KR100481092B1 - Sea island conjugate fiber having good dying property and color fastness - Google Patents

Abstract

In the present invention, terephthalic acid and ethylene glycol are the main components, and 1,4-cyclohexanedimethanol is composed of 2 to 10 mol% of all diol components, neopentyl glycol, 1,3-propanediol and 1,4-butanediol It relates to an island-in-the-sea composite fiber in which at least one compound selected from is a copolymer of copolymerized polyester having 5 mol% or less of the total diol component, and the composite fiber has excellent deep colorability not only in black but also in various colored colors. It is also excellent in color fastness and can produce high-quality knitted fabrics, and can produce the same color as existing islands-in-the-sea composite fiber even with a small amount of dyes, resulting in dye savings and side effects of reducing dye wastewater. .

Description

Sea island conjugate fiber having good dying property and color fastness {Sea island conjugate fiber having good dying property and color fastness}

The present invention relates to an island-in-the-sea composite fiber, and more particularly, to a polyester-based island-in-the-sea composite fiber having excellent color depth in various colors and excellent color fastness.

The island-in-the-sea composite fiber is produced by complex spinning of these two components using a water-soluble polymer as a sea component and a fiber-forming polymer such as polyester as a island component. Elution in a solution or the like is mainly produced for the purpose of producing ultrafine fibers having a single yarn fineness of 0.1 denier or less.

The island-in-the-sea composite fiber utilizes the flexible and smooth characteristics of ultra-fine fibers and is used in various types of artificial suede, high-grade paper, artificial leather, and silk-like materials. Increasing the specific surface area (specific surface area ∝ 1 / d ^½ , where d is the denier of the fiber) has a limitation that the deep colorability is difficult to express even in the state of fiber saturation dyeing due to the decrease in the apparent dyeing rate.

Many methods have been proposed to improve the drawbacks of dyeing. Among them, the first method is to increase the dyeing amount by increasing the dye concentration during dyeing, but the amount of dye adsorbed on the fiber surface is increased. Therefore, the dyeing fastness is extremely poor below the 1st ~ 2nd level, and it is impossible to manufacture high quality products.In addition, in extreme deep colors such as black, there is a limit of deepening even if the amount of dye is increased. have.

As another method, a method of changing the island component is proposed. There are two main methods to change the island components, one of which is a method of pursuing deepening by using a copolymer copolymerizing a dyeable group in the polymerization step, and the other is a method of using the original component as a island component. to be.

JP-A-60-34611 proposes to introduce a monomer containing a sulfonic acid group such as sodium isophthalate sulfonate by copolymerization. However, this method has a disadvantage in that the physical properties of the yarn are lowered and the alkali hydrolysis resistance of the copolymer is weak, so that the island component is also invaded when dissolving the sea component necessary to obtain the ultra-fine yarn, so the dissolution rate of the sea component needs to be very fast. There is a high possibility of occurrence of joules.

There have been many attempts on copolyesters to lower the crystallinity of polyethylene terephthalates to achieve deepening of polyesters. Attempts to achieve deepening by copolymerizing polyethylene terephthalate with a compound of a third component represented by isophthalic acid, polyethylene glycol, etc., inhibiting the crystallinity of the polyester to allow deepening by disperse dyes, but the opposite dyes Easily come out, that is, there was a problem of poor color fastness. Dyefastness, especially poor washfastness, can be attributed to not only reduced crystallinity but also excessive glass transition temperature.

In particular, attempts to deepen the microfibers represented by the island-in-the-sea composite fiber require the alkali hydrolysis resistance of the polymer because the microfibers are made through the alkali reduction process in the production of the microfibers, but the alkali hydrolysis resistance by copolymerizing existing compounds Cannot meet.

Korean Patent Laid-Open Publication No. 2002-48331 et al proposes a method of containing carbon black, pigments, dyes, and the like in the polyester, which is a component of the coating. Because it is limited to black, other colored colors are difficult to express, and in the case of black, it is difficult to produce a high-quality product because of the bleeding luster. Moreover, the color which can be expressed even if other colored pigments and dyes are added is limited. The island-in-the-sea composite fiber which attempts to deepen the color by containing the original component in the island component is poor in fastness, in particular, the level of friction fastness to the level 2 or below.

Therefore, in view of the above-mentioned problems of the prior art, it is a technical problem to provide an island-in-the-sea composite fiber having excellent deep colorability and excellent dyeing fastness not only in black but also in various colored colors.

In order to solve the above problems, the present inventors have studied the island-in-the-sea composite fiber which can be deeply colored in various colors without lowering the color fastness, and has excellent alkali hydrolysis resistance as a island component of the island-in-the-sea composite fiber. It has been found that this can be achieved by using copolyesters having a glass transition temperature and a suitable melting temperature.

Therefore, according to the present invention, in the island-in-the-sea composite fiber wherein the sea component is an alkali-soluble polymer and the island component is a polyester having a main repeating unit of polyethylene terephthalate, the island component is 90% by mole or more of the total acid component of terephthalic acid, 4-cyclo hexanedimethanol comprises 2 to 10 mol% of the total diol component, at least one compound selected from the group consisting of neopentyl glycol, 1,3-propanediol and 1,4-butanediol is 5 mol% of the total diol component An island-in-the-sea composite fiber is provided which is a copolymerized copolymerized polyester.

Hereinafter, the present invention will be described in more detail.

The island-in-the-sea composite fiber of the present invention is a polyester having terephthalic acid as a main acid component and ethylene glycol as a main diol component, wherein terephthalic acid is 90 mol% or more of all acid components and 1,4-cyclohexanedimethanol is a total diol component. Consists of a copolyester copolymer of at least 5 mol% of all diol components of at least one compound selected from the group consisting of 2 to 10 mol%, neopentyl glycol, 1,3-propanediol and 1,4-butanediol There is a main feature to letting. The copolyester is very suitable for deepening, has excellent alkali hydrolysis resistance, and there is no problem of processability even if it is made of a composite fiber even if there is no decrease in glass transition temperature, and color fastness is also excellent.

In the island-in-the-sea composite fiber of the present invention, the copolyester constituting the island component includes terephthalic acid as a main acid component and ethylene glycol as a main diol component.

As the acid component of the copolyester, terephthalic acid is 90 mol% or more of the total acid component, and isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and its ester-forming derivatives are used as acid components other than lephthalic acid. It may also be used in an amount of 10 mol% or less per minute.

In particular, as the diol component of the copolymerized polyester, ethylene glycol must contain 85 mol% or more of the total diol component, and 1,4-cyclohexanedimethanol needs to contain 2 to 10 mol% of the total diol component. It is necessary to contain 5 mol% or less of the total diol components of at least one compound selected from the group consisting of neopentyl glycol, 1,3-propanediol and 1,4-butanediol in order not to inhibit coloration and alkali hydrolysis resistance. have.

If the content of 1,4-cyclohexanedimethanol in the total diol components is less than 2 mol%, the deep color expression is insufficient. If the content exceeds 10 mol%, there is a deep color effect, but the shrinkage rate is excessive, raising the surface of the knitted fabric. As the effect decreases and the surface feel becomes rough, and the melting temperature of the copolyester becomes 220 ° C. or lower, problems such as fusion of the island component polyester during post-processing, especially in the heat setting process, occur, and the brushing effect is greatly reduced and the touch is felt. This roughening problem arises.

In addition, when the content of at least one compound selected from the group consisting of neopentyl glycol, 1,3-propanediol and 1,4-butanediol in the total diol exceeds 5 mol%, the glass transition temperature and melting temperature of the copolyester are increased. Since the wash fastness and the friction fastness may be lowered and the process control in post-processing may be difficult because it is lowered, it is not preferable.

In addition to the diol component, diethylene glycol, polyethylene glycol, bisphenol derivatives and the like may be contained within the range not impairing the physical properties of the copolyester.

The copolyester used as the island component in the island-in-the-sea composite fiber of the present invention may contain a crosslinking agent such as trimellitic acid, pentaerythritol, and trimethyl propane within a range in which the polyester is substantially linear.

In addition, the copolymerized polyester may contain other thermoplastic polymers within a range that does not impair the effects and functions of the present invention, or may be ultraviolet absorbers, heat resistant agents, fluorescent agents, antioxidants, quenchers, antistatic agents, flame retardants, lubricants, and plasticizers. Or other conventional additives such as inorganic fine particles.

The copolyester may be produced by a conventional polymerization method which is generally employed to produce a conventional polyester such as polyethylene terephthalate. For example, an acid component and a diol are esterified or transesterified to polymerize a polyester having a low degree of polymerization, and the polyester is subjected to a polycondensation reaction at a temperature of 230 to 300 ° C. under reduced pressure using a polymerization catalyst such as antimony trioxide. To produce a copolyester having a desired degree of polymerization.

Co-polyester used as the island component in the island-in-the-sea composite fiber of the present invention has an IV of at least 0.4 dl / g, preferably 0.4 to 0.9 dl / g, more preferably 0.53 to 0.70 dl / g. In order to be preferable.

It is preferable that the said copolymer polyester has a glass transition temperature of 70 degreeC or more. If the glass transition temperature is less than 70 ℃, there is a problem that the wash fastness and friction fastness after dyeing of the knitted fabric of the island-in-the-sea composite fiber in which the copolyester is used as a coating component.

Moreover, it is preferable that the melting temperature of the said copolyester is 220 degreeC-250 degreeC. If the melting temperature is lower than 220 ℃, it is difficult to select the appropriate spinning conditions such as spinning temperature in consideration of the cross-sectional formability and the physical properties of the composite fiber in the manufacturing of island-in-the-sea composite fiber, it is difficult to control the process in the post-processing. In particular, in the heat setting process of the knitted fabric, a problem arises in that the island component composed of the copolyester is fused, and thus, soft touch, which is an advantage of the island-in-the-sea microfiber knitted fabric, is difficult to be developed.

The island-in-the-sea composite fiber of the present invention uses the above-mentioned copolyester as a seaweed component and uses a conventional alkali-soluble polymer as the seaweed component to form a seaweed component and seaweed components in a ratio of 50/50 to 80/20% by weight. It is preferable to manufacture using an island-in-the-sea composite fiber spinning facility. The manufacturing method may be a direct-stretching method of spinning at high speed, and after producing undrawn or partially drawn yarn with a spinning speed of 800 to 3,500 m / min, drawing using conventional methods You can also use a method of making shrines or false twisted yarns.

The island-in-the-sea composite fiber of the present invention can be used in the form of filament, staples and the like. The island-in-the-sea composite fiber may be used alone or in a twisted yarn alone, or may be used in the form of a combustible composite yarn of the island-in-the-sea composite fiber and a high shrink yarn having a non-shrinkage ratio of 15% or more.

The island-in-the-sea composite fiber of the present invention preferably has a single yarn fineness of 2 to 5 deniers prior to sea component elution, and a single yarn fineness of 0.001 to 0.1 denier after sea component elution. Single yarn fineness after sea component elution is preferably 0.01 to 0.1 denier, and more preferably 0.03 to 0.08 denier. However, the single yarn fineness and the total fineness before and after dissolution are not necessarily limited.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

The measurement method of the evaluation item shown in the following Example is as follows.

1. Content (mol%) of the compound added to the copolymerized polyester: Content (mol%) of the compound copolymerized to the copolymerized polyester was dissolved in trifluoroacetic acid, and the Bruker DRX-300 Measurements were made using a proton nuclear magnetic resonance apparatus ( ¹ H NMR).

2. Glass transition temperature and melting point: The glass transition temperature and melting point were measured using a differential scanning calorimeter (Perkin Elmer DSC-7).

3. Intrinsic Viscosity (IV): Chips were made using a mixed solution of phenol / tetrachloroethane (weight ratio 50/50) and measured at 25 ° C. with a Uberod viscometer.

4. Feel: The touch of all finished knitted fabrics such as weight loss, dyeing and brushing was evaluated by sensory evaluation method by 5 experts in 3 levels of excellent and normal. Specifically, when four or more were judged to be good, three were judged to be good, and two or less were judged to be poor when judged to be good.

5. Dyeability Evaluation: Dyeability was evaluated by the L value obtained by measuring all processed knitted fabrics such as weight loss, dyeing and brushing with a colorimeter (Macbeth coloreye 3000) or K / S value at the maximum absorption wavelength. In this case, the K / S value is calculated as (1-R) ² / 2R, where R is the reflectance), and the higher the value, the deeper the color. The lower the value, the lower the brightness is. do. Colorimetric conditions were used with a 10 ° standard observer under a D65 light source.

6. Dyeing fastness evaluation

Dyeing fastness was measured and evaluated according to the following Korean Industrial Standards (KS).

-Wash Fastness: KS K 0430-A2

-Friction fastness: KS K 0650

Daylight fastness: KS K 0218

Example 1

Terephthalic acid was used as the acid component, and 89 mol% of ethylene glycol, 8 mol% of 1,4-cyclohexanedimethanol and 3 mol% of neopentyl glycol were used in the total diol component, and the molar ratio of the diol component and terephthalic acid was 1.2: 1. A slurry was formed, and zinc acetate was added as a catalyst to the slurry, followed by esterification at a temperature of 250 ° C. under a pressurization until the esterification rate was 95%, thereby polymerizing low-polymerization copolyester, followed by condensation polymerization. Copolyester of IV 0.65 level was prepared by polycondensation at a temperature of 280 ° C. under reduced pressure using 300 ppm of antimony trioxide and a stabilizer as a catalyst.

Using the prepared copolyester as a seaweed component, and using the alkali-soluble polyester of IV 0.6 copolymerized with an organic sulfonic acid metal salt and polyethylene glycol as the sea component, the seaweed component and the seaweed component in a ratio of 70/30 weight ratio Using a conventional island-in-the-sea composite spinning device, a pre-oriented yarn was prepared at a speed of 3000 m / min. This partially oriented yarn was combusted at a draw ratio of 1.6 and a burning rate of 400 m / min, and a high-yielding yarn with a non-shrinkage rate of 15% was combined to produce a 160d / 36f combustible composite yarn. This weaving composite yarn was used for finishing after weaving into a fabric, such as weight loss, dyeing, and brushing. Dyeing was done in two colors: black [use Lumacron Black RD-3G (made by LG Chem; Korea) as dye] and brown [use Terasil Y / R / B mixed dye (Shibagagi; Germany) as dye]. In black dyeing, dye concentration was 8% owf, deep color was evaluated by L value, brown color dye was dye concentration 8% owf, and deep color was evaluated by K / S value.

[Examples 2 to 5]

Except having changed the composition of the copolyester used as a island component as shown in Table 1, it carried out similarly to Example 1.

Example 6

 The co-polyester prepared by polymerization in the same manner as in Example 1 is used as a coating component, and an alkali-soluble polyester which is generally used as a sea component is used. Using the island-in-the-sea composite spinning device, a composite fiber was prepared by the radial direct drawing method at a spinning speed of 4100 m / min. Combustible composite yarn was prepared by compounding the island-in-the-sea composite fiber with a draw ratio of 1.005 and a burning rate of 400 m / min, and high shrink yarn having a specific shrinkage rate of 15%. This weaving composite yarn was used to finish post-processing such as weight loss, dyeing, brushing after weaving. Since the evaluation was carried out in the same manner as in Example 1.

Example 7

 The island-in-the-sea composite fiber prepared by the radial direct drawing method as in Example 6 was knitted with a warp knit, and then finished in post processing, and evaluated in the same manner as in Example 1.

Comparative Example 1

The same procedure as in Example 1 was carried out except that general polyethylene terephthalate was used as the island component.

Comparative Example 2

In order to express the same deep color as the deep color of the knitted fabric using the island-in-the-sea composite fiber of the present invention, the dye concentration was 14% o.w.f at the time of dyeing in the same manner as in Comparative Example 1.

[Comparative Examples 3 to 4]

Except having changed the composition of the copolyester used as a island component as shown in Table 1, it carried out similarly to Example 1.

[Comparative Example 5]

Except that terephthalic acid was used as acid component and diol component was polymerized with IV 0.65 as polymer as the main component, which was polymerized with ethylene glycol as a main component and polyethylene glycol having a molecular weight of 2000 at 10% by weight. It was.

The evaluation results of the physical properties of the polyester used in the components in the above Examples and Comparative Examples are shown in Table 1, and the evaluation results of the texture and color fastness and color fastness of the knitted fabric when the black color dye is used. The results of the evaluation of color depth and color fastness at the time of brown color staining are shown in Table 2.

division IV Acid component (% water) Diol component (mol%) Tg (℃) Tm (℃) TPA IPA EG CHDM NPG PEG Example One 0.65 100 - 89 8 3 - 76 230 2 0.63 100 - 92 8 - - 79 236 3 0.64 100 - 93 5 2 - 77 240 4 0.65 100 - 93 2 5 - 76 235 5 0.63 98 2 89 8 3 - 73 225 Comparative example 1,2 0.64 100 - 100 - - - 78 255 3 0.65 100 - 99 One - - 78 251 4 0.68 100 - 87 13 - - 79 218 5 0.65 100 - 10wt% 68 220  TPA: terephthalic acid, IPA: isophthalic acid, EG: ethylene glycol, CHDM: 1,4-cyclohexanedimethanol, * NPG: neopentyl glycol PEG: polyethylene glycol, Tg: glass transition temperature, Tm: melting temperature

division Feel, color, and color fastness of knitted fabric in black dyeing touch Deep color (L value) Color fastness Laundry Friction (dry / wet) daylight Example One Great 12.2 3 to 4 4/3 3 to 4 2 Great 13.0 3 to 4 4/3 4 3 usually 13.1 3 to 4 4/3 4 4 usually 13.8 3 to 4 4/3 4 5 usually 11.9 3 to 4 3 to 4/3 3 to 4 6 Great 12.4 3 to 4 4/3 3 to 4 7 Great 11.2 3 to 4 4/3 3 to 4 Comparative example One usually 17.6 2-3 3 to 4/3 3 to 4 2 usually 14.0 1 to 2 2 to 3/1 to 2 3 3 usually 15.8 3 to 4 4/3 4 4 Bad 12.1 2-3 3 to 4/3 3 5 Bad 14.6 1 to 2 2/1 3

division Tactile texture, deep color and color fastness Deep color (K / S value) Color fastness Laundry Friction (dry / wet) daylight Example One 26.0 3 to 4 4/3 3 to 4 2 25.2 3 to 4 4/3 4 3 23.6 3 to 4 4/3 4 4 22.8 3 to 4 4/3 4 5 26.4 3 to 4 3 to 4/3 3 to 4 6 25.4 4 4/3 3 to 4 7 27.2 4 4/3 3 to 4 Comparative example One 18.5 2-3 4/3 4 2 22.7 1 to 2 3/2 3 3 21.2 4 4/3 4 4 26.6 2-3 3 to 4/3 3 5 21.6 3 3/2 3

The island-in-the-sea composite fiber of the present invention significantly improves the problems of existing microfibers, and can produce high-quality knitted fabrics with excellent deep colorability and excellent dyeing fastness in not only black but also various colored colors, and also less dyes. The amount can express the same color as the existing islands-in-the-sea composite fiber, and can have a side effect of reducing dyes and reducing wastewater.

Claims (5)

In the island-in-the-sea composite fiber wherein the sea component is an alkali-soluble polymer and the island component is a polyester in which the main repeating unit is polyethylene terephthalate, the island component is 90% by mole or more of the total acid component of terephthalic acid and 1,4-cyclohexanedi Copolymerized poly copolymers in which at least one compound selected from the group consisting of 2 to 10 mol% of methanol, neopentyl glycol, 1,3-propanediol and 1,4-butanediol is copolymerized to 5 mol% or less of the total diol components Island-in-the-sea composite fiber, characterized in that the ester. The islands-in-the-sea composite fiber of Claim 1 whose glass transition temperature of co-polyester which is a island component is 70 degreeC or more. 2. The island-in-the-sea composite fiber according to claim 1, wherein the melting temperature of the copolyester as an island component is 220 ° C to 250 ° C. A woven fabric characterized in that it is produced using the island-in-the-sea composite fiber of claim 1. 5. The knitted fabric of claim 4 wherein the L value is less than 14 when black dyeing at a dye concentration of 8% o.w.f.