WO1999009238A1

WO1999009238A1 - Polyester fiber and fabric prepared therefrom

Info

Publication number: WO1999009238A1
Application number: PCT/JP1998/003660
Authority: WO
Inventors: Jinichiro Kato; Katsuhiro Fujimoto
Original assignee: Asahi Kasei Kogyo Kabushiki Kaisha
Priority date: 1997-08-18
Filing date: 1998-08-18
Publication date: 1999-02-25
Also published as: KR100359347B1; DE69837169T2; DE69837169D1; EP1489206A2; KR20010022988A; ES2278255T3; EP1006220A1; KR20020048993A; EP1489206B1; EP1489206A3; ATE354601T1; EP1006220A4; KR100359149B1; JP3226931B2

Abstract

A polyester fiber prepared from a polyester prepared by copolymerizing polytrimethylene terephthalate with a third component, wherein the third component is an ester-forming sulfonate compound used in a comonomer ratio of 0.5 to 5 % by mole, the peak temperature of the tangent loss of the fiber is 85 to 115 °C, and the relationship between the modulus of elasticity, Q (g/d), and the elastic recovery, R (%), of the fiber satisfies 0.18 ≤ Q/R ≤ 0.45. This fiber can be deeply dyed under atmospheric pressure and enables fast dyeing of fabrics prepared by blending the fiber with a lowly heat-resistant fiber material, such as stretched fiber, wool, silk, and acetate fiber, typified by a polyurethane elastic fiber. The dyeing of the blended fabric can be carried out under atmospheric pressure, so that the properties of the blended lowly heat-resistant fiber material are less likely to be deteriorated in the course of dyeing. The polyester fiber can be subjected to alkaline weight loss treatment, is soft and rich in the feeling of dryness, and permits good color development.

Description

Description Polyester fiber and fabric using the same

The present invention relates to a polymethylene terephthalate fiber, particularly a polymethylene terephthalate fiber which can be dyed in a deep color under normal pressure with one or both of a cationic dye and a disperse dye. The present invention relates to a fabric using this fiber. Background art

Polymethylene terephthalate fiber has soft texture derived from low modulus, excellent elastic recovery and similar properties to nylon fiber, and low wearability and dimensions. This is an epoch-making fiber that has properties similar to polyethylene terephthalate fiber, such as stability and yellowing resistance, and is being applied to clothing, power plants, etc. It is getting.

However, polymethylene terephthalate fiber has a problem with dyeability. That is, in the known polymethylene terephthalate fiber, the dye to be used is limited to a disperse dye, and it can be dyed in a deep color only under a high pressure of 110 to 120 ° C. There was a major problem with staining.

The fact that the dyes used to dye the fibers are limited to disperse dyes means that the resulting dyed products have low clarity, and dry cleaning fastness, wet rub fastness, and sublimation fastness are slightly inferior. means.

Moreover, the fact that the dyeing temperature for the dyeing in the dark is 1 1 0~ 1 2 0 ^D C, for example, other fibers pyrolysis occurs at these high temperatures Means that the mixed fabric cannot be dyed. For example, mixing polymethyl terephthalate fibers with other fibers, such as polyurethane elastic yarn, cotton, silk, and acetate fibers, results in a softer texture than ever before. Mixed textiles can be expected, but if these other fibers exceed 11 oC at the dyeing stage, their strength will be greatly reduced or they will be devitrified white, greatly impairing their merchantability. There was a problem.

These problems can be solved if polytrimethylene terephthalate fibers can be dyed at normal pressure with either a cation dye or a disperse dye, or with both dyes. It was not known.

In the range of known techniques, no technique is known which enables polytrimethylene terephthalate fibers to be dyeable with dyes other than disperse dyes, for example, cation dyes.

No specific application to poly (methylene terephthalate) fiber is described, but it enhances the dyeing properties of polyester fibers, mainly poly (ethylene terephthalate) fibers, to cationic dyes. As a method, a copolymer is prepared by adding isophthalic acid having a sulfonate metal base / sulfonate quaternary phosphonium base to the polyester before the completion of the polycondensation reaction (Japanese Patent Publication No. Japanese Patent Application Laid-Open No. 2004-977, Japanese Patent Publication No. Sho 47-22334, and Japanese Patent Laid-Open No. Hei 5-23013) are known. However, the fibers thus obtained do not have the dyeing properties of a normal pressure thione dye and have a high modulus of elasticity, so that they give only a firm and stiff cloth. As a method for imparting cation dyeability at normal pressure, adipic acid and isophthalic acid are used in addition to isophthalic acid having a sulfonate metal base in polyethylene phthalate. Use of dicarboxylic acids such as acids or their alkyl esters as copolymer components Are known (for example, Japanese Patent Application Laid-Open No. 57-661119). However, the fibers obtained in this way still have a high modulus of elasticity and give only rugged fabrics.

Fibers having good dyeability to disperse dyes, low elastic modulus, and excellent elastic recovery properties include, for example, a polymer disclosed in JP-A-52-530. Remethylene terephthalate fiber is an example. Furthermore, Japanese Patent Publication No. Hei 9-5092225 discloses a method of dyeing polymethylene terephthalate fibers with a disperse dye under normal pressure. However, these fibers cannot be dyed at all under normal pressure with cationic dyes. Further, as has been clarified by detailed studies by the present inventors, with regard to disperse dyes, the techniques disclosed in these known documents only dye at extremely low dye concentration at normal pressure. I realized that I couldn't. For example, the dye concentration used in the example of Japanese Patent Publication No. Hei 9-5099225 is at most 0.5% 0 wf (where the unit of% 0wί is the dye concentration in the dye solution). This is shown in terms of% by weight of the fiber that stains the same.) In the field of garments, fabrics that are dyed dark as well as light and medium colors are required. Such a deep dyeing requires a dye concentration of 4% owf or more, and sometimes 10% owf or more.However, in dyeing polymethylene terephthalate fiber, Cannot be dyed deeply at normal pressure because the dye cannot be exhausted sufficiently at normal pressure. Disclosure of the invention

An object of the present invention is to provide a polymethylethylene terephthalate fiber which can be dyed in a deep color under normal pressure by using either a cationic dye or a disperse dye or both dyes. is there.

Another object of the present invention is to provide a polyurethane elastic fiber, wool, silk, The objective is to provide polytrimethylene terephthalate-based fibers that can dye composite fiber products mixed with tea, etc., without impairing the physical properties of these relatively low heat-resistant fibers. is there.

Still another object of the present invention is to provide a cross-woven, blended, or cross-knitted fabric of a polymethylentelephthalate fiber capable of being fast dyed under normal pressure and another fiber material. That is.

One specific object of the present invention is to provide a polyurethan elastic fiber and a polymethylene terephthalate-based fiber which can be fast dyed in a simple manner using ordinary atmospheric dyeing equipment. And providing a mixed fabric.

The present inventors have used polymethylene terephthalate obtained by copolymerizing a specific third component at a specific copolymerization ratio as a polymer, and have a very limited range of loss tangent peaks. The present inventors have found that a polyester fiber prepared to have a temperature, an elastic modulus, and an elastic recovery can solve the above-mentioned problems, and have reached the present invention.

That is, the first aspect of the present invention is that, in a fiber composed of polyester obtained by copolymerizing polymethylene terephthalate with a third component, the third component has an ester formation ratio of 0.5 to 5 mol% in a copolymerization ratio of 0.5 to 5 mol%. Sulfonic acid compound, the fiber has a loss tangent peak temperature of 85 to 115 ° C, an elastic modulus Q (g / d) and an elastic recovery rate R (%) of the fiber. Is a polyester fiber characterized by satisfying the following expression (1) and a fabric using the same:

0.18 ≤ Q / R ≤ 0.45 · · · Equation (1)

A second aspect of the present invention is a fiber comprising a polyester obtained by copolymerizing a poly (methylene terephthalate) with a third component, wherein the third component is (1) a copolymerization ratio of 1.5 to 12% by weight of carbon. Aliphatic or alicyclic glycol having a number of 4 to 12; (2) a carbon number of 2 to 9 having a copolymerization ratio of 3 to 9% by weight; At least one selected from aliphatic or alicyclic dicarboxylic acids up to 14 or isophthalic acid; and (3) a polyalkylene glycol having a copolymerization ratio of 3 to 10% by weight. The loss tangent peak temperature of the fiber is 85 to 102 ° C, and the relationship between the elastic modulus Q (g / d) and the elastic recovery rate R (%) of the fiber is expressed by the following equation (1). A polyester fiber characterized by satisfying and a fabric using the same.

0.18 ≤ Q / R ≤ 0.45 ··· Formula (1) The polymer constituting the polyester fiber of the present invention has a specific amount of the third polymer in the polymethylene terephthalate. It is a polyester obtained by copolymerizing the components. Here, polymethylethylene terephthalate is a polyester containing terephthalic acid as an acid component and trimethylene glycol (also referred to as 1,3-propanediol) as a diol component. It is.

When a specific amount of an ester-forming sulfonate compound is used as the third component to be copolymerized, a normal pressure thione dye-dyable fiber can be obtained. Also, (1) aliphatic or alicyclic glycol having 4 to 12 carbon atoms, (2) aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms, or isophthalic acid When a specific amount of at least one selected from an acid and (3) polyalkylene glycol is copolymerized, a normal pressure disperse dye-dyable fiber can be obtained.

Examples of the ester-forming sulfonate compound used in the present invention include a sulfonate group-containing compound represented by the following general formula.

R,-

Where R,, R 2 are one COOH, one C〇OR, one OCOR, — (CH ₂ ) _n OH, one (CH ₂ ) _n [0 (CH ₂ ) _m ] _P OH or — CO [0 (CH 2) „] _m 0 H, where R is 1 carbon

An alkyl group of ~ 10, n, m, and p are integers of 1 or more), R,, R may be the same group or different groups. M is a metal, NH ₄ , or a phosphonium group represented by the formula PR ₃ RRR (wherein R ₃ , R ₄ , R ₅ , and R ₆ are a hydrogen atom, an alkyl group, an aryl group, and an arsenic group) And represents the same or different group selected from the droxyalkyl groups, and is preferably an alkyl group having 1 to 10 carbon atoms. When M is a metal, it is preferably an alkali metal or an alkaline earth metal. Z is a trivalent organic group, preferably a trivalent aromatic group.

By copolymerizing such an ester-forming sulfonate compound, a fiber that can be dyed to a deep color with a cationic dye under normal pressure is obtained. Also, compared to polytrimethylene terephthalate homopolymer fiber, it becomes easier to dye the disperse dye. In the present invention, the fact that dyeing can be performed at normal pressure means that the exhaustion rate to fibers at 95 ° C. is approximately 70% or more.

In addition, since the cationic dyeable yarn exhibits an appropriate amount of weight loss characteristics, it is possible to obtain a softer texture by reducing the amount of alkali after weaving. Here, the alkali weight reduction means that the fabric is heated in an aqueous alkali solution to dissolve a part of the polymer on the fiber surface. Moderate alkaline weight loss means that the amount and rate of alkaline weight loss can be controlled industrially. This is a surprisingly great feature. For example, in the case of cationic dyeable poly (ethylene terephthalate) fiber, the weight loss rate is too fast to control industrially, and in the polyester fiber of the present invention, the control is practically impossible. The weight loss rate is the same as that of ordinary polyethylene terephthalate fiber that is not dyeable by Kachion, and it is possible to perform the weight loss using a known method. In this way, the polyester fiber of the present invention, whose weight has been reduced, becomes more soft and has micropores of several // m on the surface of the fiber, so that it has a dry feeling. It is possible to provide a feature that dyeing can be performed more clearly. Specific examples of preferred ester-forming sulfonate compounds include 5_ sodium sulfeusophthalic acid, 5_ calcium sulfoisophtalic acid, 41 sodium sulfo-1,2, 6_ naphtha range Carboxylic acid, 2-sodium sulfo 4-hydroxybenzoic acid, 3,5-dicarboxylate benzenesulfonate tetramethyl phosphonium salt, 3,5-dicarboxylic acid benzene sulfonate tetrabutyl phosphonium salt, 3, 5 Tricarboxylic acid benzenesulfonic acid tributylmethylphosphonium salt, 2,6-dicarboxylic acid naphthalene 1-4,2-sulfonic acid tetrabutylphosphonium salt, 2,6-dicarboxylic acid naphthalene-1 4—snolefone Tetramethylphosphonium acid salt, 3,5—dicarboxylic acid benzenesulfonic acid ammonium salt, etc. Le, include ester derivatives such as dimethyl chill ester. In particular, these ester derivatives such as methyl and dimethyl esters are preferably used in terms of excellent polymer whiteness and polymerization rate.

The copolymerization ratio of the ester-forming sulfonate compound to the poly (methylene terephthalate) is 0.5 to 5 mol based on the total number of mols of all the acid components constituting the polyester. It needs to be%. When the copolymerization ratio of the ester-forming sulfonate compound is less than 0.5 mol%, it becomes impossible to dye with a cationic dye at normal pressure. When the proportion of the ester-forming sulfonate compound exceeds 5 mol%, the heat resistance of the polymer deteriorates, the polymerizability and the spinnability deteriorate, and the fiber is liable to yellow. From the viewpoint of having both polymerizability and spinnability while maintaining sufficient dyeability for cationic dyes, it is preferably 1 to 3 mol%, particularly preferably 1.2 to 2.5 mol%.

Specific examples of the aliphatic and alicyclic glycols having 4 to 12 carbon atoms used in the present invention include, for example, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. Butanediol, neopentyl Glycol, l, 5—pentamethylenglycol, 1, 6—hexamethylenglycol, heptamethylenglycol, octamethylenglycol, decamethylenglycol, dodecamethylenglycol, 1 1,4-cyclohexanediol, 1,3—cyclohexanediol, 1,2—cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3—cyclo Hexane dimethyl ethanol, 1,2-cyclohexane dimethyl ethanol, and the like. By copolymerizing these glycols with polymethylene terephthalate, it becomes possible to dye to a deep color with a disperse dye at normal pressure. Of these aliphatic or alicyclic glycols, 1,4-butanediol and 1,6-hexamethylenglycol are considered in view of the polymer's excellent whiteness, thermal decomposition, and light resistance. Cornole, neopentyl glycol, and cyclohexanedimethanol are preferred. Furthermore, taking into account the fact that the polymerization rate and the dry cleaning fastness are excellent, the copolymerization ratio of these glycols to polymethylene terephthalate, in which 1,4-butanediol is particularly preferred, is as follows. It should be 1.5 to 12% by weight based on the weight of the polymer. If the copolymerization ratio is less than 1.5% by weight, it becomes impossible to dye a disperse dye to a deep color at normal pressure. The copolymerization ratio of glycol has a strong correlation with the elastic modulus, elastic recovery, melting point, glass transition point, and dyeability. If the copolymerization ratio exceeds 12% by weight, the melting point and the glass transition point are greatly reduced, and the post-processing represented by heat setting and the usual use represented by ironing are performed. There are drawbacks in that the texture changes hardly in stages, and the dry cleaning fastness of the dyed fabric is reduced. Preferably it is 2 to 10% by weight, more preferably 3 to 7% by weight.

The aliphatic or alicyclic dica having 2 to 14 carbon atoms used in the present invention. Specific examples of rubonic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptane diacid, octane diacid, sebacic acid, dodecane diacid, and 2 — Methylglutaric acid, 2-Methyladipic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, 1,3—cyclohexanedicarboxylic acid, 1,2— Hexanedicarboxylic acid and the like. By copolymerizing these dicarboxylic acids with polytrimethylene terephthalate, it becomes possible to dye to a deep color using a disperse dye at normal pressure.

Among these aliphatic or alicyclic dicarboxylic acids or isophthalic acids, sebacic acid, dodecane diacid, and 1,4-cyclohexane in terms of polymerization rate and light resistance during copolymerization are excellent. Dicarboxylic acid and isophthalic acid are preferred. Furthermore, isophthalic acid is particularly preferred in view of the excellent whiteness of the polymer.

The copolymerization ratio of the aliphatic or alicyclic dicarboxylic acid or isophthalic acid to polymethylene terephthalate needs to be 3 to 9% by weight based on one weight of the polymer. If the copolymerization ratio is less than 3% by weight, it becomes impossible to dye a deep color at normal pressure. When the copolymerization ratio is more than 9% by weight, the melting point and the glass transition point are too low, so that the post-processing typified by heat setting property and the normal use stage represented by ironing are required. However, there are drawbacks in that the texture is hardly changed and the dry cleaning fastness of the dyed fabric is reduced. It is preferably from 3 to 8% by weight, more preferably from 3 to 7% by weight.

In the present invention, polyalkylene glycol may be used as the copolymerization component. When glycol or acid is copolymerized as the third component, the melting point is inevitably lowered, and the spinnability is deteriorated. Welding ゃ noticeable shrinkage, etc. This may cause poor handling. However, when polyalkylene glycol is used as the third component, the melting point hardly decreases and such a problem does not occur. This is thought to be because the polyalkylene glycol component is localized in the polymer due to its high molecular weight. The polyalkylene glycol used may be polyethylene glycol, polymethylene glycol, polytetramethylene glycol or a copolymer thereof, but polyethylene is preferred in view of thermal stability. Glycol is most preferred.

The average molecular weight of polyalkylene glycol is preferably from 300 to 20000. When the average molecular weight is less than 300, since a very low molecular weight polyalkylene glycol is contained, it is distilled off under reduced pressure during polymerization under high vacuum, and the resulting polymer is obtained. The amount of polyalkylene glycol contained is not constant. Therefore, the properties of the raw yarn such as high elongation properties, dyeing properties and thermal properties are not uniform, and the properties of the product vary.

On the other hand, if the average molecular weight is more than 20000, the amount of high-molecular-weight polyalkylene glycol not copolymerized in the polymer increases, so that the dyeing properties, dry cleaning fastness, and light fastness are increased. Degradation occurs. The average molecular weight of polyalkylene glycol is preferably from 400 to 100,000, more preferably from 500 to 500,000.

The copolymerization ratio of the polyalkylene glycol to the polymethylene terephthalate must be 3 to 10% by weight based on the weight of the polymer. When the proportion of the polyalkylene glycol is less than 3% by weight, it becomes impossible to dye the disperse dye to a deep color at normal pressure. On the other hand, if the proportion of polyalkylene glycol exceeds 10% by weight, the heat resistance of the polymer decreases, and the polymerizability and spinnability deteriorate significantly. Also The glass transition point is too low, and the texture changes to hard during normal use, such as post-processing, such as heat setting, and the drying of the fabric after dyeing. A disadvantage arises in that cleaning fastness and light fastness are greatly reduced. It is preferably 4 to 8% by weight.

The polymer constituting the polyester fiber of the present invention can be copolymerized and blended with the fourth component within a range not to impair the purpose of the present invention. Even when such a fourth component is used, it is necessary to keep the copolymerization ratio in the range described above so as not to hinder the object of the present invention. Among these combinations, in particular, ester-forming sulfonate compounds and (1) aliphatic or cycloaliphatic glycols having 4 to 12 carbon atoms, and (2) aliphatics having 2 to 14 carbon atoms. Alternatively, copolymerization of at least one selected from alicyclic dicarboxylic acid, isophthalic acid, and (3) polyalkylene glycol makes it possible to dye both cationic dyes and disperse dyes at normal pressure. Polyester fibers can be obtained. The copolymerization ratio is preferably from 2 to 2.5 mol% of the ester-forming sulfonate compound, and at least one selected from the above (1) to (3). It is preferred that one species be 3 to 7% by weight. Further, if necessary, various additives may be added to the polyester fiber of the present invention, for example, an anti-glazing agent, a heat stabilizer, an anti-foaming agent, a coloring agent, a flame retardant, an antioxidant, an ultraviolet absorber, and an infrared absorber. Agents, crystal nucleating agents, fluorescent whitening agents and the like may be copolymerized or mixed.

The molecular weight of the polyester used in the present invention can be defined by the intrinsic viscosity. The intrinsic viscosity [? 7] is preferably 0.3 to 2.0, more preferably 0.35 to 2.0. With a value of 1.5, particularly preferably of 0.4 to 2, a polyester fiber having excellent strength and spinnability can be obtained. If the intrinsic viscosity is less than 0.3, the polymerization degree of the polymer is too low. The spinnability becomes unstable. Also, the strength of the obtained fiber is low and not satisfactory. On the other hand, when the intrinsic viscosity exceeds 2.0, the melt viscosity is too high, so that the metering by the gear pump cannot be performed smoothly, and the spinnability is reduced due to poor discharge.

Regarding the method for producing the polymer constituting the polyester fiber of the present invention, polymerization can be basically carried out by using a known method. That is, in the ordinary production process of polymethylene terephthalate, a transesterification reaction followed by a polycondensation reaction of terephthalic acid or a lower ester of terephthalic acid such as dimethyl terephthalate with trimethylene glycol is carried out. The third component can be added at any stage during the process. In this case, the ester-forming sulfonate compound and the aliphatic or alicyclic dicarboxylic acid or isophthalic acid need to be added before the transesterification reaction because the reaction with trimethylene glycol must be promoted. It is preferable to add polyalkylene glycol at the end of the transesterification reaction in order to prevent yellowing of the polymer and bumping at reduced pressure. As the transesterification catalyst, it is preferable to use metal acetate, titanium alkoxide, etc. in an amount of 0.01 to 0.1% by weight, because it has the reaction speed, the whiteness of the polymer, and the thermal stability. . The reaction temperature is about 200 to 240 ° C. As the polycondensation catalyst, antimony oxide, titan alkoxide, or the like can be used. In particular, when titan alkoxide is used, it may be used also as a transesterification catalyst. The amount of the catalyst is 0.01 to 0.1% by weight based on the total amount of rubonic acid used from the viewpoint of the reaction rate and the whiteness of the polymer. The reaction temperature is 240 to 280. C, and the degree of vacuum is 0.001 to 1 t0 rr. The above-mentioned various additives may be added at any stage of the polymerization process.However, in order to minimize the inhibition of the reaction, they are added at any stage after the transesterification reaction. I prefer to do that.

Further, the polymer constituting the polyester fiber of the present invention may be obtained by increasing the molecular weight by subjecting the polymer obtained by the above method to solid phase polymerization in an inert gas such as nitrogen or argon or under reduced pressure. . By applying such a method, it is possible to suppress the yellowing of the polymer, reduce the amount of the oligomer that causes thread breakage and fluff, and increase the strength. For the method of solid-phase polymerization, for example, a known method used for polyethylene terephthalate can be applied as it is, but the intrinsic viscosity of the prepolymer before solid-phase polymerization is 0.4 to 0.8 as whiteness. The solid-state polymerization temperature is preferably 170 to 230 ° C, and the time varies depending on the desired viscosity, but is usually about 3 to 36 hours. It is. Further, the polymer constituting the polyester fiber of the present invention may be produced by blending two kinds of polymers so as to obtain a desired copolymer composition. For example, polymethylene terephthalate prepared by copolymerizing 1,4-butanediol at 5% by weight has 95% by weight of polymethylene terephthalate and 95% by weight of polybutylene terephthalate. It may be manufactured by mixing 5% by weight of tallate. Mixing here means that the mixture may be mixed in a polymerization kettle and sufficiently transesterified before being discharged, or more simply, the reaction may be performed in an extruder with the tip blended. Even with such a method, the transesterification rate is sufficiently high, so that a homogeneous polymer can be obtained.

What is important in the method for producing the polymer constituting the polyester fiber of the present invention is to maintain the whiteness of the polymer. When the third component is copolymerized with polymethylene terephthalate, it generally becomes easier to color during the polymerization process and the spinning process. Therefore, as a method for increasing the whiteness, it is preferable to use the above-mentioned preferable amount of catalyst and reaction temperature, and at the same time, use a heat stabilizer and a coloring inhibitor. As a heat stabilizer, 5 Trivalent or trivalent phosphorus compounds are preferred, e.g., trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trimethyl phosphate, triethyl phosphate And triphenylphosphite, phosphoric acid, phosphorous acid and the like, and it is preferable to add 0.01 to 0.07% by weight to the polymer. Further, examples of the coloring inhibitor include cobalt acetate and cobalt formate, and it is preferable to add 0.01 to 0.07% by weight to the polymer. When the intrinsic viscosity is increased to 0.9 or more, solid phase polymerization of prepolymer is an extremely effective method for increasing whiteness. The polymer thus obtained can maintain excellent whiteness even in fiber. Such whiteness is 12 to 10 in the b value to be described later, preferably —1 to 6.

Furthermore, when an ester-forming sulfonate compound is used, a substance that easily aggregates in the spin-back during the polymerization process is produced and the trimethylene glycol dimer (structural formula: H0CH ₂ CH ₂ CH ₂ 0CH ₂₎ Particular attention should be paid to the fact that CH ₂ CH ₂ 0H) is easily formed. If the amount of agglomerates is large, the pressure in the spout pack increases and the thread breaks easily, or if the frequency of replacing the spout pack is increased to prevent this, productivity will decrease. A problem arises. In addition, when the amount of trimethylenglycol dimer is large, there arises a problem that heat stability and light resistance during melting are reduced. To prevent such problems, it is preferable to add certain additives at any stage during the polymerization. Examples of such additives include lithium acetate, lithium carbonate, lithium formate, sodium acetate, sodium carbonate, sodium formate, sodium hydroxide, and sodium hydroxide. Basic metal salts such as calcium and potassium hydroxide may be mentioned, and the amount thereof is 20 to 400 mol%, preferably 70 to 100 mol%, based on the ester-forming sulfonate compound. ~ 200 mol%. The form of the polyester fiber of the present invention may be any of a long fiber and a short fiber, and in the case of a long fiber, any of a multifilament and a monofilament may be used. . There is no particular limitation on the total denier, and it is preferably 5 to 1000 d, and especially 5 to 200 d when used for clothing. The single yarn denier is not particularly limited, but is preferably 0.001 to 10 d. Also, the cross-sectional shape is not particularly limited, such as a round shape, a triangular shape, a flat shape, a star shape, and a w shape, and may be solid or hollow.

In the polyester fiber of the present invention, the peak temperature of the loss tangent (hereinafter abbreviated as “T max”) obtained from the dynamic viscoelasticity measurement is 85 to 85 when the third component is an ester-forming sulfonate compound. 115 ° C, the third component is (1) a copolymerization ratio of 1.5 to 〖2% by weight of an aliphatic or alicyclic glycol having 4 to 12 carbon atoms, and (2) a copolymerization ratio of 3 From 9 to 9% by weight of an aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms or isophthalic acid; (3) from a copolymerization ratio of 3 to 10% by weight of a polyalkylene glycol; It must be 85 to 102 for at least one of the selected species. This is because, in this range, normal pressure dyeability and high fastness by the thione dye or Z and the disperse dye required by the present invention can be secured. Since Tmax corresponds to the molecular density of the amorphous part, the smaller this value is, the smaller the molecular density of the amorphous part is. And the exhaustion rate increases. When Tmax is less than 85 ° C, molecules can easily move at low temperatures when any of the third components is used.Therefore, typical post-processing such as heat setting and ironing are typical examples. During normal use, the shrinkage becomes too great and the texture becomes worse, or the dry cleaning fastness of the fabric after dyeing is reduced. The third component is an ester-forming sulfonate. When the compound is used, if the Tmax exceeds 115 ° C, the dyeability, which is the object of the present invention, is reduced, and the space for the dye is too small, so that the cation dye under normal pressure is used. The dye cannot be dyed to a dark color. As the third component, (1) a copolymerization ratio of 1.5 to 12% by weight, an aliphatic or alicyclic glycol having 4 to 12 carbon atoms, and (2) a copolymerization ratio of 3 to 9% by weight. An aliphatic or alicyclic dicarboxylic acid or isophthalic acid having 2 to 14 carbon atoms, and (3) a copolymerization ratio of 3 to

When at least one member selected from the group consisting of 10% by weight of polyalkylene alcohol is used, if Tmax exceeds 102 ° C, the void space for the dye is reduced. This makes it impossible to dye the disperse dye deep under normal pressure.

As described above, since Tmax is a structural factor of a fiber, spinning temperature, spinning speed, draw ratio, heat treatment temperature, scouring conditions, and alkali reduction even for polymers having the same copolymer composition. It shows different values depending on spinning conditions such as conditions and dyeing conditions, and post-processing conditions. In particular, since this value greatly changes with the heat set temperature, it is important to change the heat set temperature to keep T max in the above range. The concept of setting the heat set temperature is roughly described. In the case of the polyester fiber specified in the present invention, T is set when the heat set temperature is in the range from room temperature to about 150 ° C. ma X is a gradually increasing force, and after about 160 ° C, it drops significantly thereafter. Since the ratio of these changes differs depending on the copolymerization ratio, it is necessary to study while examining the relationship between the heat setting temperature and Tmax. In the case of the present invention, when the temperature exceeds 115 ° C, the effect of improving the dyeability is small and the normal pressure dyeability is not exhibited. However, it is not only that the amount of the dye should be low, but also that the amorphous portion becomes too coarse, so that the dye can easily enter and simultaneously escape. That is, the fastness, especially the fastness of dry cleaning, the fastness of wet rubbing, the fastness of washing, etc. are reduced. I do. In addition, problems such as deterioration of texture due to curing during heat setting and deterioration of dimensional stability come out. The preferred range of T max varies slightly depending on the type of the third component, but when an ester-forming sulfonate compound is used as the third component, the range of 97 to 112 ° C. (1) an aliphatic or alicyclic glycol having a copolymerization ratio of 1.5 to 12% by weight having 4 to 12 carbon atoms; (2) a carbon number of 2 to 3 having a copolymerization ratio of 3 to 9% by weight. If at least one selected from aliphatic or alicyclic dicarboxylic acids up to 14 and (3) alkylene glycol having a copolymerization ratio of 3 to 10% by weight is used, 85 to 102 is used. ° C, particularly preferably 90-98 ° C.

Further, the elastic modulus Q (g / d) of the polyester fiber of the present invention and the elastic recovery rate R (%) after standing for 20 minutes after elongation of 20% may satisfy the following expression (1). is necessary. This is because, when the formula (1) is satisfied, the fabric obtained from the polyester fiber of the present invention has a soft texture equal to or higher than that of nylon, unlike the fabric obtained from the conventional polyester fiber. It is because it can have.

0.18 ≤ Q / R ≤ 0.45 * '* Equation (1)

When Q / R> 0.45, the elasticity is too high to achieve the soft texture that is the same as that of the knee, which is the object of the present invention. However, the fibers deformed by the addition of the resin do not return to the original state, and only a fabric having poor form stability can be obtained. In addition, since there is substantially no region where QZR is 0.18, 0.18 is set as the lower limit of Q / R in the present invention. The specific elastic modulus that can be in the range of the equation (1) is usually 25 to 40 g Zd, and the elastic recovery is 70 to 99%.

The ester-forming sulfonate compound having a copolymerization ratio of 1.2 to 2.5 mol% and a copolymer having a copolymerization ratio of 3 to 7% by weight (1) a fatty acid having a carbon number of 4 to 12 or Alicyclic glycol, (2) having 4 to 12 carbon atoms Aliphatic or cycloaliphatic dicarboxylic acids, or isophthalic acid, up to (

3) In the case of polymethylene terephthalate fiber in which at least one kind selected from polyalkylene glycol is copolymerized, the Tmax of the fiber is 85 to 115 ° C and The reason that the relationship between the elastic modulus Q (g / d) and the elastic recovery rate R (%) of the fiber satisfies the equation (1) is the same as the detailed T max and the basis of the equation (1) described above. Required from.

The polyester fiber of the present invention can be obtained by the following method.

The polyester fiber of the present invention is obtained by melting a polymer dried to a water content of at least 100 ppm, and preferably 50 ppm or less using an extruder or the like, and then melting the polymer. It can be obtained by winding after extruding from a spinneret and then stretching. Stretching after winding here means that the yarn is wound on a bobbin or the like after spinning, and this yarn is stretched using another device, a so-called ordinary method, or a polymer extruded from a spinneret. After it has completely cooled and solidified, it is wound several times around the first roll rotating at a constant speed, so that the tension before and after the roll is not transmitted at all, and after the first roll and the first roll, It refers to the so-called straight drawing method in which the spinning and drawing process is directly connected, such as drawing between the installed second roll.

Hereinafter, the ordinary method will be described with examples.

In the present invention, the spinning temperature for melt spinning the polymer is 240 to 320 ° C, preferably 240 to 300 ° C, and more preferably 240 to 28 ° C. A range of 0 ° C is appropriate. If the spinning temperature is lower than 240 ° C., the temperature is too low to be in a stable molten state, the resulting fibers have large spots, and no satisfactory strength and elongation are exhibited. On the other hand, when the spinning temperature exceeds 320 ° C., thermal decomposition becomes severe, and the obtained yarn is colored and does not show satisfactory strength and elongation. The winding speed of the yarn is not particularly limited, but is usually 350 m / min or less, preferably 250 m / min or less, and more preferably 200 m / min or less. Take up. If the winding speed exceeds 350 m / min, the crystallization proceeds too much before winding, and the stretching ratio cannot be increased in the stretching process. Insufficient thread strength and elastic recovery rate cannot be obtained, or winding and tightening occur, and the bobbin and the like cannot be pulled out of the winder. The stretching ratio at the time of stretching is 2 to 4 times, preferably 2.2 to 3.7 times, and more preferably 2.5 to 3.5 times. If the draw ratio is not more than 2 times, the polymer cannot be oriented sufficiently by drawing, and the elastic recovery of the obtained yarn will be low, which satisfies the expression (1). I can't do that. If it is 4 times or more, thread breakage is severe and it is not possible to perform stable elongation.

3 0 ~ 8 0 ^Q C temperature is a stretching zone during stretching, favored properly the 3 5 ~ 7 0 ° C, rather further favored good 4 0 ~ 6 5 ° C. If the temperature of the drawing zone is lower than 30 ° C., yarn breakage frequently occurs during drawing, and continuous fibers cannot be obtained. If the temperature exceeds 80 ° C, slippage of the fiber against a heating zone such as a drawing roll deteriorates, so that single yarn breakage occurs frequently and the yarn becomes full of fluff. In addition, the polymers will slip through each other, resulting in insufficient orientation and lowering the elastic recovery rate.

In addition, it is necessary to perform a heat treatment after drawing to avoid the temporal change of the fiber structure. This heat treatment is carried out at 90 to 200 ° C, preferably at 100 to 190 ° C, and more preferably at 110 to 180 ° C. If the heat treatment temperature is lower than 90 ° C, the crystallization of the fiber does not sufficiently occur, and the elastic recovery is deteriorated. At a temperature higher than 200 ° C., the fiber is cut by the heat treatment zone and cannot be drawn.

Next, the straight-rolling method will be described with examples. Melt extruded from the spout After suppressing the rapid cooling by passing the molten multifilament through a heat-retaining area of 2 to 80 cm in length maintained at an ambient temperature of 30 to 200 ° C provided directly below the spinneret. The molten multi-filament is rapidly cooled to a solid multi-filament, and heated to 40 to 70 ° C. The first roll with a rotation speed of 300 to 300 Om / min And then wound without winding on a second roll heated to 120 to 160 ° C, and between the first roll and the second roll, which has a higher speed than the first roll, 1.5. After stretching it up to 3 times, wind it up with a winder at a lower speed than the second roll. Entangling treatment may be performed as necessary during the spinning process. The undrawn yarn once wound at a spinning speed of 300 to 300 m / min may be wound through the first roll and the second roll.

The polymer is extruded in the same manner as in the conventional method, and the molten multi-filament coming out of the spinneret is not immediately quenched, but is placed immediately below the spinneret at 30 to 200 ° C. After passing through a heat retaining area of 2 to 80 cm in length maintained at the same ambient temperature to suppress rapid cooling, this molten multifilament is rapidly cooled and converted into a solid multifilament, followed by stretching. It is extremely preferred to submit to the process. By allowing the polymer to pass through this heat insulation region, it is possible to suppress the generation of fine crystals and extremely oriented amorphous parts due to rapid cooling of the polymer, and to create an amorphous structure that is easily stretched in the stretching step. As a result, the fiber properties required in the present invention can be achieved. Polyethylene terephthalate has a much faster crystallization rate than, for example, polyester such as polyethylene terephthalate. Performing such slow cooling is an extremely effective method for suppressing the formation of fine crystals and extremely oriented amorphous parts. If the temperature is lower than 30 ° C, the film is rapidly cooled, making it difficult to increase the draw ratio. Above 200 ° C., thread breakage tends to occur. The temperature of such a heat retaining region is preferably from 40 to 200 ° C, more preferably from 50 to 150 ° C. Also, this The length of the heat insulation area is preferably 5 to 30 cm.

Regarding the spinning speed of the yarn, the winding speed of the first roll is 300 to 300 m / min. When the spinning speed is less than 300 m / min, spinning stability is excellent, but productivity is greatly reduced. If it exceeds 300 m / min, the orientation of the amorphous part or partial crystallization proceeds before winding, and the stretching ratio cannot be increased in the stretching process. And it is difficult to develop sufficient yarn strength. Preferably, it is 150 to 270 m / min.

It is necessary that the speed of the winder be lower than that of the second roll to relax the orientation of the amorphous portion of the fiber, thereby weakening the large shrinkage of the polymethylene terephthalate fiber. In addition, the amorphous part becomes loose and the dye is easily penetrated, improving the dyeability. The relax ratio (winding speed Z second roll speed) is about 0.95 to 0.99, preferably 0.95 to 0.98.

The speed of the second roll is determined by the stretching ratio, but is usually from 600 to 600 m / min. The stretching ratio between the first roll and the second roll is 1.3 to 3 times, preferably 2 to 2.7 times. If the draw ratio is 1.3 or less, the polymer cannot be sufficiently oriented by stretching, and the strength and elastic recovery of the obtained fiber will be low. On the other hand, if it is three times or more, the fluff is so severe that stretching cannot be performed stably. The temperature of the first roll is 40 to 70. C, and it is possible to create a situation where stretching is easy in this range. It is preferably between 50 and 60. The heat is set at the second port, but the temperature is 120 to 160 ° C. If the temperature is lower than 120 ° C, thermal stability is poor, thermal deformation, and aging change. At a temperature of 160 ° C. or higher, fluff and yarn breakage occur, and stable spinning cannot be performed. Preferably, it is between 120 and 150 ° C. It is important to apply the favorable conditions indicated by the ordinary method and the straight-rolling method described above in order to ensure the homogeneity and quality of the obtained fiber. For example, u% can be used as a parameter for evaluating the quality of a fiber obtained by applying preferable spinning conditions. u% is a parameter that indicates the homogeneity of the fiber cross-section. Under favorable conditions, U% is less than 2.5%, and in some cases less than 1.5%.

The polyester fiber obtained as described above can be used alone or as a part of a fabric to provide a fabric having excellent softness, stretchability, and coloring. There are no particular restrictions on other fibers used in part of the fabric, but in particular stretch fibers, cellulose fibers, wool, silk, acetate, etc. represented by polyurethane elastic fibers. By mixing with the above-mentioned fibers, characteristics that cannot be obtained with a mixed fabric using nylon fibers or polyethylene terephthalate fibers can be exhibited. That is, the fabric can be dyed at normal pressure by using, for example, a cationic dye and / or a disperse dye, and has a unique texture that has a softness and a stretch property that have not existed conventionally.

In particular, the polyester fiber of the present invention can be used as a field in which either the cation dye or the disperse dye, or both dyes, can be dyed in a deep color. It can be dyed quickly and can have a different softness and sunset from the mixed fabric of nylon fiber and stretch fiber typified by polyurethane elastic fiber. In particular, a mixed fabric of the poly (methylene terephthalate) fiber and a stretch fiber represented by a polyurea elastic fiber is exemplified as a particularly preferred fabric. You.

The form and knitting and weaving method of the cloth of the present invention including the above-mentioned mixed cloth are not particularly limited, and known methods can be used. An example Examples thereof include plain woven fabrics using the polyester fiber of the present invention as warp or weft yarns, woven fabrics such as reversible woven fabrics, and knitted fabrics such as tricots and raschels. You may.

The stretch fiber used in the present invention is not particularly limited, but is a dry-spun or melt-spun polyurethane elastic fiber or a polybutylene terephthalate fiber. And polyester-based elastic fibers typified by polybutylene terephthalate fiber and polytetramethylene glycol copolymer. In the mixed fabric using stretch fibers, the content of the polyester fiber of the present invention is not particularly limited, but is preferably 60 to 98%.

The fabric of the present invention, including mixed fabrics, can be dyed, for example, after knitting and weaving, through the steps of scouring, presetting, dyeing, and final set by a conventional method. If necessary, after scouring and before dyeing, it is possible to carry out a weight reduction treatment by an ordinary method.

Refining can be performed in a temperature range of 40 to 98 ° C. In particular, in the case of blending with stretch fiber, scouring while relaxing is more preferable because it improves the elasticity.

It is possible to omit one or both of the heat setting before and after dyeing, but it is preferable to perform both in order to improve the form stability and dyeability of the fabric. The temperature of the heat set is from 120 to 190 ° C, preferably from 140 to 180 ° C, and the heat set time is 10 to 100 ° C. Seconds to 5 minutes, preferably 20 seconds to 3 minutes.

Staining is carried out at 70 to 150 ° C, preferably 90 to 120 ° C, and particularly preferably 90 to 100 ° C, without using a carrier. It can be carried out. In order to perform dyeing uniformly, it is particularly preferable to adjust the pH according to the dye using acetic acid, sodium hydroxide, or the like, and to use a dispersing agent composed of a surfactant. Also, the cation When using dyes, metal or alkaline earth metals such as sodium sulfate, sodium nitrate, potassium sulfate, sulfate sulfate, etc. to improve the sharpness of the dyed material. It is particularly preferred to add a class of metal salts to the dye bath.

After dyeing, sorbing or reduction washing can be performed by a known method. In particular, when dyeing a mixed fabric consisting of a normal pressure dispersible dye-dyeable fiber and a polyurethan elastic fiber when mixed with stretch fiber, the reducing fiber is washed and the polyurethane is used. It is important to firmly remove the disperse dye that has contaminated the elastic fiber in order to improve the robustness of the fabric. These methods are well-known methods. For example, a reducing agent such as hydrosulfite sodium is dissolved in an aqueous solution of sodium carbonate such as sodium carbonate and sodium hydroxide. The following is a special mention of the poly (methylene terephthalate) fiber of the present invention which can be dyed in a deep color with either a cationic dye or a disperse dye or both dyes at normal pressure. FIG.

(1) The polymethylene terephthalate fiber of the present invention is a heat-resistant fiber such as stretch fiber, polyester, silk, and acetate represented by polyurethane elastic fiber. When mixed with fibers with low heat resistance, it can be dyed dark under normal pressure without impairing the performance of fibers with low heat resistance. In particular, when polymethylentelephthalate fibers are mixed with polyurethane elastic fibers, the softness and sunset are different from those of mixed fabrics using nylon fibers, Create a new sense of clothing that has easy-care characteristics

(2) Polyurethane elastic fibers must be dyed at 110 ° C to 120 ° C for mixed fabrics of ordinary polymethylene terephthalate fibers and polyurethane elastic fibers. Thermal degradation. In addition, only with disperse dyes Does not stain. In the dyeing of the mixed fabric with the polyurethane elastic fiber by the disperse dye, the disperse dye is more exhausted by the polyurethane urethane fiber than by the polymethylene terephthalate fiber. Does not firmly adhere to the urethane elastic yarn fiber. For example, fiber disperse dyes are easily transferred by dry cleaning and washing, and stain the surrounding clothing.In some cases, the dyes are released and the color of the mixed fabric is faded, decreasing the color fastness. Let it. On the other hand, the above-mentioned problem has been solved by using the polytrimethylene terephthalate-based fiber of the present invention, which can dye either the cationic dye or the disperse dye or both dyes at normal pressure. it can.

That is, the first method is to use the normal-pressure thione dye-dyeable polymethylene terephthalate fiber of the present invention.

Polyurethane elastic fibers are not dyed with cationic dyes. If polytrimethylene terephthalate fiber that can be dyed under normal pressure is used as the cationic dye, the above contamination will occur because only the polymethylene terephthalate fiber is selectively dyed. No problem.

The second method is the use of the normal pressure dispersible dyeable polymethylene terephthalate fiber of the present invention. If the polymethylene terephthalate fiber is modified to have normal pressure disperse dye dyeability, the transfer of the disperse dye to the polyurethan fiber can be considerably suppressed.

(3) One of the fields of blending with stretch fibers represented by polyurethane elastic fibers is the predominant pantyhose field. In this industry, specialized dye plants do not usually have the high pressure dyeing vessels required for high pressure dyeing. The use of the normal pressure thione dye-dyeable or normal-pressure disperse dye-dyeable polymethylene terephthalate fiber of the present invention can be used for nylon fiber knitting pumps without investment in new equipment. It has the advantage of facilities that the pressure dyeing kettle can be diverted as it is. Such equipment The above advantage is a very important effect industrially.

(4) The fabric obtained using the polymethylene terephthalate fiber of the present invention is, for example, far more soft than a known mixed fabric of nylon fiber and polyurethane elastic fiber. There is no peculiar feeling unique to nylon fiber. In addition, it can be a new sensational garment with light stretch characteristics and excellent color development. Furthermore, polytrimethyl terephthalate-based fibers have a high heat setting property and are excellent in yellowing resistance. These properties indicate that there are no problems inherent to nylon fiber, and that it is easy to handle.

(5) The polyester fiber of the present invention exhibits an excellent effect even when mixed with cellulose fiber. When a reactive dye is used for dyeing cellulose fibers, the reactive dye often decomposes when the temperature of the dye bath exceeds 100 ° C. By using the poly (methylethylene terephthalate) fiber of the present invention, it is possible to perform one-step, one-bath dyeing using a cation dye or a disperse dye and a reactive dye under normal pressure. The fabric thus obtained is a new sensation garment having both the dry feeling unique to cellulose and the softness derived from polytrimethylene terephthalate.

(6) The polyester fiber of the present invention can be applied alone to a woven or knitted fabric, and the obtained fabric is rich in softness and exhibits excellent stretch characteristics and coloring properties. Becomes If there is no problem with staining at 100 ° C. or more, it is also possible to stain at 100 ° C. or more. Further, as a characteristic of the polyester fiber of the present invention, the amount and speed of the weight loss can be industrially controlled in spite of being a cationic dye-dyeable fiber. The polyester fiber of the present invention, which has been reduced in alkali content, is further softened, and has micropores of several meters on the fiber surface, so that it has a dry feeling and can be dyed clearly. Can be issued. In addition, the normal pressure disperse dye dyeable poly Ester fibers also have similar alkali weight loss characteristics. As described above, the polytrimethylene terephthalate-based fiber of the present invention can be used for clothing such as outer garments, underwear, lining, sports, etc., as well as for raw yarn and core, It can also be used for materials such as ground and flocks. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The main measurement values and evaluation values in the examples are based on the following measurement methods and evaluation methods.

(1) Measurement of intrinsic viscosity

The intrinsic viscosity [7?] Was measured using an oste-ward viscosity tube at 35 ° C and o-chlorophenol.

() Loss tangent measurement

The loss tangent (tan 5) and the dynamic elastic modulus at each temperature were measured using Orientec's Leo Vibron in dry air at a measurement frequency of 110 Hz and a heating rate of 5 ° C / min. It was measured. From the results, a loss tangent-one temperature curve was determined, and Tmax (° C), which is the peak temperature of the loss tangent, was determined on this curve.

(3) Measurement of elastic modulus

The elastic modulus was measured according to JIS-L-113.

(4) Measurement of melting point

The measurement was carried out in a nitrogen stream of 100 milliliters Z min at a heating rate of 20 ° C./min using a DSC manufactured by SEIKO ELECTRONICS CO., LTD. Here, the peak value of the melting peak was used as the melting point.

(5) Measurement of elastic recovery

Attach the fiber to a tensile tester with a chuck distance of 20 cm and stretch it. Elongate at a pulling rate of 20 cm / min to a long rate of 20% and let stand for 1 minute. After that, it is contracted again at the same speed to draw a stress-strain curve. The elongation when the stress becomes zero during shrinkage is defined as the residual elongation (X). The elastic recovery was determined according to the following equation.

2 0-X

Elastic recovery = 1 0 0 (%)

2 0

(6) Measurement of b value

The yellowness of the obtained fiber was measured using the b value. The b value was measured using a color computer of Suga Test Instruments Co., Ltd. The yellowness increases as the b value increases.

(7) Dyeability evaluation test

(1) Evaluation of dyeability of polyester fiber by cationic dye The sample is a one-piece knitted fabric of polyester fiber (circular knit, sheeting, gauge 28), and score roll 400 (Kao Corporation, non-ion interface) Activator)

70 g using hot water (bath ratio 1:50) contained in 2 g Z liter. C, scoured for 20 minutes and dried with a tumble dryer. Next, a heat set at 180 ° C for 30 seconds was performed using a pin tenter. The dye used was KACRYL BLUE GSL-ED (Cation dye manufactured by Nippon Kayaku Co., Ltd.), 4% owf, bath ratio 1:50, 95 ° C,

Stained for 30 minutes. As additives, 0.25 g / liter of acetic acid and 3 g / liter of sodium sulfate were added to adjust the pH.

② Evaluation of dyeability of polyester fiber with disperse dye

The sample was a piece of polyester fiber knitted fabric (circular knit, sheeting, gauge 28), using hot water (bath ratio 1:50) containing score roll 400 at 2 g / liter. It was scoured at 70 ° C for 20 minutes and dried with a tumble dryer. Then, a heat set at 180 ° C. for 30 seconds was performed using a pin tenter. The dye is Telblue 3 RSF (manufactured by Nippon Kayaku Co., Ltd., disperse dye) was used at 6% 0 wf, and dyed at a bath ratio of 1:50 at 95 ° C for 60 minutes. As a dispersant, 0.5 g / liter of Nikki Sansol (Nikka Chemical Co., Ltd., anionic surfactant) is used, and 0.25 milliliter of acetic acid is used. The pH was adjusted to 5 by adding torr Z liter and 1 g Z liter of sodium acetate. The exhaustion rate was determined by measuring the absorbance A of the dye stock solution and the absorbance a of the dye solution after dyeing using a spectrophotometer, and substituting into the following formula. The value at 580 nm, which is the maximum absorption wavelength of the dye, was used as the absorbance.

Exhaust rate = (A-a) / A x 1 0 0 (%)

The degree of deep chromaticity, which indicates how deep the dye was, was evaluated using KZS. This value was obtained by measuring the spectral reflectance R of the sample cloth after dyeing, and using the following Kubelka-Munk (Kubelka-Munk) equation. The larger the value, the greater the deep color effect, ie, the better the color development. As R, the value at the maximum absorption wavelength of the dye was used.

KZ S = (1 - R) 2/2 R

The lightness when dyed in black was evaluated using the L value.

(8) Dye fastness test

The fastness test of the dyed fiber was evaluated using a single-mouth knitted fabric dyed by the method of (6).

Dry cleaning fastness is JIS-L-080, light fastness is JIS-L-0842, washing fastness is JIS-L-0844, and dry and wet friction The fastness was measured in accordance with JIS-L-08449. still

The dry cleaning fastness was tested for liquid contamination.

(9) U% measurement

The measurement was carried out using USTERTESTER 3 by Twelvega-Wooster. (Example 1)

Trimethylen glycol (hereinafter abbreviated as “TMG”) 1 144 4 parts by weight, dimethyl terephthalate (hereinafter abbreviated as “DMT”) 1300 parts by weight, 5 — sulphoisophthalic acid Trabutylphosphonium salt (hereinafter abbreviated as “SIPP”) 57 parts by weight (2 m 0 1% based on the total number of moles of all acid components), and lithium acetate 0.4 as an ether formation inhibitor Transesterification at 220 ° C using 3 parts by weight, 0.1 part by weight of cobalt acetate as a coloring inhibitor, and 1.3 parts by weight of titanate traboxide as a transesterification catalyst Was done. Then, 1.3 parts by weight of titanate laboxide as a polycondensation catalyst and 0.065 parts by weight of trimethyl phosphite as a heat stabilizer were added, and the pressure was reduced at 270 ° C. Polycondensation was performed at a temperature of 0.5 t 0 rr to obtain a polymer. The intrinsic viscosity of the obtained polymer was 0.61.

After drying the obtained polymer chip, a spinning temperature of 265 ° C and a spinning speed of 120 ° C were used using a spinning hole having 36 round cross-section holes (diameter: 0.23 mm). An undrawn yarn was prepared by spinning at m / min. Next, the obtained undrawn yarn is hot-rolled at 50 ° C. and hot-plated at 140 ° C. C. Stretching was performed at a draw ratio of 3.0 and a draw speed of 600 mZmin to obtain a drawn yarn of 50 d / 36 f. Physical properties of the fibers, the melting point 2 3 1 ° C, density ^{1. 3 2 g / cm 3} , strength 3. 4 g / d, elongation of 3 7%, T maxll 0 ° C, U% 1. 2%, elastic The rate was 22 g Zd, and the elastic recovery rate was 87%. In addition, the QZR value of the drawn yarn was 0.25, which satisfied expression (1). The b value of the fiber was 6.1.

The exhaustion rate of the cationic dye of the polyester fiber obtained in this example at 95 ° C. and 30 minutes was as large as 72%, and a very clear dyed product was obtained.

Dry cleaning of bite knitted fabrics after dyeing No liquid contamination was found, and the liquid contamination was class 4-1-5. In addition, the light fastness (class 4-15), the fastness to dry and wet friction (grade 5), and the fastness to washing (grade 5) were also good.

(Examples 2 to 7)

Polymerization and spinning were carried out in the same manner as in Example 1 except that the type of the ester-forming sulfonate compound and the copolymerization ratio were changed. Table 1 shows the test and evaluation test results of the obtained fibers. The fibers of all the examples satisfied the formula (1) and exhibited good dyeability, fastness, and various physical properties.

[Comparative Example 1]

In the same manner as in Example 1, polymethylethylene phthalate homopolymer was obtained without using SIPP. The intrinsic viscosity of the obtained polymer was 0.63. This polymer chip was spun and drawn in the same manner as in Example 1 to obtain a fiber. The resulting fiber has a melting point of 23 ° C, Tmax of 11 ° C, a strength of 3.6 g / d, an elongation of 35%, an elasticity of 23 g / d, and an elastic recovery of 88%. Indicated. The Q / R value of this fiber was 0.26, which satisfied the expression (1).

However, the exhaustion rate of the cation dye at 95 ° C. and 30 minutes of the polyester fiber obtained in this comparative example was 6%, and it could not be dyed in a deep color.

(Comparative Example 2)

A polymer was prepared in the same manner as in Example 1 except that the copolymerization ratio of SIPP was 0.3 mol%, and spinning was performed. Table 1 summarizes the test and evaluation results of the obtained fibers. The copolymerization ratio of the ester-forming sulfonate compound is less than 0.5 mol%, and the dye exhaustion rate of the dye at 95 ° C and 30 min at 30 ° C is 30%. Can't do it (Comparative Example 3)

In the same manner as in Example 1, a fiber was prepared through polymerization and spinning with a copolymerization ratio of SIPP of 6 mol%. Table 1 summarizes the test and evaluation results. During the spinning of this polymer, thread breakage occurred frequently and the spinnability was poor. When the fiber was dyed at 95 ° C, the yarn shrank and became hard, and a fabric with a good texture could not be obtained. Further, the dry cleaning fastness of the obtained fabric was lower than that of Example 1.

(Comparative Example 4)

In Example 1, the stretching ratio was 3.3 times. The orientation of the obtained fiber was too advanced, and T max exceeded 115 ° C. The exhaustion rate of the cationic dye was 45%. In addition, fluff was frequently generated in the obtained fiber.

table 1

S I PM 5-Sulfoisophthalic acid ammonium dimethyl S I PA 5-Sulfoisophthalic acid ammonium salt

DC fastness Dry cleaning fastness

(Comparative Example 5)

Polymerization and spinning were carried out in the same manner as in Example 1 except that the temperature of the hot roll was 25 ° C. Many yarn breaks occurred during drawing, and fibers could not be obtained continuously. Polymerization and spinning were performed in the same manner as in Example 1 except that the temperature of the hot roll was set at 80 ° C. At the time of drawing, the yarn was fused to the hot roll, and single yarn breakage occurred frequently, and the obtained fiber was full of fluff. U% was 3.2, which was bad.

(Comparative Example 6)

Polymerization and spinning were carried out in the same manner as in Example 1 except that the temperature of the hot plate was 70 ° C. Fibers were obtained without problems such as yarn breakage and fluffing. However, the obtained fiber had a low elastic recovery of 55% and a QZR value of 0.49, which did not satisfy the expression (1).

(Comparative Example 7)

Polymerization / spinning was performed in the same manner as in Example 1 except that the temperature of the hot plate was set at 200 ° C. The fiber was cut at the hot plate and could not be drawn.

(Comparative Example 8)

Polymerization / spinning was performed in the same manner as in Example 1 except that the draw ratio was 2.3 times and the temperature of the hot plate was 180 ° C. Fibers were obtained without problems such as yarn breakage and fluffing. However, the obtained fiber had a low elastic recovery rate of 48%, a QZR value of 0.52, and could not satisfy the expression (1).

(Comparative Example 9)

Spinning was performed using poly (ethylene terephthalate) fiber obtained by copolymerizing 2.5% by mole of 5-sodium sulfoisophtalic acid. The obtained fiber had a strength of 4.2 g Zd, an elongation of 30%, an elasticity of 100 g / d, an elastic recovery of 31%, a QZR value of 3.2, and a Tmaxl of 31 ° C. Show, Katyo The exhaustion rate of the dye at 95 ° C. and 30 minutes was 36%.

(Reference Example 1)

Example 1 was repeated without using cobalt acetate and trimethyl phosphite. In this case, there was no change in the fiber properties, but the b value of the fiber was 11.2, which turned yellow.

(Example 8)

The polymer obtained in Example 2 was dried to a water content of 50 ppm, melted at 285 ° C, and spinned into a single array having 0.23 mm diameter and having 36 holes. Extruded through mouth. The extruded molten multifilament is passed through a heat retaining area with a length of 5 cm and a temperature of 100 ° C, and then quenched by blowing air at a wind speed of 0.4 m / min to obtain a solid multifilament. I changed it to a comment. Next, this solid multifilament was heated to 60 ° C, and the first roll was at a speed of 210 m / min, and the rotary speed was heated to 133 ° C, 4300 m / min Then, hot stretching and heat setting were performed between the second rolls, and then the film was wound at 418 m / min. The obtained fiber was made into a double yarn and made 75 d / 72 f.

The obtained fiber has a strength of 3.1 g Zd, an elongation of 41%, a U% of 0.7%, an elasticity of 22 gZd, a sexual recovery rate of 89%, a Q / R of 0.25, The exhaustion rate of the cationic dye at Tmax 109 ° C, 95 ° C, and 30 minutes was 98%, and the b value was 6.5.

(Example 9)

A warp knitted fabric was formed using the polyester fiber of Example 1 and a loyal force of 210 denier (polyurethane stretch fiber manufactured by Asahi Kasei Kogyo Co., Ltd.). The knitting gauge is 28 G, the polyester fiber is 108 mm / 480 course of polyester fiber, stretch fiber strength is 12 mm / 480 course, and driving is performed. The density was 90 courses Z inch. The mixing ratio of the polyester fiber was set to 75.5%. The obtained greige was subjected to relax scouring for 90 minutes and a dry heat set at 160 ° C for 1 minute. Disperse TL (Non-ionic activator manufactured by Meisei Chemical Co., Ltd.) is used as a dispersant in 1 g Z using KYARILL BLACK BS-ED (cationic dye manufactured by Nippon Kayaku Co., Ltd.) Using a liter, add 50 g of sodium sulfate and 15 g / liter of sodium carbonate, and dye by adding a dye to an aqueous solution whose pH has been adjusted to 11. Liquid. Staining was performed at 95 ° C. for 1 hour at a staining concentration of 8% 0 wf and a bath ratio of 1:50. After staining, Granup P (manufactured by Sanyo Kasei Kogyo Co., Ltd., non-ionic surfactant) 1 g Z liter, bath ratio 1: 50, 80 ° C. for 10 minutes. After dyeing, finishing was performed by a conventional method. The obtained dyed product had an L value of 11.2, which was sufficiently dyed. The dyeing fastness of the dyed materials is from the washing fastness class 5, the wet rub fastness class 5, and the light fastness class 4.

It was 5th grade. The dyed knitted fabric was soft, rich in stretch, and had an excellent texture with tightness and waist.

(Example 10)

The same operation as in Example 9 was repeated using the polyester fiber of Example 2. The L value of the obtained dyed product was 10.9, indicating that it was sufficiently dyed. The dyeing fastness of this dyed product was 5 for washing fastness, 5 for wet rub fastness, and 4 to 5 light fastness. The dyed material was soft, rich in stretchiness, and had an excellent texture with a firm and firm feel.

(Comparative Example 10)

The same knit as in Example 9 was knitted using the polymethylene terephthalate fiber prepared in Comparative Example 1.

The obtained greige was subjected to relax scouring at 90 ° C for 2 minutes and subjected to a dry heat set at 160 ° C for 1 minute. To dye in a dark color, use Dynix Black BG-FS (Disperse Dye, manufactured by Dystar Japan) 8% 0 wf, and add 0.5 g / In the presence of a little, the pH was adjusted to 6 with acetic acid, and the cells were stained at a bath ratio of 1:30 at 95 ° C for 60 minutes. The wet rub fastness of the obtained dyed product was of the second grade, and the release of the disperse dye contaminating the stretch fiber was observed.Similar to Example 9 using the fiber prepared in Comparative Example 9 Was repeated. The resulting fabric was clearly hard and was dyed only in a light color with an L value of 21.

For comparison, a warp knitted fabric of nylon 6 fiber and Roy force spun by the usual method was prepared in the same manner as in Example 9, and was prepared by using Callon Black BGL (manufactured by Nippon Kayaku Co., Ltd.). Dye) at 7% 0 wf at 100 ° C. for 60 minutes. The lightfastness of the obtained dyed fabric was 2 to 3.

(Example 11)

A 75-dZ36f polyester fiber obtained in the same manner as in Example 1 was used for warp and a 75-d / 44-f cuprammonium rayon for the weft, to give a plain weave (140-w / 25.4 mm, weft 80 / 25.4 mm). This plain fabric was scoured by a conventional method. After washing with water, 180 ° C, 3

After the 0-second preset, one-step one-bath dyeing with a cationic dye and a reactive dye was performed without using a carrier. The cation dyes used were KYRILLIL BLACK BS-ED (Cation dyes, manufactured by Nippon Kayaku Co., Ltd.) and Dori Maleble X-SGN (Sand Co., Ltd., reactive dyes). . The dispersant used was Dispar TL (manufactured by Meisei Chemical Co., Ltd.) at a rate of 1 g / liter, 50 g of sodium sulfate and 15 g / liter of sodium carbonate. The dye was added to the aqueous solution whose pH was adjusted to 11 to obtain a dye solution. Staining was performed at 100 ° C. for 1 hour at a concentration of 2% 0 wf and a bath ratio of 1:50. After staining, the granules were soaked in Granup P (manufactured by Sanyo Chemical Industry Co., Ltd.) at 1 g / liter and a bath ratio of 1:50 at 80 ° C. for 10 minutes. staining After that, finishing was performed by a conventional method. The obtained dyed product was uniformly dyed and was a clear dyed product. K / S was 24.3. In addition, despite the fact that the alkali weight reduction treatment performed with ordinary polyester fibers was not performed, the fabric was full of soft texture and dryness, and had an excellent texture that cannot be obtained with conventional fabrics. The dry cleaning fastness was grade 5, the wet friction fastness was grade 5, and the light fastness was grade 4.

Using 75 d / 36 f polyester fiber obtained in the same manner as in Example 1, a plain woven fabric was prepared using the same weft and warp yarns, and dyed. Although the obtained fabric did not have a dry feeling, it was extremely soft and the fabric showed a stretch property of about 7% in the weft direction.

(Example 12)

The fiber obtained in Example 1 was copolymerized and spun in the same manner as in Example 1, and copolymerized with 3% by mole of polyethylene terephthalate fiber and sodium 5-naphthalomisophthalate. A weight loss test was carried out using a single-knit fabric (circular knit, sheeting, gauge 28) prepared from the prepared polyethylene terephthalate fiber. After knitting, the knitted fabric is scoured at 70 ° C for 20 minutes using warm water containing score roll 400 at 2 g / liter, dried with a tumble dryer, and then dried. A heat set at 180 ° C. for 30 seconds using a pin tenter was used. Alkali weight reduction processing was carried out by placing the bite knitted fabric in a 6% by weight aqueous solution of sodium hydroxide boiled for 20 minutes. The alkali weight loss rate was evaluated by dividing the weight of the knitted fabric reduced by the weight loss by the weight of the original knitted fabric.

As a result, the weight loss rates of the single-port knitted fabric of the fiber obtained in Example 1 and the single-port knitted fabric of polyethylene terephthalate fiber were 25.4% by weight and 10.3% by weight, respectively. Thus, the polyester fiber of the present invention exhibits a weight loss rate close to that of polyethylene terephthalate fiber. did.

[Comparative Example 11]

In the same manner as in Example 12 using a one-piece knitted fabric obtained by knitting polyethylene terephthalate fiber obtained by copolymerizing sodium 5 sodium sodium sulfophthalate at 3 mol% in the same manner as in Example 12 When the weight was reduced, the knitted fabric was completely decomposed, dissolved and disappeared. Therefore, in the case of polyethylene terephthalate fiber obtained by copolymerizing 3% by mole of sodium 5-sodium sulfoisophtalate, it is practically impossible to reduce the weight loss rate because the rate of weight loss is too fast. It is possible.

(Example 13)

Using a method similar to that of Example 1, a fiber was prepared by copolymerizing 2 mol% of dimethyl sodium 5-dimethylsophthalate and 5 wt% of dimethyl ethyl adipate. The physical properties of the fiber are as follows: melting point: 220 ° C, strength: 3.6 g / d, elongation: 34%, elasticity: 22 g Zd, elastic recovery: 90%, and R value of 0.2 It was five.

The exhaustion rate of the cationic dye at 95 ° C and 30 minutes of the polyester fiber obtained in this example was 95%, and the exhaustion rate of the disperse dye at 95 ° C and 60 minutes. Showed high dyeability at 95% for both cationic dyes and disperse dyes at normal pressure.

The dry cleaning fastness of the one-necked knitted fabric after dyeing did not show any fading of the dyed material, and the cation dye and the disperse dye were in the 4th to 5th class of liquid contamination. In addition, the light fastness (four to five grades), dry / wet friction fastness (five grades), and washing fastness (five grades) of the fibers were also good.

In addition, when the same woven or knitted fabric as in Examples 9 and 11 was prepared, a fabric having the same excellent texture as in Examples 9 and 11 was obtained.

(Example 14)

The fiber obtained in Example 2 was cut to obtain a short fiber having a fiber length of 39 mm. . A 20 d / 2 f filament obtained in the same manner as in Example 2 was used as a core, and the short fibers were arranged in a sheath. The filament mixture was 11 wt%. Yarn was obtained. The composite yarn was woven into a warp (weaving density: 144, Z25.4 mm) and weft (weaving density: 77, Z25.4 mm) woven fabrics, and was woven according to the method of Example 9. Staining was performed at ° C.

The KZS of the dyed fabric was dyed deep at 25.3. The obtained fabric was excellent in tension, waist, and resilience.

(Example 15)

The polymer obtained in Example 2 was subjected to solid-state polymerization in nitrogen at 200 ° C. for 24 hours to obtain a polymer having an intrinsic viscosity of 1.0. The spinning was carried out in the same manner as in Example 1, and the strength was 4.0 (5, elongation 32%, 11% 1.0%, elastic modulus 23 g Zd, elasticity recovery rate 91%, QZR value A fiber having physical properties of 0.25, T maxll O ° C, and b value of 4.3 was obtained.

(Example 16)

TMG 103 parts by weight, 1,4-butanediol (hereinafter abbreviated as “4G”) 106 parts by weight, DMT 130 parts by weight, titanium tetrabutoxide 1.3 parts by weight After transesterification at 220 ° C using, 0.01% by weight of trimethyl phosphite was added, and the pressure was reduced to 0.5 t0 rr at 250 ° C. Then, polycondensation was performed to obtain a polymer. The intrinsic viscosity of the obtained polymer was 0.8. Further, the 4G component in the polymer measured by using NMR was 4.1% by weight.

After drying the obtained polymer chip, a spinning temperature of 265 ° C and a spinning speed of 1200 were used using a spinning hole having 36 round cross-section holes (diameter: 0.23 mm). An undrawn yarn was prepared by spinning at m / min. Next, the obtained undrawn yarn is hot-rolled 60. C, a hot plate was applied at 140 ° C, a draw ratio of 2.9 times, and a draw speed of 600 mZmin was used to obtain a drawn yarn of 50 d / 36 f. Fiber properties are as follows: melting point: 2 24 ° C, Tma x 98 ° C, strength 3.6 g Zd, elongation 40%, U% 1.2%, elastic modulus 23 g / d, elastic recovery 83%, b value 4.5 . The QZR value of this fiber was 0.28, thereby satisfying the expression (1). In addition, the exhaustion rate of the polyester fiber of this example at 95 ° C. and 60 minutes by the disperse dye was 78%, indicating a high exhaustion rate.

In the dry-cleaning fastness of the one-piece knitted fabric after dyeing, no fading of the dyed material was observed, the liquid contamination was 3.5 grade, the light fastness (5 to 4 grade), the dry • wet friction fastness (5 grade) ) The washing fastness (grade 5) was also good.

(Examples 17 to 21)

Polymerization / spinning was carried out in the same manner as in Example 16 except that the type of glycols and the ratio of glycols to TMG were changed. Table 2 summarizes the test and evaluation results for each of the obtained fibers. In each case, it was a fiber satisfying the formula (1), and exhibited good dyeing properties, dyeing fastness, and various physical properties.

(Comparative Example 1 2)

Using the polymer of Comparative Example 1, a fiber was prepared in the same manner as in Example 1, and the dyeability of the polyester fiber was evaluated by the disperse dye of the above (7) Dyeability evaluation test (1). However, the polyester fiber obtained in this comparative example had a T max of more than 102 ° C. The exhaustion rate of this fiber by the disperse dye at 95 ° C and 60 minutes was 36%, and it was not possible to dye it in a deep color. However, when the dye concentration was set at 0.5% owf, the exhaustion rate was increased to 81%. Therefore, this result indicates that polymethylethylene terephthalate fiber shows normal pressure dyeability at a low dye concentration with respect to the disperse dye, but does not show normal pressure dyeability at a high dye concentration. I understand.

(Comparative Example 13) Polymerization / spinning was performed in the same manner as in Example 16 except that the ratio of TMG to 4G was changed. The results are shown in Table 2. The proportion of the 4G component was less than 1.5% by weight and the Tmax of the fiber was 106 ° C. The exhaustion rate by the disperse dye at 95 ° C and 6 minutes was low, and it was not possible to dye in a dark color.

Table 2

4 G 1, 4 Monobutanediol 6 G 1, 6—Hexanediol

3 G-2 Neopentyl glycol C 6-2 G Cyclohexanedimethanol

(Comparative Example 14)

Polymerization / spinning was performed in the same manner as in Example 16 except that the ratio of TMG to 4G was changed. Table 2 shows the physical properties and evaluation results of the obtained fibers. The ratio of the 4G component was 10.3% by weight. The Tmax of the fiber was 85 ° C or less, and the exhaustion rate was high, but the dry cleaning fastness was very low at class 1.

(Comparative Example 15)

Hexamethylen glycol (hereinafter abbreviated as 6G) was used in place of 4G, and polymerization and spinning was performed in the same manner as in Example 16 except that the ratio of TMG to 6G was changed. Table 2 shows the test and evaluation results of the obtained fibers. The proportion of the 6G component of the polymer was 8.7% by weight. However, the Tmax of this fiber was 85 ° C or less, and when dyed at 95 ° C for 60 minutes, the exhaustion rate exceeded 70%. The ruggedness was very poor at 1st grade. In addition, the melting point of the fiber was as low as 210 ° C., and when processing such as false twisting was performed, the yarn was fused to the heater and processing could not be performed.

(Comparative Example 16)

Polymerization was carried out in the same manner as in Example 16 except that cyclohexanedimethanol (hereinafter abbreviated as C6-12G) was used instead of 4G and the ratio of TMG to C6-2G was changed. · Spinning was performed. The results are shown in Table 2. The ratio of the C 6 -2G component was 12.6% by weight. However, the elastic modulus of this yarn was 24 g Zd, the elastic recovery was 34%, and the QZR value was 0.71, which did not satisfy the expression (1). The fabric obtained from this yarn had poor elastic recovery. The Tmax of the fiber was 62 ° C. When dyed at 95 ° C for 60 minutes, the fabric shrank and became hard.

(Comparative Example 17) Polymerization spinning was carried out in the same manner as in Example 16 except that ethylene glycol (hereinafter abbreviated as 2G) was used instead of 4G and the ratio of TMG to 2G was changed. The results are shown in Table 2. The obtained polymer is colored yellow, and the obtained fiber is also colored yellow with a b value of 18.3, and should be used for uses such as inner whiteners that require whiteness. Could not be done.

(Example 22)

A warp knitted fabric was prepared using the polyester fiber of Example 16 and a 210 denier Roy force (polyurethane-based stretch fiber manufactured by Asahi Kasei Corporation). The knitting gauge of this knitted fabric is 28 G, the loop length is 1800 mm / 480 course for polyester fiber, and 11 mm / 480 course for stretch fiber. The implantation density was 90 courses Z inch. The mixing ratio of the polyester fiber was set at 75.5%.

The obtained greige was subjected to relax scouring at 90 ° C for 2 minutes and subjected to a dry heat set at 160 ° C for 1 minute. In the presence of 8% owf of Dianix Black BG-FS (Disperse Dye manufactured by Daiichi Yuichi Japan Co., Ltd.) and 0.5 g / liter of Nikka Sun Salt 1200 as a dyeing aid. The pH was adjusted to 6 with acetic acid, and the cells were stained at a bath ratio of 1:30 at 95 ° C for 60 minutes.

The black lightness L value of the obtained dyed product was 11.7, which was sufficient for coloring. The dyed product has a washing fastness of 5, a wet rub fastness of 4, and a light fastness of 4, and has a soft, stretchy, tight, and firm feel.

(Comparative Example 18)

For comparison, a warp-knitted fabric of nylon 6 fiber spun by a conventional method and Roy force was prepared in the same manner as in Example 22 and calo black BGL (Nippon Kayaku Co., Ltd.) was used as the acid dye. At 7% owf Staining was performed at 95 ° C for 60 minutes. The L value of the obtained dyed product was 12.3. The lightfastness of this fabric was 2 to 3.

(Example 23)

Using a 75 d / 36 f polyester fiber obtained in the same manner as in Example 16 as a warp and a weft as a 75 d / 44 f copper ammonia rayon, a plain woven fabric (weaving density 1 40 lines Z25.4 mm, Latitude 80 lines / 25.4 mm). This plain fabric was scoured and made into a mass by a conventional method. The mercerization process was performed at room temperature by immersion in a 75% sodium hydroxide aqueous solution. Neutralization, washing, pre-setting at 180 ° C for 30 seconds, and one-step single-bath dyeing with a disperse dye and a reactive dye without using a carrier Ester blue BRSF (manufactured by Nippon Kayaku Co., Ltd., disperse dye) and Drimaren Blue X—SGN (manufactured by Sando Co., Ltd., reactive dye) were used. As a dispersant, use 1 g of Dayspar TL (manufactured by Meisei Chemical Co., Ltd.), add 50 g of sodium sulfate and 15 g / liter of sodium carbonate and sodium carbonate, and add p. The dye was added to the aqueous solution in which H was adjusted to 11 to obtain a dye solution. Dyeing was performed at 95 ° C. for 1 hour at a dye concentration of 2% owf and a bath ratio of 1:50. After staining, the sample was rubbed with Granup P (manufactured by Sanyo Chemical Co., Ltd., nonionic surfactant) at 1 g / liter and a bath ratio of 1:50 at 80 ° C. for 10 minutes. After dyeing, finishing was performed by a conventional method. The obtained dyed product was uniformly dyed, had a soft texture, had a dry feeling, and had a good texture not seen in conventional fabrics. The dyed product had a K / S of 22.7, a dry cleaning fastness of 3 to 4, a wet rub fastness of 4, and a light fastness of 4.

Using a 75 d / 36 f polyester fiber obtained in the same manner as in Example 16, a similar plain woven fabric was prepared using the same weft and warp yarns and dyed. Although the obtained fabric had no dry feeling, the fabric was extremely soft and showed a stretch property of about 7% in the weft direction. (Example 24)

A twist of 300 TZm was applied to the polyester fiber of Example 16 and glued with a roller. Then, the warp was used, and diacetate (100 d / 150 f) was used for the weft. A plain woven fabric (120 warps / 25.4 mm, weft 80 warp Z25.4 mm) was woven.

Nippon Kayaku Polyesterable RSRS (manufactured by Nippon Kayaku Co., Ltd.) as a disperse dye for polyester fiber, and Nyakuhon Kabushiki Kaisha RD 200 (Nippon Kayaku) as a disperse dye for diacetate (Manufactured by Sharp Corporation). The dye concentration was 5% owf for each step, and one-step single-bath dyeing was carried out at 95 ° C in the presence of a dispersant with weak acidity. After staining, soda ash 1 g Z liter, nonionic detergent 0.5 g Z liter 70 in a weak alkaline bath. C. Soaking was performed for 20 minutes. The K / S of the obtained dyed product was excellent, 22.2. The dyed product had a dry cleaning fastness of 3 to 4th grade, a light fastness of 4th grade, a soft texture and excellent clarity.

(Example 25)

Transesterification was carried out at 220 ° C using 117 parts by weight of DMT, 130 parts by weight of dimethyl isophthalate, 1.3 parts by weight of TMG 763 parts, and 1.3 parts by weight of titanate laboxide. Thereafter, 0.01 part of trimethyl phosphate was further added, and polycondensation was performed at 260 ° C. at a reduced pressure of 0.5 t 0 rr to obtain a polymer. The intrinsic viscosity of the obtained polymer was 0.8. The isophthalic acid component in the polymer measured by NMR was 6.2% by weight.

After drying the obtained polymer chip, a spinning temperature of 265 ° C and a spinning speed of 1200 were used using a spinning hole having 36 round cross-section holes (diameter: 0.23 mm). An undrawn yarn was prepared by spinning at m / min. Then, the obtained undrawn yarn was heated at a hot roll of 60 ° C, a hot plate of 140 ° C, Stretching was performed at a draw ratio of 2.9 and a draw speed of 600 m / min to obtain a drawn yarn of 50 d / 36 f. The physical properties of the fiber are as follows: melting point: 21.9 ° C, Tmax: 100 ° C, strength: 3.5 g / d, elongation: 43%, U%: 1.0%, elastic modulus: 24 gd, elastic recovery The b value was 7.6%, and the b value was 7.6. In addition, the Q / R value of the fiber was 0.29, which satisfied Expression (1). The polyester fiber of this example had an exhaustion rate of 81% with a disperse dye at 95 ° C for 60 minutes, indicating a high exhaustion rate. The dry-cleaning fastness of the one-necked knitted fabric after dyeing did not show any fading of the dyed material, and the liquor contamination was grade 3. The dyeing fastness of the dyed product was good in light fastness (grade 4 to 5), dry / wet rub fastness (grade 5), and wash fastness (grade 5).

(Examples 26 to 31)

Polymer spinning was performed in the same manner as in Example 25 except that the type of the dicarboxylic acid derivative was changed. Table 3 summarizes the evaluation results of this fiber. All of the fibers satisfied the formula (1) and exhibited good dyeing properties, fastness, and various physical properties.

[Comparative Examples 19, 20]

Example 25 was repeated, except that the copolymerization ratio of dimethyl isophthalate was changed. Table 3 shows the test and evaluation results of the obtained fibers. In Comparative Example 19, the copolymerization ratio was too low, resulting in inferior dyeability of the fibers. In Comparative Example 20, the copolymerization ratio was too high, resulting in a decrease in dry cleaning fastness.

Table 3 Copolymer components Melting point Intrinsic viscosity Strength Elongation Elastic modulus Elastic recovery Q / R Tmax U% Exhaustion rate DC fastness b value Type Weight% (° C) () (g / d) (%) (g / d) (%). C% () (grade) Example 25 Dimethyl isophthalate 6.2 219 0.80 3.5 43 24 82 0.29 100 1.0 81 3 7.6 Example 26 Dimethyl isophthalate 5.2 224 0.81 3.5 43 24 75 0.43 102 0.8 75 4 7.5 Example 27 Isophthalic acid Dinutyl 7.4 216 0.75 3.4 42 20 83 0.25 96 1.0 91 3 7.3 Example 28 Dimethyl succinate 4.0 222 0.80 3.5 42 22 85 0.28 92 1.1 85 38.2 Example 29 Dimethyl adipate 5.3 222 0.77 3.5 41 23 90 0.23 89 1.2 96 3 9.6 Example 30 di- / chill sebacate 7.8 210 0.80 3.0 44 22 86 0.19 85 1.1 96 3 9.5 Example 31 1,4-six π-hexane 6.0 220 0.80 2.2 42 23 87 0.21 85 1.2 90 3 9.0

J! I-Rubonic acid

Comparative Example 19 Dimethyl isophthalate 1.8 227 0.80 3.6 40 23 89 0.26 108 54 4 7.6 Hiken Example 20 Dimethyl Nophthalate 12.3 225 0.80 2.4 54 19 70 0.27 69 96 1 7.6

(Reference Example 2)

Example 29 was repeated without using trimethyl phosphite. Although the fiber properties of the obtained fiber did not change, the b value of the fiber was 12.3, which turned slightly yellow.

(Example 32)

A warp knitted fabric was prepared using the polyester fiber of Example 25 and a loyal force of 210 denier (polyurethane stretch fiber manufactured by Asahi Kasei Corporation). The knitting gauge is 28 GG, the loop length is 1800 mm / 480 course of polyester fiber, the stretch fiber strength is 11 mm / 480 course, and the driving density is 9 0 course Z inch. The mixing ratio of polyester fiber was set at 75.5%.

The obtained greige was relaxed and scoured at 90 ° C for 2 minutes, and dried and set at 160 ° C for 1 minute. 8% owf of DYNAMIC BLACK BG-FS (Disperse Dye manufactured by Dystar Japan) and 0% of Nikka Sansalt 1200 (a dyeing aid manufactured by Nikka Chemical Co., Ltd.) The pH was adjusted to 6 with acetic acid in the presence of 0.5 g Z-liter, and staining was carried out at a bath ratio of 1:30 at 95 ° C for 60 minutes.

The black lightness L value of the obtained dyed product was 11.3, which was sufficient for color development. Washing fastness of the dyed product was class 5, wet rub fastness was class 4, and light fastness was class 4. In addition, the dyed product was soft and rich in stretch feeling, and had a firm and waisted texture.

(Example 33)

Transesterification was carried out at 220 ° C using DMT 130 parts by weight, TMG 112 1 parts by weight, titanyl tributoxide 1.3 parts by weight, and cobalt acetate 0.01 parts by weight. Thereafter, 69 parts by weight of polyethylene glycol having an average molecular weight of 1000 and 0.01 part by weight of phosphoric acid were added, and the mixture was decompressed at 260 ° C under a pressure of 0.5 t0 rr. The polymer was obtained by polycondensation. The intrinsic viscosity of the obtained polymer was 0.82. The copolymerization ratio of polyethylene glycol having an average molecular weight of 1,000 was 5% by weight. After drying the obtained polymer chip, a spinning temperature of 26 ° C. and a spinning speed of 1 using a spinning hole having 36 round cross-section holes (0.23 mm) were used.

An undrawn yarn was prepared by spinning at 200 m / min. Next, the obtained undrawn yarn was drawn at a hot roll of 50 ° C, a hot plate of 140 ° C, a draw ratio of 2.9 times, and a drawing speed of 60 Om / min. /

A 36 f drawn yarn was obtained. The physical properties of the fiber are as follows: Melting point: 23 ° C, Tmax: 92 ° C, strength: 3.1 g / d, elongation: 43%, U%: 1.1%, elastic modulus: 20 g Zd, elasticity The recovery rate was 89% and the b value was 8.2. In addition, the QZR value of the fiber was 0.22, thereby satisfying the expression (1).

95 of the polyester fiber of this example. The exhaustion rate by the disperse dye for 60 minutes at C was 92%, indicating a high exhaustion rate.

In the dry clearing fastness of the one-knit fabric after dyeing, no fading of the dyed product was observed, and the liquor contamination was class 2. In addition, the light fastness of the fiber (grade 3), dry / wet friction fastness (grade 5), and wash fastness (grade 5) were also good.

(Examples 34 to 40)

Polymerization and spinning were performed in the same manner as in Example 33, except that the type of polyalkylene glycol was changed. Table 4 summarizes the obtained tests and evaluation results. The fibers of all Examples satisfied the formula (1) and exhibited good dyeing properties, fastness, and various physical properties.

[Comparative Examples 23 and 24]

The same operation as in Example 33 was repeated, while changing the copolymerization ratio of polyethylene glycol. Table 4 shows the results. In Comparative Example 23, the copolymerization ratio was too low and the dyeability was insufficient, and in Comparative Example 24, the copolymerization ratio was too high and the dry cleaning fastness was poor. Also the whiteness of the fiber Also fell.

Table 4

PEG: polyethylene glycol

P TMG: Polytetramethylene glycol

(Example 41)

Example 33 A warp knitted fabric was prepared using the polyester fiber of Example 3 and a loyal force of 210 denier (polyurethane-based stretch fiber manufactured by Asahi Kasei Corporation). In this case, the gauge is 28 G, the loop length is 108 mm / 480 course of polyester fiber, the stretch fiber strength is 112 mm / 480 course, and the driving density is 9 0 course Z 25.4 mm. The mixing ratio of the polyester fibers was set at 75.5%.

The obtained greige was relaxed and scoured at 90 ° C for 2 minutes, and dried and set at 160 ° C for 1 minute. 8% owf of Dyanix Black BG-FS (manufactured by Dyster Japan) and 0.5 g of Nitukasan Sonoret 1200, which is a dyeing aid, with 0.5 g of Z-Little The pH was adjusted to 6, and staining was carried out at a bath ratio of 1:30 at 95 ° C for 60 minutes.

The black lightness L value of the obtained dyed product was 11.0, and the color was sufficiently developed. The washing fastness of the fiber was grade 5, the wet rub fastness was grade 4, and the light fastness was grade 4. In addition, the dyed fabric had a soft and stretchy feel, and had a tight and waisted texture.

(Example 4 2)

Polymethylene terephthalate having an intrinsic viscosity of 0.9 and polybutylene terephthalate having an intrinsic viscosity of 1.0 are mixed at a ratio of 94.8: 5.2 and extruded as it is. Then, in the same manner as in Example 17, polymethylene terephthalate fiber obtained by copolymerizing 5.2% by weight of 1,4-butanediol was obtained.

The obtained fiber is almost equivalent to the fiber of Example 17 and has a strength of 3.6 g d, an elongation of 43%, a U% of 0.7%, an elasticity of 23 g / d, and an elastic recovery. Rate: 81%, b value: 4.4, Q / R value: 0.28, Tmax: 97% at 95 ° C, 95% at 60 minutes, exhaustion rate by disperse dye was 84%. .

(Example 43) Weaving a plain woven fabric (40 warp yarns) using the 75 d Z 36 f polyester fiber obtained in Example 1 as a warp yarn and a 75 d / 44 mm copper ammonia rayon as a weft yarn / 25.4 mm, latitude 80 lines Ζ 25.4 mm). This plain fabric was scoured by a conventional method. After washing with water and pre-setting at 80 ° C. for 30 seconds, one-step one-bath dyeing with a cation dye and a reactive dye was performed without using a carrier. Cryacryl Black BS-ED (Cation Dye manufactured by Nippon Kayaku Co., Ltd.) and Drimaremble X-SGN (Reactive Dye manufactured by Sand Co., Ltd.) were used. Using 1 g Z liter of DISPER TL (Dispersant manufactured by Meisei Chemical Co., Ltd.), add 50 g / liter of sodium sulfate and 15 g Z liter of sodium carbonate. The dye was added to the aqueous solution whose pH was adjusted to 11 to obtain a dye solution. Dyeing was carried out at 100 ° C. for 1 hour at a dye concentration of 2% owi and a bath ratio of 1:50. After staining, the sample was soaked at 80 ° C. for 10 minutes at 1 g / liter, Granup P (manufactured by Sanyo Chemical Industries, Ltd.) at a bath ratio of 1:50. After dyeing, finishing was performed by a conventional method.

The obtained dyed product was uniformly dyed, was excellent in wet rub fastness, dry cleaning fastness, and light fastness, and was a clear dyed product. In addition, despite the fact that the weight loss treatment performed with ordinary polyester fibers was not performed, the texture was full of soft texture and dry feeling, and was an excellent texture that cannot be obtained with conventional woven fabrics.

The same plain woven fabric was woven and dyed using 75 d / 36 f polyester fiber obtained in the same manner as in Example 1, using the same warp and weft. Although the obtained fabric did not have a dry feeling, it was extremely soft and the fabric exhibited a stretch property of about 7% in the weft direction.

(Comparative Example 25)

In Example 43, when dyeing was performed at a temperature of 130 ° C., the reactive dye was decomposed, and the fabric was darkened.

(Example 4 4) Weaving a plain fabric using the 75 d / 36 f polyester fiber obtained in Example 1 for warp and weft (140 warp / 3.54, warp 80 / 2.54 ) did. After scouring the plain fabric by a conventional method, the alkali weight was reduced by 20% using a 10% aqueous sodium hydroxide solution. Thereafter, the same pre-setting and staining as in Example 43 were performed, and finally a final set was performed at 180 ° C. for 30 seconds.

The obtained fabric showed a soft and dry feeling that was not seen before, and also showed a stretch property of about 7% in the weft direction. Industrial applicability

The poly (methylen terephthalate) fiber of the present invention can be dyed at ordinary pressure with either a dye or a disperse dye or both dyes to a color density (shades) practically required. . In addition, the polymethylene terephthalate-based fiber of the present invention has an Ossian de-air property similar to general-purpose polyester fibers such as polyethylene terephthalate fiber, dimensional stability, yellowing resistance, and the like. It is a fiber material that has a dry feel and a workability for reducing weight, and has flexibility similar to nylon fibers.

Due to the above-mentioned performance, the polytrimethylene terephthalate fiber of the present invention can be used for heat-resistant fibers such as stretch fibers typified by polyurethane elastic fibers, wool, silk, and acetate. It is a suitable fiber material for the production of fast-dyed fabrics mixed with low-strength fiber materials and cellulosic fibers dyed at normal pressure. In particular, with respect to a fabric product obtained by mixing with the above-mentioned low heat-resistant fiber, a robust dyeing fabric can be manufactured by a simple dyeing method using a general-purpose normal-pressure dyeing facility without impairing the properties of the fiber. It is an industrial utility to be noted.

Claims

The scope of the claims

1. In a fiber composed of a polyester obtained by copolymerizing a third component with polymethylene terephthalate, the third component is an ester-forming sulfonate compound having a copolymerization ratio of 0.5 to 5 mol%, The loss tangent peak temperature of the fiber is 85 to 115 ° C., and the relationship between the elastic modulus Q (g / d) and the elastic recovery rate R (%) of the fiber is expressed by the following formula (1). Polyester fiber characterized by satisfying (1).

0.18 ≤ Q / R ≤ 0.45 · · · Equation (1)

2. The ester-forming sulfonate compound is 5-sodium sulfisophthalic acid or / and a tetraalkyl phosphonium salt of 3,5-dicarboxylic acid benzene sulfonate. Polyester fiber as described.

(Here, the alkyl group indicates an alkyl group having 1 to 10 carbon atoms.)

3. The polyester fiber according to claim 1, wherein the third component is 1.2 to 2.5 mol% of an ester-forming sulfonate compound.

4. The ester-forming sulfonate compound is 5-sodium sulfisophthalic acid or a tetraalkylphosphonium salt of Z and 3,5-dicarboxylic acid benzenesulfonate, and the copolymerization ratio is 1. 2. The polyester fiber according to claim 1, wherein the content is 2 to 2.5 mol%.

(Here, the alkyl group is an alkyl group having 1 to 10 carbon atoms.) 5. In a fiber made of polyester obtained by copolymerizing polymethylene terephthalate with a _third component, the _third component is (1) Copolymerization ratio 1

.

5 to 12% by weight of an aliphatic or alicyclic glycol having a carbon number of 4 to 12; (2) a copolymerization ratio of 3 to 9% by weight of a carbon number of 2 to 14; At least one selected from aliphatic or alicyclic dicarboxylic acid, or isophthalic acid, and (3) a polyalkylene glycol having a copolymerization ratio of 3 to 10% by weight, and a peak temperature of loss tangent of the fiber. Is 85 to 102 ° C., and the relationship between the elastic modulus Q (g / d) and the elastic recovery rate R (%) of the fiber satisfies the following expression (1). Polyester fiber.

0.18 ≤ Q / R ≤ 0.45 · · · Equation (1)

6. An ester-forming sulfonate compound having a copolymerization ratio of 1.2 to 2.5 mol%, (1) an aliphatic or alicyclic glycol having 4 to 12 carbon atoms, (2) A polymer obtained by copolymerizing at least 3 to 7% by weight of at least one selected from aliphatic or alicyclic dicarboxylic acids having 2 to 14 carbon atoms, or isophthalic acid, and (3) polyalkylene glycol. A retylene methylene terephthalate fiber having a loss tangent peak temperature of 85 to 115 ° C, an elastic modulus Q (g / d) and an elastic recovery rate R ( ) Which satisfies the following expression (1).

0.18 ≤ Q / R ≤ 0.45 · · · Equation (1)

7. The polyester fiber according to claim 1, wherein the b value is 12 to 10.

8. A fabric, wherein the polyester fiber according to any one of claims 1 to 7 is partially or entirely used.

9. A mixed fabric, comprising a mixture of the polyester fiber of claim 1 and the stretch fiber.

10. A fabric using the polyester fiber of any one of claims 1 to 7 for a part or all of the fabric, wherein the fabric is dyed with a cationic dye or a dye and a disperse dye.