclohexane dimethanol, or neopentyl glycol. Fibers or fabrics prepared from the caustic polyolefin composite resin composition prepared by mixing with a certain ratio have significantly improved the properties of dyeability and color fastness compared to the fibers or fabrics made of polyolefin only. In addition, dyeability and color fastness even in fibers or fabrics prepared from a salt-containing polyolefin composite resin composition prepared by mixing polybutylene terephthalate or polytrimethylene terephthalate with polypropylene in a proportion. The characteristics of the were improved.

Claims (12)

delete delete delete 65-95% by weight of one or more polyolefins selected from the group consisting of polyethylene, polypropylene, polyisobutylene and copolymers thereof and a portion of ethylene glycol replaced by other diols A composition comprising 5 to 35% by weight of modified modified copolymer polyester,
The modified copolymer polyester is composed of 60 to 95 mol of the second monomer and 5 to 40 mol of the third monomer relative to 100 mol of the first monomer on the basis of the monomer before the condensation polymerization,
The first monomer is at least one dicarboxylic acid or dicarboxylic acid selected from terephthalic acid, dimethyl terephthalate, diethyl terephthalate, and isophthalic acid. consisting of esters of dicarboxylic acids, the second monomer being ethylene glycol, the third monomer being diethylene glycol, 1,6-cyclohexane dimethanol, and neopentyl glycol Salting polyolefin-based composite resin composition, characterized in that consisting of at least one diol selected from the group consisting of.
5. The saltable polyolefin-based composite resin composition according to claim 4, wherein the polyolefin is polypropylene.
The method of claim 5, wherein the content of the polypropylene is 70 to 90% by weight, the content of the modified copolyester is a saltable polyolefin composite resin composition, characterized in that 10 to 30% by weight.
The method according to claim 5, wherein the modified co-polyester is a saltable polyolefin composite resin, characterized in that consisting of 60 to 90 mol of the second monomer and 10 to 40 mol of the third monomer relative to 100 mol of the first monomer on the basis of the monomer before condensation polymerization. Composition.
The salt-containing polyolefin-based composite fiber produced by melt spinning the salt-containing polyolefin-based composite resin composition according to any one of claims 4 to 7.
9. The saltable polyolefin-based composite fiber according to claim 8, wherein the fibers are short fibers or long fibers.
A salt-containing polyolefin-based composite fabric prepared from the salt-containing polyolefin-based composite fiber of claim 8.
11. The salt-resistant polyolefin-based composite fabric according to claim 10, wherein the fabric is a woven fabric, a knitted fabric, or a nonwoven fabric.
A composite fabric prepared from the salt-containing polyolefin-based composite resin composition according to any one of claims 4 to 7, wherein the form is a film.

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