KR100359347B1 - Polyester fiber and fabric prepared therefrom - Google Patents

Abstract

A polyester resin is disclosed that satisfies the following conditions (1) - (3): (1) the polyester resin comprising a copolyester obtained by copolymerizing terephthalic acid or dimethyl terephthalate, trimethylene glycol and at least one compound selected from the group consisting a glycol, an aliphatic or alicyclic dicarboxylic acid and a poly(alkylene glycol); (2) the resin has an intrinsic viscosity of 0.4 to 1.2 being measured at 35 DEG C with o-chlorophenol using an Ostwald's viscometer; and (3) the resin has a degree of yellow tinting as represented by a b value of -2 to 10.

Description

Polyester fiber and fabric using it {POLYESTER FIBER AND FABRIC PREPARED THEREFROM}

Polytrimethylene terephthalate fiber has properties similar to nylon fiber of soft texture derived from low elastic modulus, excellent elastic recovery and similar to polyethylene terephthalate fiber of wash and wear resistance, dimensional stability and yellowing resistance. It is a groundbreaking fiber to have together, and the application of clothing, carpets, etc. is advanced utilizing the characteristic.

However, polytrimethylene terephthalate fibers have a problem with dyeability. That is, in the well-known polytrimethylene terephthalate type fiber, the dye used is limited to the disperse dye, and there existed a big problem in dyeing that only dyeing in dark color under the high pressure of 110-120 degreeC is inevitable.

The fact that the dye to which the fiber is dyed is limited to the disperse dye means that the resulting dyeing is low in vividness, and the dry cleaning fastness, wet friction fastness, sublimation fastness and the like are slightly inferior.

In addition, that the dyeing temperature for dyeing dark is 110 to 120 ° C, for example, means that it is not possible to dye a mixed fabric with other fibers that cause pyrolysis at these high temperatures. For example, when mixed with polytrimethylene terephthalate fibers and other fibers such as polyurethane elastomers, wool, silk, acetate fibers, a soft and conventional texture cloth can be expected. When it exceeds 110 degreeC, there existed a problem that intensity | strength fell significantly or it devitrified white and greatly impairs a commercial property.

If polytrimethylene terephthalate fibers are made that are dyed at high pressure with a cation dye or a dye on both sides of the cation dye and the disperse dye, these problems can be solved, but such fibers are not known in the art.

In the range of known techniques, there is no known technique for dyeing polytrimethylene terephthalate fibers with dyes other than disperse dyes such as cationic dyes.

Although the specific application of polytrimethylene terephthalate fiber is not described, as a method of improving the dyeability to the cation dye of polyester fiber centered on polyethylene terephthalate fiber, it is sulfonate metal base or sulfonic acid quaternary phosphonium base in polyester. A method of adding and copolymerizing isophthalic acid having a compound before completion of the polycondensation reaction (Japanese Patent Laid-Open No. 34-10497, Japanese Patent Laid-Open No. 47-22334, and Japanese Laid-Open Patent Publication No. 5-230713) is known. However, the fiber obtained in this way has no atmospheric pressure cation dye saltability and high elastic modulus, thus giving only a hard and stiff fabric. In addition, as a method of imparting cationic saltability at atmospheric pressure, a dicarboxylic acid such as adipic acid or isophthalic acid or an alkyl ester thereof is used as a copolymerization component together with isophthalic acid having a sulfonic acid metal base in polyethylene terephthalate. It is known (for example, Unexamined-Japanese-Patent No. 57-66119). However, the fiber thus obtained also has a high modulus of elasticity, giving only a stiff fabric.

Examples of the fibers having good dyeability to the disperse dye, low elastic modulus and excellent elastic recovery properties include polytrimethylene terephthalate fibers disclosed in JP-A-52-5320. In addition, Japanese Patent Application Laid-open No. Hei 9-509225 discloses a method of dyeing polytrimethylene terephthalate fiber under normal pressure using a disperse dye. However, these fibers cannot be dyed at all with cationic dyes under normal pressure. Moreover, although it became clear by the detailed examination of the present inventors, it turned out that the dispersion | dye dye can only be dye | stained with the dye concentration very low at normal pressure by the technique shown by these publications. For example, in the examples of Japanese Patent Application Laid-open No. Hei 9-509225, the dye concentration used is at most 0.5% owf (where% owf is expressed as the weight% of the fiber dyeing the dye concentration in the saline solution. ) to be. In the field of clothing, fabrics that are dyed light and medium and dark at the same time are required. In this dark dyeing, the dye concentration is more than 4% owf, and in some cases, more than 10% owf. In dyeing polytrimethylene terephthalate fiber, dye cannot be sufficiently absorbed at normal pressure. It cannot be dyed dark.

The present invention relates to a polytrimethylene terephthalate fiber, in particular a cation dye or a polytrimethylene terephthalate fiber which can be dyed dark under normal pressure with a dye of both a cation dye and a disperse dye and a fabric using the fiber ( It is about cloth.

Disclosure of the Invention

An object of the present invention is to provide a polytrimethylene terephthalate-based fiber which can be dyed dark under normal pressure using a cation dye or a dye on both sides of a cation dye and a disperse dye.

Another object of the present invention is to provide a polytrimethylene terephthalate-based fiber which can dye a composite fiber product mixed with polyurethane elastic fiber, wool, silk, acetate and the like without harming the properties of their relatively low heat-resistant fiber. Is in.

It is another object of the present invention to provide a weaved, blended, interlaced fabric of polytrimethylene terephthalate-based fibers and other fibrous materials which can be dyed under normal pressure.

One specific object of the present invention is to provide a mixed fabric of polyurethane elastic fibers and polytrimethylene terephthalate-based fibers that can be dyed in a simple manner using a commercial atmospheric dyeing facility.

The present inventors have solved the above problems by using a polytrimethylene terephthalate copolymerized with a specific third component at a specific copolymerization ratio as a polymer to prepare a polyester fiber having a peak temperature, elastic modulus and elastic recovery rate of a loss tangent in a very limited range. It has been found that the present invention has been reached.

That is, the 1st of this invention is the fiber which consists of polyester which copolymerized the 3rd component to polytrimethylene terephthalate, 3rd component is ester formation sulfonate compound of 0.5-5 mol% of copolymerization ratios, A polyester fiber characterized in that the peak temperature of the loss tangent 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 satisfies the following formula (1); It is a fabric that used it.

18 ≤ Q / R ≤ 0. 45

The polymer which comprises the polyester fiber of this invention is polyester which copolymerized specific amount of the 3rd component with polytrimethylene terephthalate. Here, polytrimethylene terephthalate is polyester which has terephthalic acid as an acid component and trimethylene glycol (also called 1, 3- propanediol) as a diol component.

As the third component to be copolymerized, when a specific amount of an ester-forming sulfonate compound is used, an atmospheric pressure cation dye saltable fiber can be obtained.

As an ester forming sulfonate compound used by this invention, the sulfonate group containing compound represented by following General formula (1) is illustrated.

Wherein R ₁ , R ₂ are -COOH, -COOR, -OCOR,-(CH ₂ ) _n OH,-(CH ₂ ) _n [O (CH ₂ ) _m ] _p OH or -CO [O (CH ₂ ) _n ] _m OH (wherein R is an alkyl group having 1 to 10 carbon atoms, n, m, and p are integers of 1 or more), and R ₁ and R ₂ may be the same or different groups. M is a metal, NH ₄ , or a phosphonium group represented by the formula -PR ₃ R ₄ R ₅ R ₆ , wherein R ₃ , R ₄ , R ₅ , R ₆ is a hydrogen atom, an alkyl group, an aryl group or a hydroxyalkyl group The same or different group selected, and preferably an alkyl group having 1 to 10 carbon atoms. When M is a metal, Preferably it is an alkali metal and alkaline-earth metal. Z is a trivalent organic group, preferably a trivalent aromatic group.]

By copolymerizing such an ester forming sulfonate compound, a fiber which can be dyed to a dark color with a cation dye under normal pressure is obtained. Moreover, compared with polytrimethylene terephthalate homopolymer fiber, it becomes dichroic with respect to disperse dye. And, in the present invention, being able to dye at normal pressure means that the absorption rate into the fiber at 95 ° C. is about 70% or more.

In addition, since the cation chlorinated sand exhibits moderate alkali weight loss characteristics, a softer texture can also be obtained by reducing the alkali after knitting. Alkali reduction means heating a fabric in aqueous alkali solution and dissolving a part of polymer on a fiber surface. Moderate alkali reduction is the ability to industrially control the amount or rate of alkali reduction. This is a surprising big feature, for example, in cationic salt polyethylene terephthalate fibers, the rate of alkali reduction is so fast that industrial control is virtually impossible. In the polyester fiber of the present invention, the rate of alkali reduction is not conventional cationic salts. It is about polyethylene terephthalate fiber, and it becomes possible to reduce alkali using a well-known method. In this way, the polyester fiber of the present invention, which is alkali-reduced, becomes softer, and micropores of about several micrometers exist on the surface of the fiber.

Specific examples of preferred ester-forming sulfonate compounds include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, and 2-sodium sulfo-4-hydride. Roxybenzoic acid, 3, 5- dicarboxylic acid benzene sulfonic acid tetramethyl phosphonium salt, 3, 5- dicarboxylic acid benzene sulfonic acid tetrabutyl phosphonium salt, 3, 5- dicarboxylic acid benzene sulfonic acid tributyl methyl phospho Nium salt, 2,6-dicarboxylic acid naphthalene-4-sulfonic acid tetrabutyl phosphonium salt, 2,6-dicarboxylic acid naphthalene-4-sulfonic acid tetramethyl phosphonium salt, 3,5-dicarboxylic acid benzene sulfonic acid Ammonium salt etc. or ester derivatives, such as these, methyl and dimethyl ester, are mentioned. In particular, ester derivatives such as methyl and dimethyl ester are preferably used in view of excellent whiteness and polymerization rate of the polymer.

The copolymerization ratio of the ester-forming sulfonate compound to polytrimethylene terephthalate is required to be from 0.5 to 5 mol% based on the total moles of all acid components constituting the polyester. When the copolymerization ratio of the ester-forming sulfonate compound is less than 0.5 mol%, it cannot be dyed with a cation dye at normal pressure. When the proportion of the ester-forming sulfonate compound is more than 5 mol%, the heat resistance of the polymer is deteriorated, the polymerizability and the radioactivity are very deteriorated, and the fibers are easily yellowed. From the viewpoint of having both polymerizability and radioactivity while maintaining the dyeability to the cation dye sufficiently, it is preferably 1 to 3 mol%, particularly preferably 1.2 to 2.5 mol%.

The polymer constituting the polyester fiber of the present invention is, as described below, within the range of not losing the object of the present invention, as the fourth component, aliphatic or alicyclic glycol having 2 to 12 carbon atoms, aliphatic having 2 to 14 carbon atoms or Alicyclic dicarboxylic acid, polyalkylene glycol, etc. may be included. Specific examples of aliphatic glycols and alicyclic glycols having 4 to 12 carbon atoms include, for example, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 1,5-pentamethylene glycol, 1,6 Hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4- Cyclohexane dimethanol, 1, 3- cyclohexane dimethanol, 1,2-cyclohexane dimethanol, etc. are mentioned. Copolymerization of these glycols with polytrimethylene terephthalate makes it possible to dye up to dark colors using disperse dyes at normal pressure. Among these aliphatic or cycloaliphatic glycols, 1,4-butanediol, 1,6-hexamethylene glycol, neopentylglycol, and cyclohexanedimethanol are preferable in view of excellent polymer whiteness, thermal decomposition, and light resistance. In addition, 1,4-butanediol is particularly preferable in view of excellent polymerization rate and dry cleaning fastness.

The copolymerization ratio of these glycols with respect to polytrimethylene terephthalate is required to 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 will not be possible to dye the dark color with the disperse dye at normal pressure. The copolymerization ratio of glycol has a high correlation with elastic modulus, elastic recovery rate, melting point, glass transition point, and dyeing. When the copolymerization ratio exceeds 12% by weight, the melting point and the glass transition point are greatly reduced, and the texture is hardly changed at the stage of normal use such as post-processing or ironing, which is represented by thermoset, or dry cleaning of the fabric after dyeing The fault which falls in fastness arises. Preferably it is 2-10 weight%, More preferably, it is 3-7 weight%.

Specific examples of the aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms used in the present invention include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptane diacid, octane diacid, sebacic acid, and dodecane. Diacid, 2-methylglutamic acid, 2-methyladipic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2 -Cyclohexanedicarboxylic acid, etc. are mentioned. By copolymerizing these dicarboxylic acids with polytrimethylene terephthalate, it becomes possible to dye up to dark colors using a disperse dye at normal pressure.

Among these aliphatic or alicyclic dicarboxylic acids or isophthalic acid, sebacic acid, dodecane diacid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid are preferable in view of excellent polymerization rate and light resistance when copolymerizing. Do. In addition, isophthalic acid is particularly preferable in view of the excellent whiteness of the polymer.

The copolymerization ratio of these aliphatic or alicyclic dicarboxylic acids or isophthalic acid to the polytrimethylene terephthalate needs to be 3 to 9% by weight based on the weight of the polymer. If the copolymerization ratio is less than 3% by weight, it will not be possible to dye the dark color at normal pressure. If the copolymerization ratio is more than 9% by weight, the melting point or the glass transition point is too low, so that the texture is hardly changed at the stage of normal use such as post-processing or ironing, which is represented by thermoset, or dry cleaning of the fabric after dyeing The fault which falls in fastness arises. Preferably it is 3-8 weight%, More preferably, it is 3-7 weight%.

In this invention, polyalkylene glycol can also be used as a copolymerization component. In the case of copolymerizing glycol or acid as the fourth component, the melting point is lowered no matter how low, the radioactivity deteriorates, or when the obtained fiber is post-processed, heat, fusion to a heat source, remarkable shrinkage, and the like are sometimes deteriorated. have. However, when the polyalkylene glycol is used as the third component, the melting point hardly decreases and such a problem does not occur. It is considered that this is because the polyalkylene glycol component is localized in the polymer because of its high molecular weight. The polyalkylene glycol to be used may be any of polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, or a copolymer thereof. Polyethylene glycol is most preferred in view of thermal stability.

Moreover, as for the average molecular weight of polyalkylene glycol, 300-20000 are preferable. When the average molecular weight is less than 300, since a considerably low molecular weight polyalkylene glycol is contained, the amount of polyalkylene glycol contained in the obtained polymer is distilled off under reduced pressure during polymerization under high vacuum, so that the amount of polyalkylene glycol is not constant. Therefore, the yarn elongation also does not become uniform in physical properties, dyeing properties, thermal characteristics, etc., and there are variations in the characteristics as a product.

On the other hand, when the average molecular weight exceeds 20000, since the high molecular weight polyalkylene glycol which is not copolymerized in a polymer increases, dyeing property, dry cleaning fastness, and light fastness fall fall. The average molecular weight of polyalkylene glycol is 400-10000, More preferably, it is 500-5000.

The copolymerization ratio of polyalkylene glycol to polytrimethylene terephthalate is required to 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 is impossible to dye the dark color with the disperse dye at normal pressure. Moreover, when the ratio of polyalkylene glycol exceeds 10 weight%, the heat resistance of a polymer falls and polymerizability and radioactivity deteriorate very much. In addition, the glass transition point is too low, the texture turns rigid in the normal use stage, such as post-processing or ironing, which is represented by heat setability, or the dry cleaning fastness or light fastness of the fabric after dyeing significantly reduced Is generated. Preferably it is 4-8 weight%.

The polymer which comprises the polyester fiber of this invention can also copolymerize and mix a 4th component in the range which does not impair the objective of this invention. Even when using such a 4th component, it is necessary to comply with the range of the above-mentioned copolymerization ratio, since it does not impair the objective of this invention. Among these combinations, in particular, ester-forming sulfonate compounds and (1) aliphatic or cycloaliphatic glycols having 4 to 12 carbon atoms, (2) aliphatic or cycloaliphatic dicarboxylic acids having 2 to 14 carbon atoms, or isophthalic acid, (3) By copolymerizing at least one selected from polyalkylene glycols, it is possible to obtain polyester fibers which can be dyed in both cationic dyes and disperse dyes at atmospheric pressure. As such a copolymerization ratio, Preferably, it is preferable that the ester-formable sulfonate compound is 1.2-2.5 mol%, and 3-7 weight% of at least 1 sort (s) chosen from said (1)-(3).

And, if necessary, various additives, such as gloss remover, heat stabilizer, antifoaming agent, colorant, flame retardant, antioxidant, ultraviolet absorber, infrared absorber, crystal nucleating agent, fluorescence A whitening agent etc. can also be copolymerized or mixed.

The polyester molecular weight used in the present invention can be defined according to the intrinsic viscosity, and the intrinsic viscosity "η" is preferably from 0.3 to 2. 0, more preferably from 0.3 to 1.5, particularly preferably It is 0.4-4.2, and can obtain polyester fiber which is excellent in strength and spinning property. If the intrinsic viscosity is less than 0.3, the polymerizability of the polymer is too low, so that radioactivity becomes unstable. Moreover, the strength of the fiber obtained is also low and cannot be satisfied. On the contrary, when the intrinsic viscosity exceeds 2. 0, the melt viscosity is too high, so that the radioactivity is deteriorated because it cannot be metered smoothly with the gear pump and the discharge is poor.

About the manufacturing method of the polymer which comprises the polyester fiber of this invention, it can basically superpose | polymerize using a well-known method. That is, in the manufacturing process of a normal polytrimethylene terephthalate, a tertiary phthalate lower ester, such as terephthalic acid or dimethyl terephthalate, and trimethylene glycol are added in the optional stage at the time of transesterification followed by polycondensation reaction. can do. In this case, the ester-forming sulfonate compound and the aliphatic or cycloaliphatic dicarboxylic acid or isophthalic acid need to be accelerated to react with trimethylene glycol, so it is preferable to add them before the transesterification reaction. It is preferable to add len glycol at the end of the transesterification reaction in order to prevent yellowing of the polymer and bumping at reduced pressure. As a transesterification catalyst, it is preferable to use 0.01 to 0.1 weight% of metal acetate, titanium alkoxide, etc. from the point which combines reaction rate, whiteness of a polymer, and thermal stability. Reaction temperature is about 200-240 degreeC. As a polycondensation catalyst, antimony oxide, titanium alkoxide, etc. can be used, Especially when using a titanium alkoxide, it can also be combined with a transesterification catalyst. As catalyst amount, it is 0.01-1.1 weight% with respect to the quantity of all the carboxylic acids used from a viewpoint of reaction rate and the whiteness of a polymer. As reaction temperature, it is 240-280 degreeC, and a vacuum degree is 0.01-1 torr. In addition, the above-mentioned various additives may be added at any stage of the polymerization process, but in order to minimize the inhibition on the reaction, it is preferable to add at any stage after the end of the transesterification reaction.

Moreover, the polymer which comprises the polyester fiber of this invention can solidify the polymer obtained by the said method in inert gas, such as nitrogen and argon, or under reduced pressure, and can raise molecular weight. By applying such a method, yellowing of the polymer can be suppressed, the amount of oligomers causing trimming and lint can be reduced, and the strength can be increased. The method of solid phase polymerization can apply the well-known method used for polyethylene terephthalate as it is, for example, As an extreme viscosity diagram of the prepolymer before solid phase polymerization, it is preferable from the point which 0.4-4.8 raises the whiteness. The solid phase polymerization degree is preferably 170 to 230 ° C., and the time varies depending on the desired viscosity, but is usually about 3 to 36 hours.

Moreover, the polymer which comprises the polyester fiber of this invention can also be manufactured by mixing two types of polymers which become a desired copolymer composition. For example, polytrimethylene terephthalate copolymerized with 5% by weight of 1,4-butanediol may be prepared by mixing 95% by weight of polytrimethylene terephthalate and 5% by weight of polytrimethylene terephthalate. The mixing here may be carried out after mixing in the polymerization reactor and sufficiently transesterified, or may be reacted in the extruder more conveniently in a chip-blended state. Even with this method, a homogeneous polymer can be obtained because the transesterification rate is sufficiently fast.

The important thing in the manufacturing method of the polymer which comprises the polyester fiber of this invention is maintaining the whiteness of a polymer. When the third component is copolymerized with polytrimethylene terephthalate, it is generally easy to color in the polymerization process or the spinning process. Therefore, as a method of raising whiteness, it is preferable to apply the said preferable catalyst amount and reaction temperature, and to use a heat stabilizer or a coloring inhibitor. As the heat stabilizer, a pentavalent or trivalent phosphorus compound is preferable, and examples thereof include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, phosphoric acid and phosphorous acid. In addition, it is preferable to add 0.01-0.07 weight% with respect to a polymer. Moreover, cobalt acetate, cobalt formate, etc. are mentioned as a coloring inhibitor, It is preferable to add 0.01-0.07 weight% with respect to a polymer. In addition, when raising the intrinsic viscosity above 0.9, solid-phase polymerization of the prepolymer is a very effective method for increasing the whiteness. The polymer thus obtained can maintain excellent whiteness as a fiber. Such whiteness is -2 to 10, preferably -1 to 6, with a value of b to be described later.

In addition, when using an ester-forming sulfonate compound, it is easy to produce a substance which tends to aggregate in a spinneret pack during the polymerization process and trimethylene glycol dimer (Structure Formula: HOCH ₂ CH ₂ CH ₂ Particular attention should be paid to the fact that OCH ₂ CH ₂ CH ₂ OH) is likely to be produced. When the amount of the aggregate is large, the pressure rise in the spinneret pack becomes large and trimming occurs easily. In order to prevent this, there is a problem in that the productivity of the spinneret pack is increased and the productivity decreases. Moreover, when there is much quantity of trimethylene glycol dimer, the problem that thermal stability and light resistance at the time of melting fall will arise. In order to avoid this problem, it is preferable to add a kind of additive at any stage in the polymerization. Examples of such additives include basic metal salts such as lithium acetate, lithium carbonate, lithium formate, sodium acetate, sodium carbonate, sodium formate, sodium hydroxide, calcium hydroxide, potassium hydroxide, and the amount of the additive to the ester-forming sulfonate compound. 20 to 400 mol%, preferably 70 to 200 mol%.

The form of the polyester fiber of this invention may be either long fiber or short fiber, and in the case of long fiber, it may be any of a multifilament and a monofilament. The total denier is not particularly limited, but is preferably 5 to 1000 d and particularly preferably 5 to 200 d when used for clothing. Single yarn denier is not particularly limited, but is preferably 0.001 to 10 d. Also in the cross-sectional shape, there is no particular limitation such as an annular shape, a triangle, a flat shape, a star shape, and a w shape, and the inside may be cold or hollow.

In the polyester fiber of the present invention, the peak temperature (hereinafter referred to as "Tmax") of the loss tangent, which can be obtained by dynamic viscoelasticity measurement, needs to be 85 to 115 ° C when the third component is an ester-forming sulfonate compound. have. This is because in this range, atmospheric pressure saltability and high fastness by the cation dye or the cation dye and disperse dye which the present invention obtains can be ensured. Since Tmax corresponds to the molecular density of the amorphous portion, the smaller the value is, the smaller the molecular density of the amorphous portion is, so that the gap portion for the dye to enter becomes larger and the dye enters easily, thereby increasing the rate of absorption. Even when using any of the third components, since Tmax is less likely to move molecules at a lower temperature when the temperature is less than 85 ° C, the shrinkage becomes excessively large in the normal use stage represented by the usual post-processing, ironing, and the like represented by the heat set. The texture deteriorates, or the dry cleaning fastness of the fabric after dyeing is lowered. In addition, when using an ester forming sulfonate compound as a 3rd component, when Tmax exceeds 115 degreeC, the dyeability which is the objective of this invention will fall, and the clearance part for dye entry will become small too much, Since Tmax is a structural factor of the fiber, even if it is a polymer having the same copolymerization composition, it is possible to spin yarns such as spinning temperature, spinning speed, draw ratio, heat treatment temperature, refining conditions, alkali reduction conditions, dyeing conditions, and the like. It shows a different value according to conditions and post-processing conditions. In particular, since this value greatly changes at the heat set temperature, it is important to change the heat set temperature to make Tmax within the above range. Roughly showing the setting of the heat set temperature, in the case of the polyester fiber stipulated in the present invention, the Tmax gradually increases in the range where the heat set temperature is from room temperature to about 150 ° C, but after exceeding about 160 ° C, Is greatly reduced. Since the ratio of this change differs for every copolymerization ratio, it is necessary to examine, examining the relationship between hot set temperature and Tmax. In the case of the present invention, when it exceeds 115 ° C, the dyeability improving effect is small and the atmospheric pressure saltability does not appear. However, the lower the value is, the better, and since the amorphous portion becomes too rough, it is easy to enter the dye and has the drawback that it is easy to come out. That is, fastness, especially dry cleaning fastness, wet friction fastness, washing fastness, etc. fall. In addition, problems such as deterioration of texture due to curing at the time of heat set, reduction of dimensional stability, and the like appear. The preferable range of Tmax is slightly different depending on the kind of the third component, but is 97 to 112 ° C when the ester-forming sulfonate compound is used as the third component.

Moreover, the elasticity modulus Q (g / d) of the polyester fiber of this invention and the elasticity recovery rate R (%) after leaving for 1 minute after 20% elongation need to satisfy following formula (1). This is because, by satisfying the formula (1), the fabric obtained from the polyester fiber of the present invention is different from the fabric obtained from the conventional polyester fiber, and may have a soft texture of nylon level or more.

[Equation 1]

18 ≤ Q / R ≤ 0. 45

At Q / R> 0.45, the elastic modulus is too high, so the soft texture of the desired nylon level can not be obtained or the elastic recovery is insufficient, and once the stress is applied, the deformed fiber does not recover as it is. You can only get fabric with poor stability. In addition, since the area | region to which Q / R <0.018 does not exist substantially, 0.018 is made into the lower limit of Q / R in this invention. The specific elastic modulus which can be in the range of Equation 1 is usually 25 to 40 g / d, and the elastic recovery rate is 70 to 99%.

(1) aliphatic or cycloaliphatic glycols having 4 to 12 carbon atoms, (2) having 4 to 12% by weight of an ester-forming sulfonate compound having a copolymerization ratio of 1.2 to 2.5 mol% and a copolymerization ratio of 3 to 7 wt% In the case of polytrimethylene terephthalate fibers copolymerized with at least one member selected from aliphatic or alicyclic dicarboxylic acids of 12 to 12 or isophthalic acid and (3) polyalkylene glycol, the Tmax of the fibers is 85 to 115 ° C. Moreover, it is necessary for the relationship between the elasticity modulus Q (g / d) and the elastic recovery rate R (%) of the said fiber to satisfy Formula (1) for the same reason as the above-mentioned detailed Tmax and Formula (1).

The polyester fiber of this invention can be obtained by the method shown next.

The polyester fiber of this invention melt | dissolves the polymer dried to the moisture content of at least 100 ppm, Preferably it is 50 ppm or less using an extruder etc., after that, after extruding the melted polymer in a spinneret, it is then stretched Can be obtained by Here, stretching after winding means so-called conventional method, which winds up a bobbin or the like after spinning and stretches the yarn using another apparatus, or after the polymer extruded from the spinneret is completely cooled and solidified, By winding up more than once on the first roll rotating at a constant speed, the tension is not transmitted at all before and after the roll, and the stretching is performed between the first roll and the second roll provided after the first roll. In other words, the so-called direct method directly connected to the spinning-drawing process.

Hereinafter, the conventional method will be described with an example.

In this invention, the spinning temperature at the time of melt-spinning a polymer is 240-320 degreeC, Preferably it is 240-300 degreeC, More preferably, the range of 240-280 degreeC is suitable. If the spinning temperature is less than 240 ° C, the temperature is too low to be in a stable molten state, and the unevenness of the obtained fiber becomes large, and the satisfactory strength and elongation are not exhibited. In addition, when the spinning temperature exceeds 320 ° C., thermal decomposition becomes severe, and the resultant yarn is colored and no satisfactory strength and elongation are exhibited.

The winding speed of the yarn is not particularly limited, but is usually wound at 3500 m / min or less, preferably 2500 m / min or less, more preferably 2000 m / min or less. If the winding speed exceeds 3500 m / min, crystallization proceeds excessively before winding, and the stretching ratio cannot be increased in the stretching process, so that the molecules cannot be oriented, sufficient thread strength or elastic recovery cannot be obtained, or it is tightened and fails. Your back will not fall out of the winder. The draw ratio at the time of stretching is 2 to 4 times, preferably 2. 2 to 3. 7 times, more preferably 2. 5 to 3. 5 times. When the draw ratio is 2 times or less, the polymer cannot be oriented sufficiently by stretching, and the elastic recovery rate of the obtained yarn is lowered, so that the formula (1) cannot be satisfied. In addition, more than four times the trimming is severe, and stretching cannot be performed stably.

The temperature at the time of extending | stretching is 30-80 degreeC in a extending range, Preferably it is 35-70 degreeC, More preferably, 40-65 degreeC is good. If the temperature in the stretching range is less than 30 ° C, the trimming occurs frequently at the time of stretching, and fibers cannot be obtained continuously. Moreover, when it exceeds 80 degreeC, since the sliding of a fiber with respect to heating ranges, such as an extending | stretching roll, deteriorates, single yarn break is frequent and it becomes a fluffy thread. In addition, since the polymers are pulled out, sufficient orientation is not applied and the elastic recovery rate is lowered.

In addition, in order to avoid a change in the elapse of the fiber structure, it is necessary to perform heat treatment after stretching. This heat treatment is 90 to 200 ° C, preferably 100 to 190 ° C, more preferably 110 to 180 ° C. If the heat treatment temperature is less than 90 ° C., crystallization of the fiber does not occur sufficiently, and the elastic recovery is deteriorated. In addition, at a temperature higher than 200 ° C, the fibers are broken in the heat treatment range and cannot be stretched.

Next, the straight-line method is described with an example. The molten multifilament extruded from the spinneret is passed through a heat insulating zone having a length of 2 to 80 cm maintained at an ambient temperature of 30 to 200 ° C formed immediately below the spinneret, thereby suppressing rapid cooling, and then quenching the molten multifilament. It was wound into a first roll having a rotational speed of 300 to 3000 m / min heated to 40 to 70 ° C., and then wound to a second roll heated to 120 to 160 ° C. without being wound to a solid multifilament. After extending | stretching by 1.5 to 3 times between the 2nd roll which made speed faster than the 1st roll, it winds up using a winding machine at a lower speed than a 2nd roll. If necessary in the spinning process, interlacing treatment may be performed. In addition, the undrawn yarn wound once at a spinning speed of 300 to 3000 m / min may be wound up through the first roll and the second roll.

The melt extrusion of the polymer is carried out in the same manner as in the conventional method, and the molten multifilament from the spinneret is not immediately quenched, but passes through a heat insulating zone having a length of 2 to 80 cm maintained at an ambient temperature of 30 to 200 ° C formed directly below the spinneret. It is very desirable to rapidly cool the molten multifilament after changing the solid multifilament to suppress the rapid cooling, and to provide it to the subsequent stretching step. By passing through the heat insulating zone, it is possible to suppress the formation of fine crystals or extremely oriented amorphous portions by quenching the polymer and to produce 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. Since polytrimethylene terephthalate has a much faster crystallization rate than a polyester, for example polyethylene terephthalate, such slow cooling is very effective in suppressing the formation of fine crystals or extremely oriented amorphous portions. Way. If it is less than 30 degreeC, it will be quenched and it will become difficult to raise draw ratio. In addition, the trimming easily occurs at 200 ° C or higher. As for the temperature of such a thermal insulation area | region, 40-200 degreeC is preferable, More preferably, it is 50-150 degreeC. Moreover, as for the length of this heat insulation area | region, 5-30 cm is preferable.

About the spinning speed of a yarn, the winding speed of a 1st roll is 300-3000 m / min. If the spinning speed is less than 300 m / min, the spinning stability is excellent, but the productivity is greatly reduced. In addition, if it exceeds 3000 m / min, the orientation and partial crystallization of the amorphous portion proceeds before winding, and the stretching magnification cannot be increased during the stretching process, so that the molecules cannot be oriented and it is difficult to express sufficient strength of the yarn. . Preferably it is 1500-2700 m / min.

It is necessary to lower the speed of the winder than the second roll in order to cause the loosening of the amorphous portion of the fiber, thereby weakening the large shrinkage of the polytrimethylene terephthalate fiber and loosening the amorphous portion so that dyes do not enter. Easy structure improves dyeability. The relaxation ratio (winding speed / 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 draw ratio, which is usually 600 to 6000 m / min. As for the draw ratio between a 1st roll and a 2nd roll, 1.3 to 3 times, Preferably 2 to 2.7 times are preferable. When the draw ratio is 1.3 times or less, the polymer cannot be oriented sufficiently by stretching, and the strength and elastic recovery rate of the obtained fiber are lowered. Moreover, in 3 times or more, fluff becomes severe, and extending | stretching cannot be performed stably. The temperature of a 1st roll is 40-70 degreeC, and the situation which is easy to extend | stretch in this range can be created. Preferably, it is 50-60 degreeC. The heat treatment is performed on the second roll, which is 120 to 160 ° C. If it is less than 120 degreeC, heat stability is poor, it will become a fiber which is easy to change with heat deformation and elapses, and color development will fall. Further, at 160 ° C. or higher, fluff or trimming may occur, and thus it may not stably spin. Preferably, it is 120-150 degreeC.

It is important to apply the preferable conditions shown by the above-mentioned conventional method and the straight line method to make the homogeneity and quality of the fiber obtained sufficient. As a parameter for evaluating the quality of the fiber obtained by applying preferable spinning conditions, for example, U% can be used. U% is a parameter representing the homogeneity of the fiber cross section, and when a preferable condition is applied, U% has a value of 2.5% or less, and in some cases, 1.5% or less.

The polyester fiber obtained as mentioned above becomes a cloth excellent in the softness | flexibility, elasticity, and color development by using individually or a part of fabric. There is no particular limitation on the fibers other than those used for a part of the fabric, but in particular, nylon fibers or polyethylene terephthalate fibers are entangled with fibers such as stretch fibers, cellulose fibers, wool, silk, and acetates represented by polyurethane elastic fibers. It is possible to express the characteristic which cannot be obtained in the mixed fabric using That is, for example, a cation dye, or a cationic dye and a disperse dye can be dyed at atmospheric pressure, and at the same time, it is a fabric giving a unique texture having flexibility and elasticity not previously seen.

In particular, the polyester fiber of the present invention is a field utilizing the characteristic that can be dyed in a dark color to any one or both of the cation dye or the cation dye and disperse dyes, dyeing without contaminating the polyurethane elastic fibers The polytrimethylene terephthalate fiber and the polyurethane elastic fiber are represented in that it can be made soft and feel different from the mixed fabric of the stretch fiber represented by nylon fiber and polyurethane elastic fiber. Mixed fabrics with stretch fibers are exemplified as particularly preferred fabrics.

The fabric of the present invention includes the above-mentioned mixed fabric, and there is no particular limitation on the form and the knitting method, and a known method can be used. Examples thereof include plain fabrics using the polyester fibers of the present invention for warp or weft yarns, woven fabrics such as reversible woven fabrics, knitted fabrics such as tricot and raschel, and the like. Iii), envoys and entanglements may be used.

The stretch fibers used in the present invention are not particularly limited, but are polys represented by dry-spun or melt-spun polyurethane elastic fibers or polybutylene terephthalate fibers or polytetramethylene glycol copolymerized polybutylene terephthalate fibers. Ester elastic fiber etc. are mentioned. In the mixed fabric using the stretch fiber, the content of the polyester fiber of the present invention is not particularly limited, but is preferably from 60 to 98%.

The fabric of the present invention also includes a mixed fabric, and can be dyed, for example, after weaving by knitting, through a process of refining, preliminary, dyeing, and final set by conventional methods. In addition, it is also possible to carry out alkali weight loss treatment by a conventional method after scouring and before dyeing, if necessary.

Refining can be performed in the temperature range of 40-98 degreeC. In particular, in the case of mixing with stretch fibers, refining while relaxing improves elasticity.

It is also possible to omit one or both sets of heat before and after dyeing, but in order to improve the form stability and dyeability of the fabric, it is preferable to carry out both. As temperature of a thermoset, it is the temperature of 120-190 degreeC, Preferably it is 140-180 degreeC, and it is 10 second-5 minutes, Preferably it is 20 second-3 minutes as a thermoset time.

Dyeing can be performed at 70-150 degreeC, Preferably it is 90-120 degreeC, Especially preferably, it is 90-100 degreeC, without using an adjuvant. In order to perform dyeing homogeneously, it is especially preferable to adjust to pH suitable for dye using acetic acid, sodium hydroxide, etc., and to use the dispersing agent comprised from surfactant. Moreover, when using a cation dye, it is especially preferable to add alkali metal or alkaline earth metal salts, such as sodium sulfate, sodium nitrate, potassium sulfate, and calcium sulfate, in order to improve the sharpness of a dyestuff.

After dyeing, soaping or reduction washing can be performed by a known method. In particular, in the case of mixing with stretch fibers, in the case of dyeing a mixed fabric composed of an atmospheric pressure dispersible dye salting fiber and a polyurethane elastic fiber, reducing fiber cleaning is performed to completely disperse the disperse dye contaminating the polyurethane elastic fiber. Removing it is important to improve the fabric's fastness. These methods may be well-known methods, and can be processed using reducing agents, such as hydrosulfite sodium, in aqueous alkali solution, such as sodium carbonate and sodium hydroxide, for example.

The following is an illustration of the use mode as a feature of the polytrimethylene terephthalate-based fiber of the present invention that can be dyed dark with both a cation dye or a cation dye and a disperse dye at normal pressure.

(1) The polytrimethylene terephthalate fiber of the present invention impairs the performance of a fiber having low heat resistance when mixed with a fiber having low heat resistance such as stretch fiber, wool, silk, acetate, etc. represented by polyurethane elastic fiber. It can be dyed dark under normal pressure. In particular, when polytrimethylene terephthalate-based fibers are mixed with polyurethane elastic fibers, they show a softness and feel different from the mixed fabric using nylon fibers, and create a new sense of clothing with easy-care characteristics. Can be.

(2) Since the mixed fabric of normal polytrimethylene terephthalate fiber and polyurethane elastic fiber needs to be dyed at 110-120 degreeC, polyurethane elastic fiber deteriorates by heat. Moreover, it is not dyed only with disperse dyes. In the dyeing of the mixed fabric with the polyurethane elastic fiber by the disperse dye, the disperse dye is not only absorbed more into the polyurethane elastic fiber than the polytrimethylene terephthalate fiber but also hardly adheres to the polyurethane elastic fiber. Do not. For example, the fiber disperse dye is easily dyed by dry cleaning and washing to contaminate surrounding clothing, or in some cases, the dye detaches and discolors the color of the mixed fabric, thereby decreasing dyeing fastness. On the other hand, the above-mentioned problem can be solved by using the polytrimethylene terephthalate type fiber of this invention which can be dyed dark with respect to the dye of both a cation dye or a cation dye and a disperse dye at normal pressure.

That is, the use of atmospheric pressure cation dye salted polytrimethylene terephthalate fiber of the present invention.

Polyurethane elastic fibers are not dyed with cationic dyes. Therefore, the use of polytrimethylene terephthalate-based fiber which can be dyed at normal pressure in a cation dye does not cause the above-mentioned contamination problem because it selectively dyes only polytrimethylene terephthalate-based fiber.

(3) There is a potent field of pantyhose as one of the fields of mixing with elastic fibers represented by polyurethane elastic fibers. In this industry, specialized dyeing plants do not usually have a high pressure dyeing machine for high pressure dyeing. The use of the atmospheric pressure cation dye chlorinated polytrimethylene terephthalate fiber of the present invention has the advantage of equipment that the atmospheric dyeing machine used for new equipment investment or nylon fiber alternating pantyhose can be used as it is. This facility advantage is a very important effect industrially.

(4) A fabric obtained by using the polytrimethylene terephthalate-based fiber of the present invention is much softer than a mixed fabric of a known nylon fiber and a polyurethane elastic fiber, for example, and has no waxy sensitivity peculiar to nylon fiber. Moreover, it can be a garment of a new sense, such as having stretch-contraction characteristics and excellent color development. Moreover, polytrimethylene terephthalate type fiber is high in heat setability and is excellent also in yellowing resistance. This characteristic shows that there is no problem peculiar to nylon fibers, and the garment is easy to handle.

(5) The polyester fiber of this invention shows the outstanding effect also in mixing with a cellulose fiber. In the case of using a reactive dye in the dyeing of cellulose fibers, the reactive dye often causes decomposition when the temperature of the salt bath exceeds 100 ° C. By using the polytrimethylene terephthalate-based fiber of the present invention, it is also possible to dye one bath once using a cation dye, a cation dye and a reactive dye under normal pressure. The fabric thus obtained becomes a new sense garment having both dryness peculiar to cellulose and softness derived from polytrimethylene terephthalate.

(6) The polyester fiber of the present invention can also be applied to a knitted fabric alone, and the fabric obtained is very soft and exhibits excellent stretch characteristics and color development. Moreover, when there is no problem even if it dyes at 100 degreeC or more, it is also possible to dye at 100 degreeC or more. Moreover, the characteristic of the polyester fiber of this invention is that it is industrially possible to control the amount and speed | rate of alkali weight loss, although it is a cation dye salt-soluble fiber. Alkali-reduced polyester fibers of the present invention are not only softened, but also have micropores on the surface of the fiber, which are about several micrometers, and therefore, there is a feeling of drying and can be dyed vividly. In addition, the atmospheric pressure disperse dye salty polyester fiber of the present invention also has an alkali reduction characteristic close thereto.

As described above, the polytrimethylene terephthalate-based fiber of the present invention can be used for garments such as outerwear, underwear, lining, and sports, as well as for yarns for carpets, wicks, and flocks. Can also be used for materials.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to description of the following Example. And the main measured value and the evaluated value in an Example depend on the following measuring methods and evaluation methods.

(1) measurement of intrinsic viscosity

This intrinsic viscosity [η] was measured using 35 degreeC and o-chlorophenol using Ostwald's viscosity tube.

(2) Measurement of loss tangent

The loss tangent (tan δ) and the dynamic modulus at each temperature were measured using a REOVIBRON manufactured by Orientech Co., Ltd. at a measurement frequency of 110 Hz and a heating rate of 5 ° C./min in dry air. From the result, the loss tangent-temperature curve was calculated | required and Tmax (degreeC) which is the peak temperature of a loss tangent was calculated | required on this curve.

(3) measurement of elastic modulus

Elastic modulus was measured according to JIS-L-1013.

(4) measurement of melting point

Using DSC manufactured by Seiko Denshi Co., Ltd., the temperature was measured under a nitrogen stream of 100 ml / min at a temperature increase rate of 20 ° C / min. Here, the peak value of the peak of fusion was made into melting | fusing point.

(5) measurement of elastic recovery rate

The fibers are attached to a tensile tester at a distance of 20 cm between chucks, stretched at a tensile rate of 20 cm / min to an elongation of 20%, and left for 1 minute. After that, it contracts again at the same speed to draw a stress-strain curve. The elongation at the time of zero stress during shrinkage is referred to as the residual elongation (X). Elastic recovery rate was calculated | required according to the following formula.

Elastic recovery = [(20-X) / 20] × 100 (%)

(6) measurement of b value

The yellow color of the obtained fiber was measured using the b value. The b value was measured using the color computer of Suga Shikenki Co., Ltd. The yellow value increases as the value of b increases.

(7) Dyeing test

① Evaluation of dyeing property of polyester fiber by cation dye

The sample uses a single knit knitted fabric (ring knit, plain stitch knitted fabric, gauge 28) made of polyester fiber, and contains hot water (Scoring ratio 1:50) containing 2 g / l of Scoreroll 400 (Kao Co., nonionic surfactant). ), The mixture was refined at 70 ° C. for 20 minutes, and dried in a tumbler dryer. Subsequently, the thing which performed 30 second heat set at 180 degreeC using the pin tenter was used. Dye was dyed for 30 minutes at 4% owf, bath ratio 1:50, and 95 degreeC using Kayakryl blue GSL-ED (Cateon dye by Nihon Kayaku Co., Ltd.). As an additive, acetic acid 0.25 g / l and sodium sulfate 3 g / l were added and pH was adjusted.

② Evaluation of dyeability of polyester fiber by disperse dye

The sample used a single knit knitted fabric of polyester fibers (round knit, plain stitch knitted fabric, gauge 28), and hot water (bath ratio 1:50) containing 2 g / L of score roll 400 for 20 minutes at 70 ° C. It was refined and dried in a tumble dryer. Subsequently, the thing which performed 30 second heat set at 180 degreeC using the pin tenter was used. The dye was dyed for 60 minutes at 95 ° C at a bath ratio of 1:50 using Kayalon Polyester Blue 3RSF (manufactured by Nihon Kayaku Co., Ltd., disperse dye) at 6% owf. As a dispersant, 0.5 g / L of Nikasan Salt 7000 (manufactured by Nikka Chemical Co., Ltd., anionic surfactant) was used, 0.5 ml of acetic acid and 1 g / L of acetic acid were added, and the pH was 5 Adjusted to.

The removal rate was obtained by substituting the absorbance (A) of the dye stock solution and the absorbance (a) of the salt solution after dyeing with a spectrophotometer and substituting the following formula. The absorbance was used as the maximum absorption wavelength of the dye at 580 nm.

Absorption rate = (A-a) / A × 100 (%)

The deep color indicating how dark the color was, was evaluated using K / S. This value measured the spectral reflectance (R) of the sample cloth after dyeing, and calculated | required it by the formula of Kubelka-Munk shown below. The larger this value is, the larger the deep color effect is, that is, the color is well developed. R used the value in the maximum absorption wavelength of the said dye.

K / S = (1-R) ² / 2R

In addition, the brightness at the time of dyeing in black was evaluated using L value.

(8) dyeing fastness test

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

Dry cleaning fastness was performed according to JIS-L-0860, light fastness to JIS-L-0842, washing fastness to JIS-L-0844, and dry and wet friction fastness according to JIS-L-0849. In addition, dry cleaning fastness tested liquid contamination.

(9) Measurement of U%

It was measured using Zerveger Uster K.K. USTER TESTER 3.

Example 1

Trimethylene glycol (hereinafter referred to as "TMG") 1144 parts by weight, dimethyl terephthalate (hereinafter referred to as "DMT") 1300 parts by weight, 5-sulfoisophthalate tetrabutylphosphonium salt (hereinafter referred to as "SIPP") 57 Parts by weight (2 mol% relative to the total moles of the total acid component), lithium acetate as an ether forming inhibitor, 43 parts by weight, cobalt acetate as a coloring inhibitor 0.13 parts by weight, titanium tetrabutoxide as a transesterification catalyst 1.3 Using a weight part, the transesterification reaction was performed at 220 degreeC. Subsequently, 1.3 parts by weight of titanium tetrabutoxide as a polycondensation catalyst and 0.065 parts by weight of trimethyl phosphite were added as a heat stabilizer, and polycondensation was carried out at 270 ° C and a reduced pressure of 0.5 torr to obtain a polymer. The intrinsic viscosity of the obtained polymer was 0.61.

After drying the obtained polymer chip, the unstretched yarn was produced by spinning at a spinning speed of 265 ° C. at a spinning speed of 1200 m / min, using a spinneret having 36 circular cross-section holes (diameter 0.23 mm). Subsequently, the obtained undrawn yarn was drawn-twisted at a hot roll of 50 ° C., a hot plate of 140 ° C., a draw ratio of 3. 0 times, and a drawing speed of 600 m / min to draw 50 d / 36 f. Got a gentleman. The physical properties of the fiber were: melting point 231 ° C., density 1.32 g / cm 3, strength 3. 4 g / d, elongation 37%, Tmax 110 ° C., U% 1.2%, elastic modulus 22 g / d, elastic recovery rate 87 Was%. In addition, the Q / R value of the stretched yarn was 0. 25 so that the equation (1) could be satisfied. Moreover, b value of the fiber was 6.1.

The rate of reduction of the cation dye at 95 ° C and 30 minutes of the polyester fiber obtained in this example is 72%, so that a very clear dyeing product can be obtained.

In the dry cleaning fastness of the single knit knitted fabric after dyeing, no fading of the dyeing product was observed, and the liquid contamination was grade 4-5. Moreover, the light fastness (grade 4-5), dry and wet friction fastness (grade 5) and washing fastness (grade 5) were also good.

Examples 2-7

The polymerization and spinning were carried out by changing the type and copolymerization ratio of the ester-forming sulfonate compound in the same manner as in Example 1. Table 1 shows the test and evaluation test results of the obtained fibers. Fibers in any of the embodiments also satisfy Equation 1, and exhibit good dyeing, fastness, and physical properties.

Comparative Example 1

In the same manner as in Example 1, a polytrimethylene terephthalate homopolymer was obtained without using SIPP. The intrinsic viscosity of the obtained polymer was 0.63. This polymer chip was spun and stretched in the same manner as in Example 1 to obtain a fiber. The obtained fiber shows melting | fusing point 236 degreeC, Tmax 111 degreeC, strength 3.6 g / d, elongation 35%, elasticity modulus 23g / d, and elastic recovery rate 88%. Moreover, the Q / R value of this fiber is 0.26 and satisfy | fills Formula (1).

However, the dust removal rate of the cation dye at 95 degreeC and 30 minutes of the polyester fiber obtained by this comparative example is 6%, and it could not be dyed dark.

Comparative Example 2

In the same manner as in Example 1, a polymer was prepared in a copolymerization ratio of SIPP of 0.3 mol%, and spinning was performed. The test and evaluation result of the obtained fiber were put together in Table 1. The copolymerization ratio of the ester-formable sulfonate compound was less than 0.5 mol%, and the removal rate of the cation fuel at 95 ° C. for 30 minutes of the fiber was 30%, which could not be dyed dark.

Comparative Example 3

In the same manner as in Example 1, the copolymerization ratio of SIPP was 6 mol% to prepare fibers through polymerization and spinning. As a result, the evaluation results are summarized in Table 1. At the time of spinning of this polymer, a lot of trimming occurred and the radioactivity was bad. Moreover, when the fiber was dyed at 95 ° C, the yarn contracted and hardened, and a fabric of good texture could not be obtained. Moreover, the dry cleaning fastness of the obtained fabric fell compared with Example 1.

Comparative Example 4

In Example 1, the draw ratio was 3. 3 times. Orientation advanced too much and the obtained fiber exceeded 115 degreeC. The removal rate of the cation dye was 45%. Moreover, a lot of fluff generate | occur | produced in the obtained fiber.

Copolymerization component Melting point Extreme viscosity burglar Elongation Modulus Elastic recovery Q / R Tmax U% Reduction rate DC color fastness b value Kinds mole% (℃) [η] (g / d) (%) (g / d) (%) ℃ % (%) (class) Example 1 SIPP 2 231 0.61 3.4 37 22 87 0.25 110 1.2 72 4-5 6.1 Example 2 SIPM 2 232 0.48 3.4 34 24 76 0.32 110 0.9 94 4-5 6.2 Example 3 SIPA 2 219 0.50 2.0 30 20 70 0.29 110 1.1 78 4-5 6.3 Example 4 SIPP One 234 0.63 3.3 40 22 88 0.25 112 1.2 70 4-5 6.5 Example 5 SIPP 5 228 0.59 3.4 39 23 88 0.26 107 1.4 83 4-5 6.7 Example 6 SIPM 1.5 232 0.60 3.0 32 22 88 0.25 109 1.2 94 5 6.7 Example 7 SIPM 3.0 230 0.57 2.7 33 23 85 0.27 108 1.0 95 4-5 6.5 Comparative Example 1 - 0 236 0.63 3.6 35 23 88 0.26 111 - 6 - 6.2 Comparative Example 2 SIPP 0.3 234 0.62 3.5 35 24 88 0.27 111 - 30 - 6.3 Comparative Example 3 SIPP 6 225 0.59 3.3 38 21 63 0.33 106 - 98 3-4 6.4 Comparative Example 4 SIPP 2 231 0.61 4.1 20 25 95 0.26 116 3.1 45 4-5 6.2 SIPM: 5-sodium sulfoisophthalate dimethyl, SIPA: 5-sulfoisophthalic acid dimethyl dimethyl DC fastness: dry cleaning fastness

Comparative Example 5

Polymerization and spinning were performed in the same manner as in Example 1 except that the temperature of the hot roll was 25 ° C. A lot of trimming occurred at the time of stretching, and a fiber was not obtained continuously. Moreover, superposition | polymerization and spinning were performed by the method similar to Example 1 except having set the temperature of the hot roll to 80 degreeC. Since the yarn fused to the hot rolls at the time of stretching, a large number of single yarn trimmings occurred, and the fibers obtained were fluffy. U% was bad with 3. 2

Comparative Example 6

Polymerization and spinning were performed in the same manner as in Example 1 except that the temperature of the hot plate was changed to 70 ° C. Fibers could be obtained without problems such as trimming and fluffing. However, the fiber obtained had a low elastic recovery rate of 55% and a Q / R value of 0.49, which did not satisfy the equation (1).

Comparative Example 7

Polymerization and spinning were performed in the same manner as in Example 1 except that the temperature of the hot plate was 200 ° C. The fibers were broken at the hot plate portion and could not be stretched.

Comparative Example 8

Polymerization and spinning were 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 could be obtained without problems such as trimming and fluffing. However, the obtained fiber had a low elastic recovery rate of 48%, a Q / R value of 0.52, and could not satisfy the equation (1).

Comparative Example 9

Spinning was performed using polyethylene terephthalate fiber copolymerized with 2.5 mol% of 5-sodium sulfoisophthalic acid. The obtained fiber shows strength 4.2 g / d, elongation 30%, elastic modulus 100 g / d, elastic recovery rate 31%, Q / R value 3.2, Tmax 131 ° C, 95 ° C, 30 ° C of cation dye. The rate of dust reduction in 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 and yellowed.

Example 8

The polymer obtained in Example 2 was dried and the water content was 50 ppm, followed by melting at 285 ° C, followed by extrusion through a single-row spinneret with 36 holes having a diameter of 0.23 mm. The extruded molten multifilament is passed through a thermal insulation region having a length of 5 cm and a temperature of 100 ° C., followed by quenching with a wind speed of 0.4 m / min, and is turned into a solid multifilament. Next, the solid multifilament was subjected to hot stretching and hot set through a first roll having a rotational speed of 2100 m / min heated at 60 ° C and a second roll having a rotational speed of 4300 m / min heated at 133 ° C. , 4180 m / min. The obtained fiber was set to 75 d / 72f as bi yarn.

The obtained fiber had a strength of 3.1 g / d, an elongation of 41%, a U% of 0.7%, an elastic modulus of 22 g / d, an elastic recovery rate of 89%, a Q / R value of 0.25, a Tmax of 109 ° C, 95 ° C, The removal rate of the cation dye in 30 minutes was 98%, and showed the b value 6.5.

Example 9

The warp knitted fabric was knitted using the polyester fiber of Example 1 and the 210 denier leuca (polyurethane type expansion fiber manufactured by Asahi Kasei Kogyo Co., Ltd.). The knitted gauge was 28G, the loop length was 1080 mm / 480 course of polyester fiber, 112 mm / 480 course of stretch fiber, and cloth density was 90 course / inch. Moreover, the mixing ratio of the polyester fiber was set to 75.5%.

The obtained fiber was relax-refined at 90 degreeC for 2 minutes, and dry heat set was performed at 160 degreeC for 1 minute. Kayakryl black BS-ED (Cateon dye manufactured by Nippon Kayaku Co., Ltd.) was used, and 1 g / l of Disper TL (manufactured by Meisei Chemical Co., Ltd., nonionic activator) was used as a dispersant, 50 g / L sodium sulfate and 15 g / L sodium carbonate were added, and dye was added to the aqueous solution which adjusted pH to 11, and it was set as the salt solution. Dyeing was carried out at 95 ° C. for 1 hour at a dyeing concentration of 8% owf and a bath ratio of 1:50. After dyeing, it was soaped for 10 minutes at glan up P (Sanyo Chemical Co., Ltd. make, nonionic surfactant) 1g / L, bath ratio 1:50, and 80 degreeC. After dyeing, finishing was carried out according to a conventional method. The L value of the obtained dye was sufficiently dyed at 11.2. The dyeing fastnesses of the dyeings were wash fastness grade 5, wet friction fastness grade 5, and light fastness grades 4-5. This dyed letter also has a soft, stretchy texture with excellent elasticity and elasticity.

Example 10

The same operation as in Example 9 was repeated using the polyester fiber of Example 2. The L value of the obtained dye was 10.9, and it was sufficiently dyed. The dyeing fastness of this dyeing product was wash fastness grade 5, wet friction fastness grade 5, and light fastness grades 4-5. The dyeings are soft, elastic and have a good elasticity and elasticity.

Comparative Example 10

The same knitted fabric as in Example 9 was knitted using the polytrimethylene terephthalate fiber produced in Comparative Example 1.

The obtained fiber was relax-refined at 90 degreeC for 2 minutes, and dry heat set was performed at 160 degreeC for 1 minute. For dyeing to darker colors, Niacane Salt 1200, a dyeing aid, was used with acetic acid in the presence of 0.5 g / l using Dianics Black BG-FS (disperse dye manufactured by Dyster Japan) 8% owf. It adjusted and dyed for 60 minutes at 95 degreeC by bath ratio 1:30. The wet friction fastness of the obtained dyeing was secondary, and the glass of the disperse dye which contaminated the stretch fiber was confirmed.

In addition, the same operation as in Example 9 was repeated using the fiber produced in Comparative Example 9. The fabric obtained was certainly hard, and was dyed only lightly with an L value of 21.

Also, for comparison, nylon 6 fibers spun by conventional methods and Loika's warp knitted fabrics were prepared in the same manner as in Example 9, and were prepared using Kayalon Black BGL (acid dyes manufactured by Nippon Kayaku Co., Ltd.) at 100% by 7% owf. It dyed at 60 degreeC for 60 minutes. The light fastness of the obtained dyed fabric was 2 to 3 grade.

Example 11

75d / 36f polyester fiber obtained in the same manner as in Example 1 was inclined, weaving plain fabric (140 140 / 25.4 mm, 80 upper / 25.4 mm) using 75d / 44f copper ammonia rayon. ) Was prepared. This plain fabric was refined by a conventional method. After washing with water, a pre-set of 180 ° C. for 30 seconds was followed by one-time dyeing with a cation dye and a reactive dye without using an auxiliary agent. As the cation dye, Kayakryl black BS-ED (Cateon dye manufactured by Nippon Kayaku Co., Ltd.) and Drimarene Blue X-SGN (Reaction dye manufactured by Sandoz Co., Ltd.) were used. Dispersing agent was used 1 g / L of Disper TL (manufactured by Meisei Chemical Industries, Ltd.), 50 g / L of sodium sulfate and 15 g / L of sodium carbonate were added, and the dye was added to an aqueous solution whose pH was adjusted to 11. A saline solution was used. Dyeing was carried out at 100 ° C. for 1 hour at a concentration of 2% owf and a bath ratio of 1:50. After dyeing, 1 g / L of Gran Up P (manufactured by Sanyokasei Kogyo Co., Ltd.) and a bath ratio of 1:50 were soaped at 80 ° C for 10 minutes. After dyeing, it was finished by the usual method. The resulting dye was uniformly dyed and a clear dye. K / S was 24.3. In addition, even though the alkali weight loss treatment performed on ordinary polyester fibers was not performed, the soft texture and the dryness were sufficient, and the excellent texture was not obtained in the conventional fabric. Dry cleaning fastness was grade 5, wet friction fastness was grade 5, and light fastness was grade 4.

Further, using a 75d / 36f polyester fiber obtained in the same manner as in Example 1, weaving and weaving were made by weaving a plain weave fabric with the same inclination as the weft yarn. The fabric obtained had no dryness but was very soft and the fabric had a 7% stretch in the upward direction.

Example 12

Single knit knitted fabric made from the fiber obtained in Example 1 and polyethylene terephthalate fiber polymerized and spun in the same manner as in Example 1 and polyethylene terephthalate fiber copolymerized with 3-mol% of 5-sodium sulfoisophthalic acid (cyclic knitted fabric, An alkali weight loss test was conducted using a plain stitch knitted fabric, gauge 28). After knitting, the single knit knitted fabric was refined at 70 ° C. for 20 minutes using hot water containing 2 g / l of score roll 400, dried in a temper dryer, and then heat set at 180 ° C. for 30 seconds using a pin tenter. Was used. Alkali weight loss processing was performed by putting a single knit knitted fabric for 20 minutes in 6 wt% aqueous solution of boiled sodium hydroxide. Alkali weight loss was evaluated by the weight of the letter reduced by alkali weight divided by the weight of the original letter.

As a result, the reduction ratios in the single knit knit of the fiber obtained in Example 1 and the single knit knit of polyethylene terephthalate fiber were 25.4 weight% and 10.3 weight%, respectively. As described above, the polyester fiber of the present invention exhibits an alkali weight loss rate close to that of polyethylene terephthalate fiber.

Comparative Example 11

Alkali weight loss was carried out in the same manner as in Example 12 using a single knit knitted fabric obtained by copolymerizing polyethylene terephthalate fiber copolymerized with 3 mol% of 5-sodium sulfoisophthalic acid in the same manner as in Example 12 to completely decompose the letter. And dissolved and lost. Therefore, in the polyethylenetephthalate fiber copolymerized with 3 mol% of 5-sodium sulfoisophthalic acid, the weight loss rate is too fast to perform alkali weight loss processing.

Example 13

Using the same method as in Example 1, a fiber obtained by copolymerizing 2 mol% of 5-dimethyl sulfoisophthalate and 5% by weight of dimethyl adipic acid was produced. The physical properties of the fiber were melting point 220 ° C., strength 3. 6 g / d, elongation 34%, elastic modulus 22 g / d, elastic recovery 90%, and Q / R value of 0.24.

The reduction rate of the cation dye at 95 ° C and 30 minutes of the polyester fiber obtained in this example is 95%, and the reduction rate of the disperse dye at 95 ° C and 60 minutes is 95%, cationic dye and dispersion. Both of the dyes show high dyeability at normal pressure.

The dry-cleaning fastness of the single knit knitted fabric after dyeing did not show any fading of the dyeing, and the liquid contamination of cationic dyes and disperse dyes was 4 to 5 grades. Moreover, it is also favorable about the light fastness (class 4-5), dry and wet friction fastness (class 5), and wash fastness (class 5) of a fiber.

As a result of fabrication of the same knitted fabric as in Examples 9 and 11, a fabric having excellent texture similar to those of Examples 9 and 11 was obtained.

Example 14

The fiber obtained in Example 2 was cut and the short fiber of 39 mm of fiber length was obtained. The filament of 20d / 2f obtained by the method similar to Example 2 was made into the core, and the composite yarn which the filament mixing rate of this filament arrange | positioned on the outer shell was 11 weight%. This composite yarn was made of a woven fabric of warp yarn (fiber density 146 bone / 25.4 mm) and weft yarn (77 fiber density / 25.4 mm) and dyed at 95 ° C in accordance with the method of Example 9. .

K / S of dyed cloth is 25. 3 and dyed dark. In addition, the fabric obtained was excellent in elasticity, elasticity and resilience.

Example 15

The polymer obtained in Example 2 was solid-phase polymerized in nitrogen at 200 degreeC for 24 hours, and the polymer of intrinsic viscosity 1.0 was obtained. As a result of spinning in the same manner as in Example 1, strength 4.0 g / d, elongation 32%, U% 1.0%, elastic modulus 23 g / d, elastic recovery 91%, Q / R value 0.5, A fiber having a physical property of Tmax 110 ° C. and a b value of 4. 3 was obtained. Example 16 A 75 d / 36f polyester fiber obtained in Example 1 was inclined, and a plain fabric was produced using 75 d / 44f of copper ammonia rayon as a weft yarn (40 diameter / 25.4 mm, upper 80 pattern / 25). 4 mm). This plain fabric was refined by a conventional method. After water washing, after preliminary set of 180 degreeC and 30 second, cation dye and single-use dyeing with reactive dye were done without using an adjuvant. Kayakryl black BS-ED (Cateon Dye from Nippon Kayaku Co., Ltd.) and Drimarene Blue X-SGN (Sandoz Co., Ltd. reaction dye) were used. 50 g / L sodium sulfate and 15 g / L of sodium carbonate were added using 1 g / L of Disper TL (Meisei Kagaku Co., Ltd. dispersing agent), dye was added to the aqueous solution which adjusted pH to 11, and it was set as the salt solution. . Dyeing was carried out at 100 ° C. for 1 hour at a dye concentration of 2% owf and a ratio of 1:50. After dyeing, 1 g / L of Gran Up P (manufactured by Sanyo Kasei Kogyo Co., Ltd.) and a ratio of 1:50 were soaped at 80 ° C for 10 minutes. After dyeing, the treatment was carried out by a conventional method. The obtained dye was uniformly dyed, and was excellent in wet friction fastness, dry cleaning fastness, light fastness, and clear dyeing. In addition, although the alkali weight loss treatment performed by ordinary polyester fibers was not performed, the soft texture and dryness were overflowing, and the excellent texture was not obtained in the conventional textiles. 75d / 36f poly obtained in the same manner as in Example 1 The same plain weave fabric was manufactured and dyed by using the ester fiber in the same manner as the warp and the weft yarn. The fabric obtained had no feeling of drying, but was very soft and the fabric had about 7% stretch in the upward direction. Comparative Example 12 In Example 42, as a result of dyeing at a temperature of 130 ° C., the reaction dye decomposed and the fabric became dark. Example 17

The plain fabric which used the 75d / 36f polyester fiber obtained in Example 1 as a warp and weft was manufactured (140 inclination / 3 / 3.54, 80 weft yarn / 2.54). After refining this plain fabric by the conventional method, 20% alkali reduction was carried out using 10% sodium hydroxide aqueous solution. Thereafter, the same preliminary set and dyeing as in Example 42 were performed, and finally, a final set was performed at 180 ° C for 30 seconds.

The resulting fabric is soft and gives a dry texture that is unprecedented, and exhibits about 7% stretch in the upward direction.

The polytrimethylene terephthalate-based fiber of the present invention can be dyed to a color shade practically required with both dyes of cation dye, cation dye and disperse dye under normal pressure. In addition, the polytrimethylene terephthalate-based fiber of the present invention has wash and wear properties, dimensional stability, yellowing resistance, dryness, alkali loss processability close to general-purpose polyester fibers such as polyethylene terephthalate fibers, and flexibility similar to nylon fibers. It is a fiber material.

Because of the above-described performance, the polytrimethylene terephthalate-based fiber of the present invention is a low-heat-resistant fibrous material such as stretch fibers, wool, silk, acetate, and the like represented by polyurethane elastic fibers, and cellulose fibers dyed at normal pressure. It is a textile material suitable for the production of firm dyeing of fabrics mixed with. Particularly, it is a feature of the present invention that a firmly dyed fabric for a fabric product by mixing with the low heat-resistant fiber can be produced without damaging the properties of the fiber by using a simple dyeing method with a normal pressure dyeing facility. It is an industrial utility to do.

Claims (15)

In a fiber made of polyester obtained by copolymerizing polytrimethylene terephthalate with a third component, the third component is an ester-forming sulfonate compound having a copolymerization ratio of 0.5 to 5 mol%, and the peak temperature of the loss tangent of the fiber 85-115 degreeC, The relationship between the elasticity modulus Q (g / d) and the elastic recovery rate R (%) of the said fiber satisfy | fills Formula (1). [Equation 1] 18 ≤ Q / R ≤ 0. 45 The polyester fiber according to claim 1, wherein the ester-forming sulfonate compound is 5-sodium sulfoisophthalic acid or / and 3,5-dicarboxylic acid benzenesulfonic acid tetraalkylphosphonium salt. (Here, the alkyl group represents an alkyl group having 1 to 10 carbon atoms.) The polyester fiber according to claim 1, wherein the third component is an ester-forming sulfonate compound having 1.2 to 2.5 mol%. The ester-forming sulfonate compound according to claim 1, wherein the ester-forming sulfonate compound is 5-sodium sulfoisophthalic acid or / and 3,5-dicarboxylic acid benzenesulfonic acid tetraalkylphosphonium salt, and the copolymerization ratio is 1.2 to 2. Polyester fiber, characterized in that 5 mol%. (Here, the alkyl group represents an alkyl group having 1 to 10 carbon atoms.) delete Ester forming sulfonate compound having a copolymerization ratio of 1.2 to 2.5 mol%, (1) aliphatic or cycloaliphatic glycol having 4 to 12 carbon atoms, and (2) aliphatic or alicyclic dicarboxyl having 2 to 14 carbon atoms. A polytrimethylene terephthalate fiber obtained by copolymerizing at least 3% by weight of one or more selected from acids, isophthalic acid and (3) polyalkylene glycol, wherein the peak temperature of the loss tangent of the fiber is from 85 to 115 ° C. The relationship between the elasticity modulus Q (g / d) and the elastic recovery rate R (%) of a fiber satisfy | fills Formula (1). [Equation 1] 18 ≤ Q / R ≤ 0. 45 The polyester fiber of Claims 1-4 or 6 WHEREIN: b value is -2-10, The polyester fiber characterized by the above-mentioned. The fabric of Claim 1 to 4 or 6 which used the polyester fiber of one part or all part. The mixed fabric of Claim 1 to 4 or 6 which mixed the polyester fiber and elastic fiber. A fabric using the polyester fibers of claims 1 to 4 or 6 in part or all, which is dyed with a cation dye or / and a disperse dye. Polytrimethylene terephthalate resin which satisfy | fills following condition (1)-(3). (1) 0.5 to 5 mol% of ester-forming sulfonate compounds are copolymerized resins (2) Intrinsic viscosity of resin is 0.4 to 1.2 (3) b value of resin is -2 to 10 Polytrimethylene terephthalate resin which satisfy | fills following condition (1)-(4). (1) 1.2 to 2.5 mol% of esterogenic sulfonate compound is a copolymerized resin (2) 3 to 7% by weight of a copolymer of at least one member selected from aliphatic or cycloaliphatic glycols having 4 to 12 carbon atoms, aliphatic or cycloaliphatic dicarboxylic acids having 2 to 14 carbon atoms, isophthalic acid and polyalkylene glycol; Added to (3) Intrinsic viscosity of resin is 0.4 to 1.2 (4) b value of resin is -2 to 10 The polytrimethylene terephthalate resin according to claim 11 or 12, which contains 20 to 400 mol% of one or more compounds selected from basic metal salts with respect to the ester-forming sulfone salt compound. The polytrimethylene terephthalate resin according to claim 13, wherein the basic metal salt is lithium salt, sodium salt, potassium salt or calcium salt. Polytrimethylene terephthalate resin which satisfy | fills following condition (1)-(3). (1) ① 1.5 to 12% by weight aliphatic or cycloaliphatic glycol having 4 to 12 carbon atoms, ② a copolymerization ratio of 3 to 9% by weight aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms, or isophthalic acid, and ③ One or more types selected from the group of polyalkylene glycols having a copolymerization ratio of 3 to 10% by weight are copolymerized. (2) Intrinsic viscosity of resin is 0.4 to 1.2 (3) b value of resin is -2 to 10