JP3226931B2 - Polyester fiber and fabric using the same - 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

TECHNICAL FIELD The present invention relates to a polytrimethylene terephthalate fiber,
In particular, the present invention relates to a polytrimethylene 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, and a fabric using the fiber.

Background ArtPolytrimethylene terephthalate fiber has properties similar to nylon fiber such as soft texture derived from low elastic modulus and excellent elastic recovery, and polyethylene terephthalate fiber such as wash and wear property, dimensional stability and yellowing resistance. It is an epoch-making fiber having similar properties, and its characteristics are being applied to clothing, carpets and the like.

However, polytrimethylene terephthalate fibers have problems with dyeability. That is, in the known polytrimethylene terephthalate fiber, the dye to be used is limited to the disperse dye, and there is a serious problem in dyeing that the dye can be dyed only under a high pressure of 110 to 120 ° C.

The fact that the dye to be used for dyeing the fiber is limited to the disperse dye means that the obtained dyed product has low clarity, and the dry cleaning fastness, wet rub fastness, and sublimation fastness are slightly inferior.

Further, the fact that the dyeing temperature for dyeing a dark color is 110 to 120 ° C. means, for example, that it is not possible to dye a mixed fabric with other fibers that undergo thermal decomposition at these high temperatures. For example, if polytrimethylene terephthalate fibers and other fibers such as polyurethane elastic yarn, wool, silk, and acetate fibers are mixed, a mixed cloth having a soft and uncomfortable texture can be expected. If the temperature is higher than 110 ° C., there is a problem that the strength is greatly reduced or the glass is devitrified to white, thereby greatly impairing the merchantability.

If polytrimethylene terephthalate fibers which can be dyed at a high pressure with one or both of a cationic dye and a disperse dye at normal pressure can solve these problems, such fibers have not been known.

In the range of known techniques, no technique is known which makes it possible to dye polytrimethylene terephthalate fiber with a dye other than the disperse dye, for example, a cationic dye.

Although no specific application to polytrimethylene terephthalate fiber is described, as a method for improving the dyeability of polyester fibers, mainly polyethylene terephthalate fibers, to cationic dyes, polyesters such as sulfonic acid metal bases and sulfones are used. A method of adding isophthalic acid having a quaternary phosphonium acid base before completion of the polycondensation reaction and copolymerizing (JP-B-34-10497, JP-B-47-22334, JP-A-5-230713) Are known. However, the fibers thus obtained are not dyeable under normal pressure cationic dyes and have a high modulus of elasticity, so that they give only stiff and rugged fabrics. In addition, as a method for imparting cationic dyeability at normal pressure, a dicarboxylic acid such as adipic acid or isophthalic acid or an alkyl ester thereof is used as a copolymer component together with isophthalic acid having a sulfonic acid metal base in polyethylene terephthalate. Are known (for example, see JP-A-57-6611).
No. 9). However, the fibers thus obtained also have a high modulus of elasticity and give only stiff fabrics.

Fibers having good dyeing properties for disperse dyes, low elastic modulus, and excellent elastic recovery properties include, for example, JP-A-52-53.
The polytrimethylene terephthalate fiber disclosed in Japanese Patent Publication No. 20 is cited. Furthermore, Japanese Patent Publication No. 9-509225 discloses a method of dyeing polytrimethylene terephthalate fiber 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 respect to disperse dyes, the technique disclosed in these known documents can only be dyed at a very low dye concentration at normal pressure. I understand. For example, in the example of JP-A-9-509225, the dye concentration used is at most 0.5% owf (where,
The unit of% owf is the concentration of the dye in the dye liquor expressed in terms of% by weight of the fiber to be dyed). In the field of clothing, fabrics dyed dark as well as light and medium colors are required.
In such a deep color dyeing, the dye concentration is required to be 4% owf or more, and in some cases 10% owf or more. However, in dyeing polytrimethylene terephthalate fiber, the dye can be sufficiently exhausted at normal pressure. It cannot be dyed dark because it cannot.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a polytrimethylene terephthalate-based fiber that can be dyed in a deep color under normal pressure by using one or both of a cationic dye and a disperse dye.

Another object of the present invention is to provide a polytrimethylene terephthalate capable of dyeing a composite fiber product mixed with polyurethane elastic fiber, wool, silk, acetate, etc. without impairing the properties of these relatively low heat-resistant fibers. It is to provide a system fiber.

Still another object of the present invention is to provide a cross-woven, blended and cross-knitted fabric of a polytrimethylene terephthalate-based fiber and other fiber materials which can be fast dyed under normal pressure.

One specific object of the present invention is to provide a mixed fabric of a polyurethane elastic fiber and a polytrimethylene terephthalate-based fiber, which can be fast dyed in a simple manner using a conventional atmospheric pressure dyeing facility. include.

The present inventors have used polytrimethylene 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 peak temperature, elastic modulus, and elastic recovery rate. The inventors have found that a polyester fiber prepared to have the above-mentioned problem can solve the above-mentioned problems, and have reached the present invention.

That is, the first of the present invention is an ester-forming sulfonate compound having a copolymerization ratio of 0.5 to 5 mol% in a fiber made of a polyester obtained by copolymerizing a third component with polytrimethylene terephthalate, 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 satisfies the following equation (1). 0.18 ≦ Q / R ≦ 0.45 (1) A second aspect of the present invention is a polyester fiber obtained by copolymerizing a third component with polytrimethylene terephthalate. In the fiber, the third component is (1) an aliphatic or alicyclic glycol having a copolymerization ratio of 1.5 to 12% by weight and a carbon number of 4 to 12;
(2) an aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms having a copolymerization ratio of 3 to 9% by weight, or isophthalic acid;
(3) at least one selected from polyalkylene glycols having a copolymerization ratio of 3 to 10% by weight, the fiber has a loss tangent peak temperature of 85 to 102 ° C., and an elastic modulus Q ( g / d) and an elastic recovery ratio R (%) satisfy the following formula (1): a polyester fiber and a fabric using the same.

0.18 ≦ Q / R ≦ 0.45 Formula (1) The polymer constituting the polyester fiber of the present invention is a polyester obtained by copolymerizing polytrimethylene terephthalate with a specific amount of a third component. Here, polytrimethylene terephthalate means terephthalic acid as an acid component and trimethylene glycol (also called 1,3-propanediol).
Are diol components.

When a specific amount of the ester-forming sulfonate compound is used as the third component to be copolymerized, a normal pressure cationic dye-dyeable fiber can be obtained. Also, (1) the number of carbon atoms is 4 to
A specified amount of at least one selected from aliphatic or alicyclic glycols up to 12, (2) aliphatic or alicyclic dicarboxylic acids having 2 to 14 carbon atoms, or isophthalic acid, and (3) polyalkylene glycols Upon copolymerization, a normal pressure disperse dye dyeable 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.

Here, R ₁ and 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 (where R is an alkyl group having 1 to 10 carbon atoms, n, m, and p are integers of 1 or more), and R ₁ , R ₂
May be the same group or different groups. M is metal, N
H ₄ or a phosphonium group represented by the formula —PR ₃ R ₄ R ₅ R ₆ (wherein R ₃ , R ₄ , R ₅ and R ₆ are selected from a hydrogen atom, an alkyl group, an aryl group and a hydroxyalkyl group) The same or different groups, 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 3
It is a valent 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. Further, 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 of fibers at 95 ° C. is approximately 70%.
It means that the above is achieved.

In addition, since the cationic dyeable yarn has an appropriate alkali weight loss characteristic, a softer texture can be obtained by reducing the alkali weight after weaving and weaving. Here, the alkali weight loss means that the fabric is heated in an aqueous alkali solution to dissolve a part of the polymer on the fiber surface. Moderate alkali weight loss means that the amount and rate of alkali weight loss can be controlled industrially. This is a surprisingly significant feature.For example, in the case of cationic dyeable polyethylene terephthalate fiber, the rate of alkali weight loss is too fast to control industrially practically. However, it is the same as ordinary polyethylene terephthalate fiber, and it is possible to reduce the alkali using a known method. The polyester fiber of the present invention, which has been reduced in alkali in this way, can be characterized in that it becomes softer, has micropores of about several μm on the fiber surface, and has a dry feeling and can be dyed more clearly. .

Specific examples of preferred ester-forming sulfonate compounds include 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 4-sodium sulfo-2,
6-naphthalenedicarboxylic acid, 2-sodium sulfo-
4-hydroxybenzoic acid, 3,5-dicarboxylic acid benzenesulfonic acid tetramethylphosphonium salt, 3,5-dicarboxylic acid benzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxylic acid benzenesulfonic acid tributylmethylphosphonium salt, 2, 6-dicarboxylic acid naphthalene-4-sulfonic acid tetrabutylphosphonium salt, 2,6-
Examples include dicarboxylic acid naphthalene-4-sulfonic acid tetramethylphosphonium salt, 3,5-dicarboxylic acid benzenesulfonic acid ammonium salt and the like, and ester derivatives thereof such as methyl and dimethyl esters. In particular, these ester derivatives such as methyl and dimethyl esters are preferably used in view of excellent polymer whiteness and polymerization rate.

It is necessary that the copolymerization ratio of the ester-forming sulfonate compound to polytrimethylene terephthalate is 0.5 to 5 mol% based on the total number of moles of all the acid components constituting the polyester. 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. On the other hand, 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 the cationic dye, preferably from 1 to 3 mol%, particularly preferably,
1.2 to 2.5 mol%.

Specific examples of the aliphatic glycol having 4 to 12 carbon atoms and the alicyclic glycol used in the present invention include, for example, 1,2-
Butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol, dodeca Methylene glycol, 1,
4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and the like. By copolymerizing these glycols with polytrimethylene terephthalate, it becomes possible to dye to a deep color using a disperse dye at normal pressure. Among these aliphatic or cycloaliphatic glycols, 1,4-butanediol, 1,6-hexamethylene glycol, neopentyl glycol, in consideration of the polymer's whiteness, thermal decomposability, and excellent light resistance, Cyclohexanedimethanol is preferred. Further polymerization rate,
In view of the excellent dry cleaning fastness, 1,4-butanediol is particularly preferred.

The copolymerization ratio of these glycols to polytrimethylene terephthalate is 1.5 to 1 based on the weight of the polymer.
It needs to be 2% by weight. If the copolymerization ratio is less than 1.5% by weight, it will not be possible to dye the disperse dye to a deep color at normal pressure. The copolymerization ratio of glycol has a great correlation with the elastic modulus, elastic recovery rate, 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 texture changes hardly in the normal use stage represented by post-processing such as heat setting and ironing. There is a drawback that the fabric after dyeing is deteriorated in the fastness to dry cleaning after dyeing. Preferably it is 2 to 10% by weight, more preferably 3 to 7% by 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, heptandioic acid, octanedioic acid , Sebacic acid, dodecanedioic acid, 2-methylglutaric acid, 2-methyladipic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
Examples thereof include 1,2-cyclohexanedicarboxylic acid. 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 acid, sebacic acid, dodecane diacid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid in terms of polymerization rate during copolymerization and excellent light resistance Is preferred. Furthermore, isophthalic acid is particularly preferred in view of the fact that the whiteness of the polymer is excellent.

The copolymerization ratio of these aliphatic or alicyclic dicarboxylic acid or isophthalic acid to 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 a deep color at normal pressure. If the copolymerization ratio is more than 9% by weight, the melting point and the glass transition point are too low, so that the texture changes firmly at the stage of normal use such as post-processing such as heat setting and ironing. There is a drawback in that the fabric is dyed and the fastness to dry cleaning of the dyed fabric is reduced. Preferably 3
-8% by weight, more preferably 3-7% by weight.

In the present invention, a polyalkylene glycol can be used as a copolymer component. When a glycol or an acid is copolymerized as the third component, the melting point is inevitably lowered, and the spinnability is deteriorated. When the obtained fiber is subjected to post-processing, heat, fusion to a heat source, remarkable shrinkage, and the like occur. May be observed and the handling may be poor. However, when polyalkylene glycol is used as the third component, the melting point hardly decreases, and such a problem does not occur. This is considered to be because the polyalkylene glycol component was localized in the polymer because of its high molecular weight. As the polyalkylene glycol to be used, any of polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol or a copolymer thereof may be used, but polyethylene glycol is most preferable in consideration of thermal stability.

The average molecular weight of the polyalkylene glycol is 300
~ 20,000 is preferred. If the average molecular weight is less than 300,
Since a polyalkylene glycol having a considerably low molecular weight is contained, the polyalkylene glycol is distilled off under reduced pressure during polymerization under a high vacuum, and the amount of the polyalkylene glycol contained in the obtained polymer is not constant. Therefore, the strength and elongation properties of the yarn, dyeability,
The thermal characteristics and the like are not uniform, resulting in variations in product characteristics.

On the other hand, if the average molecular weight exceeds 20,000, the amount of high-molecular-weight polyalkylene glycol that is not copolymerized in the polymer increases, so that the dyeing properties, dry cleaning fastness, and light fastness are reduced. The average molecular weight of the polyalkylene glycol is 400 to 10,000, more preferably 500 to 5
000 is good.

The copolymerization ratio of polyalkylene glycol to polytrimethylene terephthalate is 3 based on the weight of the polymer.
It needs to be ~ 10% by weight. If the proportion of the polyalkylene glycol is less than 3% by weight, the disperse dye cannot be dyed to a deep color at normal pressure. On the other hand, when the proportion of the polyalkylene glycol exceeds 10% by weight, the heat resistance of the polymer decreases, and the polymerizability and spinnability deteriorate significantly. In addition, the glass transition point becomes too low, and the texture changes hardly in the post-process represented by heat setting and in the stage of normal use represented by ironing, and the dry-cleaning fastness of the fabric after dyeing. And a disadvantage that light fastness is significantly reduced. Preferably 4 to 8% by weight
It is.

The polymer constituting the polyester fiber of the present invention includes:
The fourth component can be copolymerized or blended without impairing the object of the present invention. Even when such a fourth component is used, it is necessary to keep within the above-mentioned range of the copolymerization ratio so as not to hinder the object of the present invention. Among these combinations, in particular, the ester-forming sulfonate compound and (1) an aliphatic or alicyclic glycol having 4 to 12 carbon atoms, and (2) an aliphatic or alicyclic compound having 2 to 14 carbon atoms. Dicarboxylic acid or isophthalic acid,
(3) When at least one selected from polyalkylene glycols is copolymerized, polyester fibers that can be dyed with both cationic dyes and disperse dyes at normal pressure can be obtained. As such a copolymerization ratio, preferably, the ester-forming sulfonate compound is 1.2 to 2.5 mol%, and at least one selected from the above (1) to (3) is 3 to 7% by weight. preferable.

Further, if necessary, various additives to the polyester fiber of the present invention, for example, matting agents, heat stabilizers, antifoaming agents, tinting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, A crystal nucleating agent, a fluorescent whitening agent and the like may be copolymerized or mixed.

The polyester used in the present invention can define the molecular weight by the intrinsic viscosity, and the intrinsic viscosity [η] is preferably 0.3 to 2.0, more preferably 0.35 to 1.5, and particularly preferably.
When it is 0.4 to 1.2, a polyester fiber having excellent strength and spinnability can be obtained. When the intrinsic viscosity is less than 0.3, the spinning property becomes unstable because the degree of polymerization of the polymer is too low.
In addition, 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 is not performed smoothly, and the spinnability is reduced due to poor discharge or the like.

Regarding the method for producing the polymer constituting the polyester fiber of the present invention, the polymerization can be basically carried out using a known method. That is, in an ordinary step of producing polytrimethylene terephthalate, a transesterification reaction and a polycondensation reaction of a lower ester of terephthalic acid such as terephthalic acid or dimethyl terephthalate with trimethylene glycol are carried out at an optional stage. Ingredients can be added. In this case, the ester-forming sulfonate compound and the aliphatic or alicyclic dicarboxylic acid, or isophthalic acid need to promote the reaction with trimethylene glycol, and therefore it is preferable to add them before the transesterification reaction. The polyalkylene glycol is preferably added at the end of the transesterification to prevent yellowing of the polymer and bumping at reduced pressure. It is preferable to use 0.01 to 0.1% by weight of a metal acetate, titanium alkoxide, or the like as the transesterification catalyst, since it has both the reaction rate, the whiteness of the polymer, and the thermal stability. The reaction temperature is about 200 to 240 ° C. As the polycondensation catalyst, antimony oxide, titanium alkoxide, or the like can be used. In particular, when a titanium alkoxide is used, the polycondensation catalyst may also be used as a transesterification catalyst. As the amount of catalyst,
From the viewpoint of the reaction rate and the whiteness of the polymer, it is 0.01 to 0.1% by weight based on the total amount of the carboxylic acid used. The reaction temperature is 240 to 280 ° C, and the degree of vacuum is 0.001 to 1 torr. The various additives described above may be added at any stage in the polymerization process, but are preferably added at any stage after the end of the transesterification reaction in order to minimize the inhibition of the reaction.

The polymer constituting the polyester fiber of the present invention may be obtained by solid-state polymerization of the polymer obtained by the above method in an inert gas such as nitrogen or argon or under reduced pressure to increase the molecular weight. When such a method is applied, yellowing of the polymer can be suppressed, the amount of oligomers that cause thread breakage or fluff can be reduced, and the strength can be increased. For the method of solid phase polymerization, for example, a known method used for polyethylene terephthalate can be applied as it is,
The intrinsic viscosity of the prepolymer before solid phase polymerization is 0.4 to
0.8 is preferred from the viewpoint of increasing the whiteness, and the solid phase polymerization temperature is preferably 170 to 230 ° C. The time varies depending on the desired viscosity, but is usually about 3 to 36 hours.

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, polytrimethylene terephthalate obtained by copolymerizing 5% by weight of 1,4-butanediol may be produced by mixing 95% by weight of polytrimethylene terephthalate and 5% by weight of polybutylene terephthalate. Mixing here means that the mixture may be mixed in a polymerization kettle and sufficiently transesterified and then discharged, or more simply, the mixture may be reacted in an extruder in a chip-blended state. Even if such a method is employed, a homogeneous polymer can be obtained because the transesterification rate is sufficiently high.

What is important about 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 polytrimethylene terephthalate, it is generally easy 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 the catalyst and the reaction temperature, and at the same time, use a heat stabilizer and a coloring inhibitor. As the heat stabilizer, a pentavalent or trivalent phosphorus compound is preferable, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, phosphoric acid, phosphorous acid and the like. 0.1 for polymers.
It is preferable to add from 01 to 0.07% by weight. 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 a prepolymer is an extremely effective method for increasing whiteness. The polymer thus obtained can maintain excellent whiteness even in the case of fibers. Such whiteness is -2 to 10, and preferably -1 to 6 in b value described later.

Furthermore, when an ester-forming sulfonate compound is used, a substance that easily aggregates in the spinning pack during the polymerization process is likely to be formed, and trimethylene glycol dimer (structural formula: HOCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH Particular attention should be paid to the fact that ₂ OH) is easily formed. When the amount of aggregates is large, the pressure in the spinning pack increases and the yarn breaks easily. In order to prevent this, the frequency of exchanging the spinning pack is increased and the productivity is lowered. Further, when the amount of trimethylene glycol dimer is large, there arises a problem that heat stability and light resistance at the time of melting are reduced. In order to prevent such a problem, it is preferable to add a certain additive at an arbitrary stage during polymerization. Examples of such an additive include basic metal salts such as lithium acetate, lithium carbonate, lithium formate, sodium acetate, sodium carbonate, sodium formate, sodium hydroxide, calcium hydroxide, and potassium hydroxide. As the ester-forming sulfonate compound, 20 to 400
Mol%, preferably 70 to 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 total denier, but 5-1000
d, when used for clothing, 5-200 d is particularly preferred. Single yarn denier is also not particularly limited, but is preferably 0.0001 to 10d
It is. Also, the cross-sectional shape is not particularly limited, such as a round shape, a triangular shape, a flat shape, a star shape, 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 “Tmax”) determined from the dynamic viscoelasticity measurement is 85 to 115 ° C. when the third component is an ester-forming sulfonate compound, The three components are (1) a copolymerization ratio of 1.5 to
12% by weight of an aliphatic or alicyclic glycol having 4 to 12 carbon atoms, (2) copolymerization ratio of 3 to 9% by weight of carbon number 2 to 2
Up to 14 aliphatic or cycloaliphatic dicarboxylic acids, or isophthalic acid; (3) at least one polyalkylene glycol selected from the copolymerization ratio of 3 to 10% by weight;
It needs to be ~ 102 ° C. This is because, in this range, normal pressure dyeability and high fastness by the cationic dye and / or disperse dye required by the present invention can be secured. Tm
ax corresponds to the molecular density of the amorphous part, so the smaller this value is, the smaller the molecular density of the amorphous part is.
The space for the dye to enter is large, and the dye is easy to enter and the exhaustion rate is high. When any of the third components is used, if the Tmax is less than 85 ° C., the molecules can easily move at a low temperature. Therefore, in a normal post-processing represented by a heat set, in a normal use stage represented by ironing, etc. The shrinkage becomes too large and the texture deteriorates, or the dry cleaning fastness of the fabric after dyeing is reduced. When an ester-forming sulfonate compound is used as the third component, when Tmax exceeds 115 ° C.,
The dyeability, which is the object of the present invention, is reduced, and the void portion for the dye is too small, so that it is impossible to dye the cationic dye to a deep color under normal pressure. As the third component, (1) a copolymerization ratio of 1.5 to 12% by weight having 4 to 1 carbon atoms;
Up to 2 aliphatic or alicyclic glycols, (2) a copolymerization ratio of 3 to 9% by weight of an aliphatic or alicyclic dicarboxylic acid or isophthalic acid having 2 to 14 carbon atoms, and (3) a copolymerization ratio of 3 When at least one member selected from the group consisting of polyalkylene glycols of 10 to 10% by weight is used, Tmax is 102.
When the temperature exceeds ℃, the void portion for the dye is too small, and it becomes impossible to dye the disperse dye to a deep color under normal pressure.

Thus, Tmax is a structural factor of the fiber, so even if the polymers have the same copolymer composition, spinning temperature, spinning speed, draw ratio, heat treatment temperature, scouring conditions, alkali weight reduction conditions, dyeing conditions, etc. It shows different values depending on spinning conditions and post-processing conditions. In particular, since this value greatly changes at the heat setting temperature, the heat setting temperature is changed to
Is within the above range. The concept of setting the heat setting temperature is roughly described.In the case of the polyester fiber specified in the present invention, the heat setting temperature is set at room temperature to 15%.
Tmax gradually increases up to about 0 ° C, but 160 ° C
If it exceeds this level, it will decrease significantly thereafter. Since the ratio of these changes differs for each 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 always better to be low, because the amorphous part becomes too coarse,
It has the drawback that the dye is easy to enter and easy to escape. That is, the fastness, especially the fastness to dry cleaning, the fastness to wet friction, the fastness to washing, and the like are reduced. In addition, problems such as deterioration of texture due to curing during heat setting and decrease in dimensional stability arise. The preferred range of Tmax 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 is preferred.
° C, (1) a copolymerization ratio of 1.5 to 12% by weight having 4 to 12 carbon atoms
(2) an aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms having a copolymerization ratio of 3 to 9% by weight, and (3) a copolymerizing ratio of 3 to 10% by weight. When at least one selected from alkylene glycols is used, the temperature is 85 to 102 ° C, particularly preferably 90 to 98 ° C.

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

0.18 ≦ Q / R ≦ 0.45 Expression (1) If Q / R> 0.45, the elasticity is too high, so that a soft feel comparable to nylon aimed at in the present invention cannot be obtained.
Alternatively, the elastic recovery properties are insufficient, and the fibers once deformed by the application of stress cannot return to the original state, and only a fabric having poor form stability can be obtained. Also, Q / R
Since there is substantially no region where <0.18, the present invention sets 0.18 as the lower limit of Q / R. The specific elastic modulus that can be in the range of the formula (1) is usually 25 to 40 g / d, and the elastic recovery is 70 to 99%.

Incidentally, an ester-forming sulfonate compound having a copolymerization ratio of 1.2 to 2.5 mol% and a copolymerization ratio of 3 to 7% by weight (1) a fatty or alicyclic glycol having 4 to 12 carbon atoms, (2) In the case of a polytrimethylene terephthalate fiber obtained by copolymerizing at least one selected from aliphatic or alicyclic dicarboxylic acids having 4 to 12 carbon atoms, or isophthalic acid, and (3) polyalkylene glycol, Of the fiber at 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 expression (1). It is required for the same reason as in 1).

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

The polyester fiber of the present invention is at least 100 ppm, preferably a polymer dried to a water content of 50 ppm or less is melted using an extruder or the like, and then the melted polymer is extruded from a spinneret, wound up, and then stretched. Can be obtained. Here, drawing after winding means that after spinning, the yarn is wound on a bobbin or the like, and the yarn is drawn using another device. After cooling and solidifying
By being wound around the first roll rotating at a constant speed several times or more, the tension before and after the roll is not transmitted at all, and the second roll installed next to the first roll and the first roll And a so-called direct drawing method in which a spinning-drawing step is directly connected.

 Hereinafter, the ordinary method will be described with reference to examples.

In the present invention, the spinning temperature at the time of melt spinning the polymer is 240 to 320 ° C, preferably 240 to 300 ° C, more preferably
A range from 240 to 280 ° C is suitable. When the spinning temperature is lower than 240 ° C., the temperature is too low and it is difficult to obtain a stable molten state, the resulting fiber has large unevenness, and does not exhibit satisfactory strength and elongation. On the other hand, when the spinning temperature exceeds 320 ° C., the 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 3500 m / min or less, preferably 2500 m / min or less, more preferably 200 m / min or less. Winding speed is 3500m / min
Is exceeded, crystallization proceeds too much before winding, and the stretching ratio cannot be increased in the stretching step, so that the molecules cannot be oriented, and sufficient yarn strength and elastic recovery cannot be obtained. In this case, tightening of the bobbin occurs, and the bobbin and the like cannot be pulled out from the winder. The stretching ratio during 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 2 or less, the polymer cannot be sufficiently oriented by drawing, and the elastic recovery of the obtained yarn will be low, and the formula (1) cannot be satisfied. On the other hand, if it is four times or more, thread breakage is severe and stretching cannot be performed stably.

The temperature at the time of stretching in the stretching zone is 30 to 80 ° C, preferably 35 to 70 ° C, and more preferably 40 to 65 ° C. If the temperature of the drawing zone is lower than 30 ° C., yarn breakage occurs frequently during drawing, and fibers cannot be obtained continuously. On the other hand, if the temperature exceeds 80 ° C., the slipperiness of the fiber with respect to a heating zone such as a drawing roll deteriorates, so that single yarn breakage occurs frequently and the yarn is full of fluff. In addition, since the polymers slip through each other, sufficient orientation is not obtained, and the elastic recovery rate decreases.

In addition, it is necessary to perform a heat treatment after the stretching in order to avoid a temporal change of the fiber structure. This heat treatment is at 90 to 200C, preferably 100 to 190C, more preferably 110 to 180C.
It is better to do it. 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. Also, 20
At a temperature higher than 0 ° C., the fibers are cut in the heat treatment zone and cannot be drawn.

Next, the straightening method will be described with reference to examples. The molten multifilament extruded from the spinneret was provided directly below the spinneret.
After suppressing the rapid cooling by passing through a heat retaining area of 2-80 cm in length maintained at an ambient temperature of ~ 200 ° C, this molten multifilament was rapidly cooled and changed to a solid multifilament, and heated to 40-70 ° C. Wound around the first roll at a rotation speed of 300 to 3000 m / min, then wound around the second roll heated to 120 to 160 ° C without winding, between the first roll and the second roll, which has a higher speed than the first roll Then, the film is stretched 1.5 to 3 times by using a winding machine at a lower speed than the second roll. A confounding treatment may be performed as necessary in the spinning process. Further, the undrawn yarn once wound at a spinning speed of 300 to 3000 m / min may be wound through the first roll and the second roll.

Melt extrusion of the polymer is performed in the same manner as in the ordinary method, and the molten multifilament that has come out of the spinneret is not immediately quenched,
After suppressing the rapid cooling by passing through a heat retaining area of 2 to 80 cm in length maintained at an ambient temperature of 30 to 200 ° C. provided immediately below the spinneret, the molten multifilament is rapidly cooled and changed to a solid multifilament. It is highly preferred to subject it to a subsequent stretching step. By allowing the polymer to pass through this heat retaining region, it is possible to suppress the generation of fine crystals and extremely oriented amorphous portions due to quenching of the polymer, and to form an amorphous structure that is easily stretched in the stretching step. Required fiber properties can be achieved. Since polytrimethylene terephthalate has, for example, a much faster crystallization rate than polyester such as polyethylene terephthalate, performing such slow cooling can reduce fine crystals or extremely oriented amorphous portions. This is an extremely effective method for suppressing the generation of. If the temperature is lower than 30 ° C., rapid cooling occurs, making it difficult to increase the stretching ratio. If the temperature is 200 ° C. or higher, 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. Further, the length of the heat retaining region is preferably 5 to 30 cm.

Regarding the spinning speed of the yarn, the winding speed of the first roll is 300 to 3000 m / min. When the spinning speed is less than 300 m / min, spinning stability is excellent, but productivity is significantly reduced.
Also, if it exceeds 3000 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, so that the molecules cannot be oriented, and Low yarn strength. Preferably, 1500
~ 2700m / min.

It is necessary that the speed of the winder be lower than that of the second roll, in order to cause the orientation of the amorphous portion of the fiber to be relaxed, and thereby, the large shrinkage of the polytrimethylene terephthalate fiber is reduced, and the amorphous portion is also reduced. It becomes loose and has a structure in which the dye easily enters, so that the dyeability is improved. Relaxation ratio (winding speed / second roll speed) is about 0.95-0.99,
Preferably it is 0.95 to 0.98.

The speed of the second roll is determined by the stretching ratio, but is usually 600 to 6000 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 drawing, and the strength and elastic recovery of the obtained fiber will be low. On the other hand, if it is three times or more, fluff is severe and stretching cannot be performed stably. The temperature of the first roll is 40 to 70 ° C., and in this range, a state where stretching is easy can be created. Preferably, 50-60 ° C
It is. Perform heat setting on the second roll, but with a temperature of 12
0-160 ° C. If the temperature is lower than 120 ° C., the fiber becomes poor in heat stability, easily deformed due to heat deformation and changes with time, and the coloring property is lowered. On the other hand, if the temperature is 160 ° C. or higher, fluff and yarn breakage occur, and stable spinning cannot be performed. Preferably, it is 120 to 150 ° C.

It is important to apply the preferable conditions shown in the ordinary method and the straight-drawing method described above in order to ensure the uniformity and quality of the obtained fiber. The parameters for evaluating the quality of the fiber obtained by applying the preferred spinning conditions include:
For example, U% can be used. U% is a parameter indicating the homogeneity of the cross section of the fiber, and when preferable conditions are applied, U% shows a value of 2.5% or less, and sometimes 1.5% or less.

The polyester fiber obtained as described above can be used alone or by using a part of a fabric to provide softness,
The resulting fabric has excellent stretchability and coloring properties. There is no particular limitation on other fibers when used for part of the fabric,
In particular, by mixing with fibers such as stretch fibers typified by polyurethane elastic fibers, cellulose fibers, wool, silk, and acetate, characteristics that cannot be obtained with a mixed fabric using nylon fibers or polyethylene terephthalate fibers can be exhibited. . That is, for example, while normal pressure dyeing can be performed using a cationic dye or / and a disperse dye,
It is a fabric with a unique texture with softness and stretchability that has never existed before.

Particularly in the field of the polyester fiber of the present invention, in which one of the cationic dye and the disperse dye, or both dyes, can be used for dyeing dark color without contaminating polyurethane elastic fiber, nylon fiber and A mixed fabric of the polytrimethylene terephthalate fiber and a stretch fiber represented by a polyurethane elastic fiber in that it can have a different softness touch than a mixed fabric of a stretch fiber represented by a polyurethane elastic fiber. Are exemplified as particularly preferred fabrics.

The fabric of the present invention includes the mixed fabric described above,
The knitting and weaving method is not particularly limited, and a known method can be used. For example, a plain woven fabric using the polyester fiber of the present invention as a warp or a weft, a woven fabric such as a reversible woven fabric, a knitted fabric such as a tricot or a raschel, and the like may be used.

The stretch fiber used in the present invention is not particularly limited, but is represented by dry-spun or melt-spun polyurethane elastic fiber, or polybutylene terephthalate fiber or polytetramethylene glycol copolymerized polybutylene terephthalate fiber. Examples include polyester-based elastic fibers. 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, for example, after knitting and weaving,
Dyeing can be carried out through the steps of scouring, presetting, dyeing, and final setting by a conventional method. Further, if necessary, after scouring and before dyeing, alkali reduction treatment can be performed by a conventional method.

Refining can be performed in a temperature range of 40-98 ° C. In particular, in the case of mixing with stretch fibers, scouring while relaxing is more preferable because the elasticity is improved.

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

Dyeing can be carried out without using a carrier at a temperature of 70 to 150 ° C, preferably 90 to 120 ° C, particularly preferably 90 to 100 ° C. 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 dispersant composed of a surfactant. When using a cationic dye, it is not possible to add an alkali metal or alkaline earth metal salt such as sodium sulfate, sodium nitrate, potassium sulfate, and calcium sulfate to the dye bath in order to improve the sharpness of the dyed product. Particularly preferred.

After dyeing, soaping or reduction washing can be performed by a known method. In particular, in the case of mixing with stretch fibers, when dyeing a mixed fabric consisting of dyeable fibers with normal pressure dispersible dye and polyurethane elastic fiber, perform reducible fiber washing to firmly remove the disperse dye that has contaminated the polyurethane elastic fiber. This is important in improving the fastness of the fabric. These methods may be known methods. For example, the treatment can be performed in an aqueous alkali solution such as sodium carbonate or sodium hydroxide using a reducing agent such as sodium hydrosulfite.

The following is a cationic dye at normal pressure, one of the disperse dye,
Alternatively, it is an example of a special use mode of the polytrimethylene terephthalate-based fiber of the present invention which can be dyed in a deep color with both dyes.

(1) The polytrimethylene terephthalate fiber of the present invention impairs the performance of the fiber having low heat resistance when mixed with a fiber having low heat resistance, such as a stretch fiber represented by polyurethane elastic fiber, wool, silk, or acetate. Can be dyed dark under normal pressure. In particular, when a polytrimethylene terephthalate fiber is mixed with a polyurethane elastic fiber, a new sensation of clothing can be created that exhibits softness and touch different from those of a mixed fabric using a nylon fiber and also has easy care characteristics.

(2) Since a mixed fabric of ordinary polytrimethylene terephthalate fiber and polyurethane elastic fiber needs to be dyed at 110 to 120 ° C., the polyurethane elastic fiber is thermally degraded. In addition, they can only be dyed with disperse dyes. In dyeing a mixed fabric with a polyurethane elastic fiber by a disperse dye, the disperse dye is more exhausted by the polyurethane elastic fiber than by the polytrimethylene terephthalate fiber, and does not firmly adhere to the polyurethane elastic yarn fiber. For example, the fiber-dispersed dye is easily dyed by dry cleaning and washing, and contaminates the surrounding clothing. In some cases, the dye is released, fading the color of the mixed fabric, and lowering the color fastness. On the other hand, the above-mentioned problem can be solved by using the polytrimethylene terephthalate fiber of the present invention, which can be dyed in a deep color with respect to either the cationic dye or the disperse dye or both dyes at normal pressure.

That is, the first method is to use the normal pressure cationic dyeable polytrimethylene terephthalate fiber of the present invention.

Polyurethane elastic fibers are not dyed with cationic dyes. Therefore, if polytrimethylene terephthalate-based fibers that can be dyed under normal pressure are used as the cationic dye, only the polytrimethylene terephthalate-based fibers are selectively dyed, so that the above-mentioned contamination problem does not occur.

The second method is the use of the normal pressure disperse dyeable polytrimethylene terephthalate fiber of the present invention. When the polytrimethylene terephthalate fiber is modified to have normal pressure disperse dye dyeability, transfer of the disperse dye to the polyurethane elastic fiber can be considerably suppressed.

(3) One of the fields of mixed use with stretch fibers typified 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 cationic dye-dyeable or normal pressure disperse dye-dyeable polytrimethylene terephthalate fiber of the present invention uses the normal pressure dyeing kettle used for nylon fiber knitting pantyhose without new capital investment. It has the advantages of facilities such as being able to. Such an advantage in equipment is a very important effect industrially.

(4) The fabric obtained by using the polytrimethylene terephthalate-based fiber of the present invention is much softer than, for example, a mixed fabric of a known nylon fiber and a polyurethane elastic fiber, and does not have a waxy feeling peculiar to nylon fiber. In addition, it can be a clothing of a new sensation such as having a light stretch property and excellent coloring properties. Furthermore, the polytrimethylene terephthalate fiber has a high heat setting property and an excellent yellowing resistance. These properties indicate that there are no problems inherent in nylon fibers, and that the garment 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 polytrimethylene terephthalate fiber of the present invention, it is possible to perform one-step one-bath dyeing using a cationic 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 resulting fabric is rich in softness and exhibits excellent stretch characteristics and coloring properties.
If there is no problem with dyeing at 100 ° C or higher, 100 ° C
Dyeing is also possible with the above.

Further, as a characteristic of the polyester fiber of the present invention, although it is a cationic dye-dyeable fiber, the amount and speed of alkali reduction can be industrially controlled. The polyester fiber of the present invention in which the alkali weight is reduced becomes softer, and a micropore of about several μm exists on the fiber surface,
Therefore, it has a dry feeling and can be dyed sharply. Further, the normal pressure disperse dye dyeable polyester fiber of the present invention also has an alkali weight loss property close to this.

As described above, the polytrimethylene terephthalate-based fiber of the present invention, in accordance with the above-described usage mode, outerwear, underwear, lining,
It can be used not only for clothing such as sports, but also for materials such as raw yarn for carpet, interlining, and flocky.

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 description of 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 This intrinsic viscosity [η] was measured using an Ostwald viscosity tube,
It was measured at 35 ° C using o-chlorophenol.

(2) Measurement of loss tangent Loss tangent (tan δ) and dynamic elastic modulus at each temperature were measured in dry air at a measurement frequency of 110 Hz and a heating rate of 5 ° C./min using a Leo vibron manufactured by Orientec. . From the results, a loss tangent-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-1013.

(4) Measurement of melting point Using a DSC manufactured by Seiko Denshi Co., Ltd., at a heating rate of 20 ° C./min.
The measurement was performed under a nitrogen stream of 00 ml / min. Here, the peak value of the melting peak was defined as the melting point.

(5) Measurement of elastic recovery The fiber was attached to a tensile tester with a distance between chucks of 20 cm, stretched at a stretching speed of 20 cm / min to an elongation of 20%, and left for 1 minute. After that, it is contracted again at the same speed and stress-
Draw a distortion curve. The elongation when the stress becomes zero during the shrinkage is defined as the residual elongation (X). The elastic recovery was determined according to the following equation.

(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) Dyeing property evaluation test Evaluation of dyeing property of polyester fiber by cationic dye A sample was prepared using a single-knit knitted fabric of polyester fiber (circular knit, sheeting, gauge 28) and score roll 400 (manufactured by Kao Corporation, nonionic surfactant) ) At 2 g / liter (bath ratio 1:50)
Was scoured at 70 ° C. for 20 minutes, and dried with a tumbler drier. Then, using a pin tenter, 180
A heat-set at 30 ° C. for 30 seconds was used. The dye is
Using Kayacryl Blue GSL-ED (cationic dye manufactured by Nippon Kayaku Co., Ltd.), staining was carried out at 4% owf, bath ratio 1:50, 95 ° C. 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.

Evaluation of dyeability of polyester fiber with disperse dye The sample is made of one-piece knitted fabric of polyester fiber (circular knitting, sheeting, gauge 28), and using hot water (bath ratio 1:50) containing score roll 400 at 2 g / l. , Scouring at 70 ° C for 20 minutes,
It was dried in a tumbler dryer. Next, a heat set at 180 ° C. for 30 seconds using a pin tenter was used. The dye used was Kayalon Polyester Blue 3RSF (Disperse Dye, manufactured by Nippon Kayaku Co., Ltd.) at 6% owf.
Stained at 60 ° C for 60 minutes. Nikka Sun Salt 70 as dispersant
Using 0.5 g / liter of 00 (manufactured by Nikka Chemical Co., Ltd., anionic surfactant), the pH was adjusted to 5 by adding 0.25 ml / liter of acetic acid and 1 g / liter of sodium acetate.

The exhaustion rate was determined by measuring the absorbance A of the stock dye solution and the absorbance a of the dye solution after dyeing using a spectrophotometer, and substituting into the following formula. The absorbance used was a value at 580 nm, which is the maximum absorption wavelength of the dye.

Exhaustion rate = (A−a) / A × 100 (%) The deep chromaticity, which indicates how deeply the color was dyed, was evaluated using K / S. This value is obtained by measuring the spectral reflectance R of the sampled cloth after dyeing, and obtaining the following Kubelk-Munch.
a-Munk). The larger the value, the greater the deep color effect, that is, the better the color development. As R, the value at the maximum absorption wavelength of the dye was used.

K / S = (1-R) ² / 2R The lightness when dyed in black was evaluated using the L value.

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

The dry cleaning fastness is JIS-L-0860, the light fastness is JIS-L-0842, and the washing fastness is JIS-L-0844.
The dry / wet friction fastness was measured in accordance with JIS-L-0849. In addition, the dry cleaning fastness tested the liquid contamination.

(9) Measurement of U% The measurement was performed using USTER TESTER3 manufactured by Zellbeger Worcester.

[Example 1] Trimethylene glycol (hereinafter abbreviated as "TMG") 1
144 parts by weight, 1300 parts by weight of dimethyl terephthalate (hereinafter abbreviated as "DMT"), 57 parts by weight of tetrabutylphosphonium 5-sulfoisophthalate (hereinafter abbreviated as "SIPP") (based on the total moles of all acid components) Transesterification reaction was performed at 220 ° C. using 0.43 parts by weight of lithium acetate as an ether formation inhibitor, 0.13 parts by weight of cobalt acetate as a coloring inhibitor, and 1.3 parts by weight of titanium tetrabutoxide as a transesterification catalyst. . Next, 1.3 parts by weight of titanium tetrabutoxide as a polycondensation catalyst and 0.065 parts by weight of trimethyl phosphite as a heat stabilizer were added, and polycondensation was performed 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, a spinning temperature of 265 was used using a spinner having 36 round cross-section holes (diameter 0.23 mm).
The fiber was spun at 1200 ° C. and a spinning speed of 1200 m / min to prepare an undrawn yarn. Next, the obtained undrawn yarn is hot rolled at 50 ° C., a hot plate at 140 ° C., a draw ratio of 3.0 times, and a drawing speed of 600 m / min.
To obtain a drawn yarn of 50d / 36f. The physical properties of the fiber are: melting point 231 ° C, density 1.32 g / cm ³ , strength 3.4 g / d, elongation 37
%, Tmax110 ℃, U% 1.2%, elasticity 22g / d, elastic recovery 8
7%. In addition, the Q / R value of the drawn yarn was 0.25, which satisfied Expression (1). The b value of the fiber is 6.
Was one.

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

The dry cleaning fastness of the one-necked knitted fabric after dyeing did not show any fading of the dyed product, and the liquid contamination was grade 4-5.
Light fastness (4-5 class), dry / wet friction fastness (5
Grade) and washing fastness (grade 5).

[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 Examples satisfied the formula (1) and exhibited good dyeing properties, fastness, and various 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 drawn in the same manner as in Example 1 to obtain a fiber. The obtained fiber had a melting point of 236 ° C., a Tmax of 111 ° C., a strength of 3.6 g / d, an elongation of 35%, an elastic modulus of 23 g / d, and an elastic recovery of 88%. The Q / R value of this fiber was 0.26, which satisfied the expression (1).

However, the polyester fiber obtained in this comparative example had an exhaustion rate of the cationic dye at 95 ° C. and 30 minutes of 6%, and 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 exhaustion rate of the cationic dye at 95% of the fiber for 30 minutes is
It could not be dyed as deep as 30%.

Comparative Example 3 In the same manner as in Example 1, the copolymerization ratio of SIPP was 6 mol%.
Was prepared through polymerization and spinning. Table 1 summarizes the test and evaluation results. During spinning of this polymer, yarn breakage frequently occurred and spinning properties were poor. When the fiber was dyed at 95 ° C., the yarn shrank and became hard, and a fabric having a good texture could not be obtained. 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 set to 3.3 times. The orientation of the obtained fiber was too advanced, and Tmax exceeded 115 ° C. The exhaustion rate of the cationic dye was 45%. In addition, fluff was frequently generated in the obtained fiber.

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

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 fluff. However, the obtained fiber has a low elastic recovery rate of 55%, a Q / R value of 0.49, and the formula (1)
Was not satisfactory.

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 set to 200 ° C. The fibers broke at the hot plate 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 were obtained without problems such as yarn breakage and fluff.
However, the obtained fiber had a low elastic recovery rate of 48%, and the Q / R
The value was 0.52, so that Expression (1) could not be satisfied.

[Comparative Example 9] Spinning was performed using polyethylene terephthalate fiber obtained by copolymerizing 2.5% by mole of 5-sodium sulfoisophthalic acid. The obtained fiber showed a strength of 4.2 g / d, an elongation of 30%, an elastic modulus of 100 g / d, an elastic recovery of 31%, a Q / R value of 3.2, and a Tmax of 131 ° C. The exhaustion rate was 36%.

[Reference Example 1] Without using cobalt acetate and trimethyl phosphite,
Example 1 was repeated. 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 extruded through a single-arrayed nozzle having a diameter of 0.23 mm and having 36 holes. After passing the extruded molten multifilament through a heat retaining area with a length of 5 cm and a temperature of 100 ° C., it is rapidly cooled by applying a wind of 0.4 m / min.
Changed to a solid multifilament. Next, the solid multifilament was heated at 60 ° C. and passed between a first roll having a rotation speed of 2100 m / min and a second roll having a rotation speed of 4300 m / min heated to 133 ° C., and subjected to hot stretching and heat setting.
Winded at 80m / min. The obtained fiber is made into twin yarn and 75d / 72f
And

The obtained fiber had a strength of 3.1 g / d, an elongation of 41%, and a U% of 0.7.
%, Elastic modulus 22g / d, elastic recovery 89%, Q / R0.25, Tmax109
98% at 98 ° C, 95 ° C, 30 minutes
It showed a b value of 6.5.

[Example 9] Polyester fiber of Example 1 and 210 denier Leica (polyurethane stretch fiber manufactured by Asahi Kasei Kogyo Co., Ltd.)
Was used to knit warp knitted fabric. The knitting gauge was 28 G, the loop length was 1080 mm / 480 course for polyester fiber, 112 mm / 480 course for stretch fiber, and the driving density was 90 course / inch. Also, the mixing ratio of polyester fiber is
It was set to 75.5%.

The obtained greige was relaxed and scoured at 90 ° C for 2 minutes.
A dry heat setting was performed at 1 ° C for 1 minute. Kayaacryl Black BS
Using 1 g / liter of Dispers TL (manufactured by Meisei Chemical Co., Ltd., nonionic activator) as a dispersant using ED (cationic dye manufactured by Nippon Kayaku Co., Ltd.) and 50 g / liter of sodium sulfate
Liters and sodium carbonate 15 g / l, add pH 11
A dye was added to the aqueous solution adjusted to give a dye solution. Dyeing was performed at 95 ° C. for 1 hour at a dyeing concentration of 8% owf and a bath ratio of 1:50. After the dyeing, soaping was performed at 1 g / liter of Gran-up P (manufactured by Sanyo Chemical Industries, Ltd., nonionic surfactant) at a bath ratio of 1:50 and 80 ° C. for 10 minutes. After dyeing, finishing was performed by a conventional method.
The L value of the obtained dyed product was 11.2, indicating that the dyed product was sufficiently dyed. The dyeing fastness of the dyed product was a washing fastness class 5, a warm rub fastness class 5, and a light fastness class 4 to 5. Further, the dyed knitted fabric was soft, rich in stretchability, and exhibited an excellent texture with tension 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.
And had been sufficiently stained. The dyeing fastness of this dyed product was as follows: washing fastness 5th grade, wet rubbing fastness 5th grade, light fastness 4th grade.
To 5th grade. The dyed product was soft, rich in stretchability, and had an excellent texture with tension and waist.

Comparative Example 10 The same knit as in Example 9 was knitted using the polytrimethylene terephthalate fiber prepared in Comparative Example 1.

The obtained greige was relaxed and scoured at 90 ° C for 2 minutes.
A dry heat setting was performed at 1 ° C for 1 minute. In order to dye a deep color, 8% owf of Dianix Black BG-FS (Dyestar Japan Co., Ltd.) was used.
Was adjusted to 6 and dyeing was performed at 95 ° C. for 60 minutes at a bath ratio of 1:30. The wet dyeing fastness of the obtained dyed product was second grade, and release of the disperse dye contaminating the stretch fibers was observed.

The same operation as in Example 9 was repeated using the fiber prepared in Comparative Example 9. The resulting fabric is clearly hard,
It was dyed only in a light color with an L value of 21.

For comparison, nylon 6 spun by a conventional method was used.
A warp knitted fabric of fibers and Loica was prepared in the same manner as in Example 9, and dyed with Kayaron Black BGL (acid dye manufactured by Nippon Kayaku Co., Ltd.) at 7% owf at 100 ° C. for 60 minutes. The light fastness of the obtained dyed fabric was 2 to 3.

Example 11 Using a 75d / 36f polyester fiber obtained in the same manner as in Example 1 as a warp and a 75d / 44f copper ammonia rayon as a weft, a plain fabric (140 warp / 25.4mm, weft 80 / 25.4 mm). This plain fabric was scoured by a conventional method. After washing with water, 18
After presetting at 0 ° C. for 30 seconds, one-step single-bath dyeing with a cationic dye and a reactive dye was performed without using a carrier. Examples of the cationic dye include Kayacryl Black BS-ED (a cationic dye manufactured by Nippon Kayaku Co., Ltd.) and Dorimaren Blue X-SG
N (manufactured by Sando Co., Ltd., reactive dye) was used. The dispersant used was 1 g / liter of Disper TL (manufactured by Meisei Chemical Co., Ltd.), 50 g / liter of sodium sulfate and 15 g / liter of sodium carbonate.
One liter was added, and a 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% owf and a bath ratio of 1:50. After dyeing, soaping was performed at 80 ° C. for 10 minutes at 1 g / liter of Gran Up 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 and was a clear dyed product. K / S was 24.3. In addition, despite the absence of alkali weight reduction treatment performed with ordinary polyester fibers, the fabric was full of soft texture and dry feeling, and was an excellent texture that could not be obtained with conventional woven fabrics. The dry cleaning fastness was grade 5, the wet rub fastness was grade 5, and the light fastness was grade 4.

Using a 75d / 36f 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 stretchability of about 7% in the weft direction.

[Example 12] Prepared from the fiber obtained in Example 1, a polyethylene terephthalate fiber polymerized and spun in the same manner as in Example 1, and a polyethylene terephthalate fiber obtained by copolymerizing 3 mol% of sodium 5-sodium isophthalate. An alkali weight loss test was performed using the prepared single-mouth knitted fabric (circular knit, sheeting, gauge 28). After knitting, score roll 40
Using warm water containing 0 at 2 g / liter, scouring treatment was performed at 70 ° C. for 20 minutes, and dried with a tumbler dryer.Then, using a pin tenter, a heat set at 180 ° C. for 30 seconds was used. . The alkali weight reduction processing was performed 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 alkali weight loss by the weight of the original knitted fabric.

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

[Comparative Example 11] Alkali weight loss was performed in the same manner as in Example 12 using a one-neck knitted fabric obtained by knitting polyethylene terephthalate fiber obtained by copolymerizing 3 mol% of sodium 5-sodium sulfoisophthalate in the same manner as in Example 12. The knitted fabric was completely decomposed, dissolved and disappeared. Therefore, in the case of polyethylene terephthalate fiber obtained by copolymerizing sodium 5-sodium sulfoisophthalate at 3 mol%, it is practically impossible to perform alkali weight reduction processing because the weight reduction rate is too high.

Example 13 Using the same method as in Example 1, 2 mol% of dimethyl 5-sodium isophthalate and 5 mol of dimethyl adipate were used.
Weight percent copolymerized fibers were made. The physical properties of the fiber were a melting point of 220 ° C., a strength of 3.6 g / d, an elongation of 34%, an elastic modulus of 22 g / d, and an elastic recovery of 90%, and the Q / R value was 0.24.

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 was 95%, both of the cationic dye and the disperse dye. Showed high dyeability under normal pressure.

The fastness to dry cleaning of the one-piece knitting value after dyeing did not show any fading of the dyed material, and the cationic dye and the disperse dye both had a liquid contamination of 4 to 5 grades. 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.

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 20d / 2f filament obtained in the same manner as in Example 2 was used as a core, and a short yarn was arranged in a sheath to obtain a composite yarn having a filament mixing ratio of 11% by weight. The composite yarn was woven into a warp (146 yarn / 25.4 mm) weft (77 yarn / 25.4 mm) weft and dyed at 95 ° C. according to the method of Example 9.

The K / S of the dyed fabric was 25.3 and it was dyed dark. The obtained fabric was excellent in tension, waist, and resilience.

Example 15 The polymer obtained in Example 2 was subjected to solid-phase polymerization in nitrogen at 200 ° C. for 24 hours to obtain a polymer having an intrinsic viscosity of 1.0. When spinning was performed in the same manner as in Example 1, the strength was 4.0 g / d and the elongation was 32.
%, U% 1.0%, elastic modulus 23g / d, elastic recovery 91%, Q / R value
A fiber having physical properties of 0.25, Tmax of 110 ° C. and b value of 4.3 was obtained.

Example 16 Transesterification was performed at 220 ° C. using TMG1031 parts by weight, 1,4-butanediol (hereinafter abbreviated as “4G”) 106 parts by weight, DMT 1300 parts by weight, and titanium tetrabutoxide 1.3 parts by weight. Thereafter, 0.01% by weight of trimethyl phosphate was added, and polycondensation was performed at 250 ° C. at a reduced pressure of 0.5 torr to obtain a polymer. The intrinsic viscosity of the obtained polymer was 0.8.
The 4G component in the polymer measured by NMR was 4.1% by weight.

After drying the obtained polymer chip, a spinning temperature of 265 was used using a spinner having 36 round cross-section holes (diameter 0.23 mm).
The fiber was spun at 1200 ° C. and a spinning speed of 1200 m / min to prepare an undrawn yarn. Next, the obtained undrawn yarn is hot rolled at 60 ° C., a hot plate at 140 ° C., a draw ratio of 2.9 times, and a drawing speed of 600 m / min.
To obtain a drawn yarn of 50d / 36f. The physical properties of the fiber are as follows: melting point: 224 ° C, Tmax: 98 ° C, strength: 3.6 g / d, elongation: 40%, U
%, Elastic modulus 23 g / d, elastic recovery 83%, and b value 4.5. The Q / R value of this fiber was 0.28, thus satisfying the expression (1).

Further, the exhaustion rate of the polyester fiber of this example by the disperse dye at 95 ° C. for 60 minutes was 78%, indicating a high exhaustion rate.

No color fading was observed in the dry-cleaning fastness of the one-piece knitted fabric after dyeing, and the liquid stain was 3.5 grade, light fastness (5 to 4 grade), dry / wet rub fastness (5 grade), washing fastness The degree (grade 5) was also good.

Examples 17 to 21 Polymerization and spinning were carried out in the same manner as in Example 16, except that the kind 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 12 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 with the disperse dye in the above (7) Dyeability evaluation test was evaluated. However, the polyester fiber obtained in this comparative example has a Tmax
Was above 102 ° C. The exhaustion rate of this fiber by a disperse dye at 95 ° C. for 60 minutes was 36%, and it could not be dyed in a dark color. However, the liquor concentration is 0.5% o
When performed with wf, the exhaustion rate improved to 81%. Accordingly, the results show that the polytrimethylene terephthalate fiber exhibits normal pressure dyeability at a low dye concentration with respect to the disperse dye, but does not exhibit normal pressure dyeability at a high dye concentration.

Comparative Example 13 Polymerization and spinning were carried out in the same manner as in Example 16, except that the ratio of TMG to 4G was changed. Table 2 shows the results. The proportion of the 4G component was less than 1.5% by weight and the fiber had a Tmax of 106 ° C. The exhaustion rate by the disperse dye at 95 ° C. for 6 minutes was low, and it was not possible to dye in a deep color.

Comparative Example 14 Polymerization and spinning were carried out 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 fastness to dry cleaning was very low at class 1.

Comparative Example 15 Polymerization and spinning were carried out in the same manner as in Example 16, except that hexamethylene glycol (hereinafter abbreviated as 6G) was used instead of 4G and the ratio of TMG to 6G was changed. Table 2 shows the test and evaluation results of the obtained fibers. The ratio of the 6G component of the polymer is
It was 8.7% by weight. However, the Tmax of this fiber is 85 ° C or less, and the exhaustion rate is 70% when dyed at 95 ° C for 60 minutes.
, But the fastness to dry cleaning was very poor at class 1. Further, the melting point of the fiber was as low as 210 ° C., and when performing processing such as false twisting, the yarn was fused to the heater and processing could not be performed.

[Comparative Example 16] Instead of 4G, cyclohexanedimethanol (hereinafter referred to as C6-
2G) and the ratio between TMG and C6-2G was changed.
Polymerization and spinning were carried out in the same manner as in Example 16. Table 2 shows the results. The ratio of the C6-2G component was 12.6% by weight. However, the elastic modulus of this yarn is 24g / d, and the elastic recovery is 34%
The Q / R value was 0.71 and could not satisfy the expression (1). The fabric obtained from this yarn was poor in elastic recovery. The Tmax of the fiber is 62 ° C, 95 ° C, 60 ° C.
When dyed in minutes, the fabric shrank and became hard.

[Comparative Example 17] Polymerization and spinning were performed 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. Table 2 shows the results. The obtained polymer was colored yellow, and the resulting fiber was also colored yellow with a b value of 18.3, and could not be used for applications such as inners requiring whiteness.

Example 22 A warp knitted fabric was prepared using the polyester fiber of Example 16 and 210 denier Leica (a polyurethane-based stretch fiber manufactured by Asahi Kasei Corporation). The knitting gauge of this knitted fabric is 28G,
The loop length is 1080 mm / 480 course for polyester fiber and 112 mm / 480 course for stretch fiber, and the driving density is 90
Course / inch. 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.
A dry heat setting was performed at 1 ° C for 1 minute. Dianix Black BG-FS (Disperse dye manufactured by Dystar Japan) 8% ow
f, Nikkasan Salt 1200 as a dyeing aid was adjusted to pH 6 with acetic acid in the presence of 0.5 g / liter, and the bath ratio was adjusted to 95 at a bath ratio of 1:30.
Staining was performed at 60 ° C. for 60 minutes.

The black lightness L value of the obtained dyed product was 11.7, and the color was sufficiently developed. The dyed product had a washing fastness of 5th grade, a wet rub fastness of 4th grade, and a light fastness of 4th grade, and had a soft, stretchy, tight and firm texture.

[Comparative Example 18] For comparison, a warp-knitted fabric of nylon 6 fiber and Loica spun by a conventional method was prepared in the same manner as in Example 22, and Kayaron Black BGL (manufactured by Nippon Kayaku Co., Ltd., (Acid dye) at 95 ° C. for 60 minutes at 7% owf. The L value of the obtained dyed product was 12.3. The light fastness of this fabric was 2 to 3.

Example 23 A 75d / 36f polyester fiber obtained in the same manner as in Example 16 was used as a warp and a weft as a 75d / 44f copper ammonia rayon to give a plain woven fabric (woven density: 140 yarns / 25.4mm, weft: 80 Book / 25.4m
m) created. This plain fabric was scoured and mercerized by a conventional method. Mercerization was performed by immersing in a 75% aqueous sodium hydroxide solution at room temperature. Neutralization, water washing, 180 ℃, 30
After presetting for 2 seconds, one-step single-bath dyeing with a disperse dye and a reactive dye was performed without using a carrier. As disperse dyes, Kayaron polyester blue BRSF (manufactured by Nippon Kayaku Co., Ltd., disperse dye) and Dorimaren Blue X-SGN (manufactured by Sando Co., Ltd., reactive dye) were used. As a dispersant, 1 g / liter of Disper TL (manufactured by Meisei Chemical Co., Ltd.) was used, and 50 g / l of sodium sulfate and 15 g / l of sodium carbonate were added. Dye concentration 2% ow
f, dyeing at 95 ° C for 1 hour at a bath ratio of 1:50. After dyeing, Gran Up P (Sanyo Kasei Co., nonionic surfactant) 1g /
1 liter, at a bath ratio of 1:50, soaped 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 and a dry feeling, and had a good texture not seen in conventional woven fabrics. The K / S of the dyed product is 22.7, the fastness to dry cleaning is grade 3 to 4, and the fastness to wet friction is 4.
Grade and light fastness were grade 4.

Using a 75d / 36f 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 did not have a dry feeling, it was extremely soft and the fabric showed stretchability of about 7% in the weft direction.

[Example 24] A twist of 300 T / m was applied to the polyester fiber of Example 16, and after sizing with a roller, the warp was used as the warp, and a plain woven fabric (warp 120 / p) was used as the weft using diacetate (100d / 150f). 25.4mm,
80 weft / 25.4mm).

Kayaron polyester blue 3RSF (manufactured by Nippon Kayaku Co., Ltd.) was used as a disperse dye for polyester fibers, and Kayaron Fast Blue RD200 (manufactured by Nippon Kayaku Co., Ltd.) was used as a disperse dye for diacetate. The dye concentration is 5% owf each,
One-step, one-bath dyeing was performed at 95 ° C. in the presence of a dispersing agent in a weakly acidic condition. After staining, soda ash 1g / liter, non-ionic detergent 0.5
The soaping was performed at 70 ° C. for 20 minutes in a weak alkaline bath of g / liter. The K / S of the obtained dyed product was 22.2, which was excellent. The dyed product has a fastness to dry cleaning of 3 to 4
Grade and light fastness were grade 4, and the texture was soft and excellent in clarity.

(Example 25) DMT1170 parts by weight, dimethyl isophthalate 130 parts by weight, TM
After transesterification at 220 ° C. with G763 parts by weight and 1.3 parts by weight of titanium tetrabutoxide, 0.01 part by weight of trimethyl phosphate was further added, and the pressure was reduced at 260 ° C.
Polycondensation was performed at 0.5 torr 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 was used using a spinner having 36 round cross-section holes (diameter 0.23 mm).
The fiber was spun at 1200 ° C. and a spinning speed of 1200 m / min to prepare an undrawn yarn. Next, the obtained undrawn yarn is hot rolled at 60 ° C., a hot plate at 140 ° C., a draw ratio of 2.9 times, and a drawing speed of 600 m / min.
To obtain a drawn yarn of 50d / 36f. Physical properties of fiber: melting point 219 ° C, Tmax 100 ° C, strength 3.5g / d, elongation 43%, U
% 1.0%, elastic modulus 24 g / d, elastic recovery 82%, and b value 7.6. In addition, the Q / R value of the fiber was 0.29, which satisfied Expression (1). Of the polyester fiber of this embodiment
The exhaustion rate of the disperse dye at 95 ° C. for 60 minutes was 81%, indicating a high exhaustion rate. In the dry-cleaning fastness of the one-necked knitted fabric after dyeing, no fading of the dyed product was observed, and the liquid contamination was tertiary. The dyeing fastness of the dyed product was good in light fastness (grade 4 to 5), fastness to dry / wet friction (grade 5), and fastness to washing (grade 5).

Examples 26 to 31 Polymerization and spinning were carried out in the same manner as in Example 25, except that the type of the dicarboxylic acid derivative was changed. Table 3 shows the evaluation results of the fibers.
Summarized in All of the fibers satisfied the formula (1) and exhibited good dyeing properties, fastness, and various physical properties.

[Comparative Examples 19 and 20] Examples in which the copolymerization ratio of dimethyl isophthalate was changed
25 was repeated. Table 3 shows the test and evaluation results of the obtained fibers.
It writes in. 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, and the dry cleaning fastness was reduced.

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, and it became slightly yellow.

Example 32 A warp knitted fabric was prepared using the polyester fiber of Example 25 and 210 denier Loica (a polyurethane-based stretch fiber manufactured by Asahi Kasei Corporation). Knitting gauge is 28GG, loop length is 1080mm / 480 course for polyester fiber, stretch fiber is
The course was 112 mm / 480 courses, and the driving density was 90 courses / inch. 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.
A dry heat setting was performed at 1 ° C for 1 minute. Dianix Black BG-FS (Disperse dye manufactured by Dystar Japan) 8% ow
f, Nikka Sun Salt 1200 (a dyeing aid manufactured by Nikka Chemical Co., Ltd.), a dyeing aid, is adjusted to pH 6 with acetic acid in the presence of 0.5 g / liter.
The dyeing was performed at 95 ° C. for 60 minutes at a bath ratio of 1:30.

The black lightness L value of the obtained dyed product was 11.3, and the color was sufficiently developed. Washing fastness of the dyed product was grade 5, wet rub fastness was grade 4, and light fastness was grade 4. In addition, the dyed product had a soft and rich stretch feeling, a tight and waisted texture.

(Example 33) DTM1300 parts by weight, TMG1121 parts by weight, titanium tetrabutoxide 1.3 parts by weight, 220 ° C. using cobalt acetate 0.01 parts by weight
After transesterification, 69 parts by weight of polyethylene glycol having an average molecular weight of 1,000 and 0.01 part by weight of phosphoric acid were added, and polycondensation was performed at 260 ° C. at a reduced pressure of 0.5 torr to obtain a polymer. 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, the spinning temperature was 265 ° C. using a spinning hole having 36 round cross-section holes (0.23 mm).
An undrawn yarn was prepared by spinning at a spinning speed of 1200 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 600 m / min to obtain a drawn yarn of 50d / 36f. Fiber properties: melting point 2
32 ° C, Tmax92 ° C, strength 3.1 g / d, elongation 43%, U% 1.1%,
The elastic modulus was 20 g / d, the elastic recovery was 89%, and the b value was 8.2. Further, the Q / R value of the fiber was 0.22, which was able to satisfy the expression (1).

The exhaustion rate of the polyester fiber of this example with a disperse dye at 95 ° C. for 60 minutes was 92%, 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 product, and the liquid contamination was second class. In addition, the light fastness of fibers (grade 3), the fastness to dry and wet friction (5
Grade) and washing fastness (grade 5).

Examples 34 to 39 Polymerization and spinning were carried out 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 21 and 22] The same operation as in Example 33 was repeated, except that the copolymerization ratio of polyethylene glycol was changed. Table 4 shows the results. In Comparative Example 21, the copolymerization ratio was too low and the dyeability was insufficient, and in Comparative Example 22, the copolymerization ratio was too high and the dry cleaning fastness was poor. Also, the whiteness of the fiber was reduced.

Example 40 A warp knitted fabric was prepared using the polyester fiber of Example 33 and 210 denier Loica (a polyurethane-based stretch fiber manufactured by Asahi Kasei Corporation). In this case, the gauge is 28 G, the loop length is 1080 mm / 480 course for polyester fiber, 112 mm / 480 course for stretch fiber, and the driving density is 90 course /
25.4 mm. In addition, the mixing ratio of polyester fiber is 75.5%
Set to.

The obtained greige was relaxed and scoured at 90 ° C for 2 minutes.
A dry heat setting was performed at 1 ° C for 1 minute. The pH was adjusted to 6 with acetic acid in the presence of 8% owf of Dianix Black BG-FS (manufactured by Dystar Japan) and 0.5 g / l of Nikka Sun Salt 1200 as a dyeing aid, and the bath ratio was 1: Staining was performed at 95 ° C. for 60 minutes at 30.

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. The dyed fabric was soft, rich in stretch, and had a firm and stiff texture.

(Example 41) Polytrimethylene terephthalate with an intrinsic viscosity of 0.9 and polybutylene terephthalate with an intrinsic viscosity of 1.0 were mixed at a ratio of 94.8: 5.2, extruded as it was, and 5.2 parts by weight of 1,4-butanediol was obtained in the same manner as in Example 17. % Copolymerized polytrimethylene terephthalate fiber was obtained.

The resulting fiber is almost equivalent to the fiber of Example 17,
Strength 3.6g / d, elongation 43%, U% 0.7%, elastic modulus 23g / d, elastic recovery 81%, b value 4.4, Q / R value 0.28, Tmax 97 ° C, 95 ° C, 60
The exhaustion by the disperse dye in minutes was 84%.

Example 42 The 75d / 36f polyester fiber obtained in Example 1 was subjected to warp,
Plain fabrics were woven (40 warps / 25.4 mm, wefts 80 / 25.4 mm) using 75d / 44f copper ammonia rayon as the weft. This plain fabric was scoured by a conventional method. After washing with water, 180 ° C, after 30 seconds of presetting, with a cationic dye without using a carrier,
One-step one-bath dyeing with a reactive dye was performed. Kayacryl Black BS-ED (cationic dye manufactured by Nippon Kayaku Co., Ltd.) and Dorimaren Blue X-SGN (reactive dye manufactured by Sando Co., Ltd.) were used. Disper TL (Dispersant manufactured by Meisei Chemical Co., Ltd.) was used in an amount of 1 g / liter, 50 g / liter of sodium sulfate and 15 g / liter of sodium carbonate were added, and a dye was added to an aqueous solution whose pH was adjusted to 11 to obtain a dye solution. Dye concentration 2% owf, bath ratio 1:50
At 100 ° C. for 1 hour. After dyeing, Gran Up P (manufactured by Sanyo Chemical Industry Co., Ltd.) 1 g / liter, bath ratio 1:50, 8
It soaped at 0 degreeC for 10 minutes. After dyeing, finishing was performed by a conventional method.

The resulting dyed product is uniformly dyed and has excellent wet rub fastness, dry cleaning fastness, and light fastness.
It was a clear dyed product. In addition, despite the fact that alkali weight reduction 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 could not be obtained with conventional woven fabrics.

The same plain woven fabric was woven and dyed using 75d / 36f 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 showed stretchability of about 7% in the weft direction.

(Comparative Example 23) In Example 42, when dyeing at a temperature of 130 ° C.,
The reactive dye was decomposed and the fabric was darkened.

[Example 43] The 75d / 36f polyester fiber obtained in Example 1 was subjected to warp,
Weaving plain weave used for weft (140 warp / 3.54, 80 warp
/2.54). 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 42 were performed, and finally, final setting was performed at 180 ° C. for 30 seconds.

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

Polytrimethylene terephthalate fiber of the present invention
The dye can be dyed under normal pressure with either the cationic dye or the disperse dye, or with both dyes, to the color density (shades) practically required. In addition, the polytrimethylene terephthalate fiber of the present invention has wash and wear properties similar to general-purpose polyester fibers such as polyethylene terephthalate fibers, dimensional stability, yellowing resistance, dry feel, and alkali weight reduction processability. Is a fiber material having flexibility similar to nylon fibers.

Due to having the above-described performance, the polytrimethylene terephthalate-based fiber of the present invention is dyed at a low heat-resistant fiber material such as a stretch fiber represented by a polyurethane elastic fiber, wool, silk, acetate, or the like, or at normal pressure. It is a fibrous material suitable for the production of fast dyed fabrics mixed with cellulose fibers. In particular, for a fabric product obtained by mixing with the low heat-resistant fiber, a fast dyeing fabric can be manufactured using a simple dyeing method in a general-purpose normal-pressure dyeing facility without impairing the properties of the fiber. It is an industrial utility to be noted.

Continuation of the front page (56) References JP-A-5-331710 (JP, A) JP-A-8-325841 (JP, A) JP-A-5-98512 (JP, A) JP-A-8-269820 (JP) , A) JP-A-8-284018 (JP, A) WO 97/5308 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 6/84

Claims (10)

(57) [Claims] 1. A fiber made of a polyester obtained by copolymerizing a third component with polytrimethylene terephthalate, wherein the third component is an ester-forming sulfonate compound having a copolymerization ratio of 0.5 to 5 mol%, and the loss of the fiber is reduced. The tangent peak temperature is 85 to 115 ° C, and the elastic modulus Q (g / d) of the fiber
A polyester fiber, wherein the relationship between the modulus and the elastic recovery rate R (%) satisfies the following formula (1). 0.18 ≦ Q / R ≦ 0.5 Expression (1) 2. The method of claim 1, wherein the ester-forming sulfonate compound is 5
The polyester fiber according to claim 1, wherein the polyester fiber is sodium sulfoisophthalic acid or / and a tetraalkylphosphonium salt of 3,5-dicarboxylic acid benzenesulfonic acid. (Here, the alkyl group indicates an alkyl group having 1 to 10 carbon atoms.) 3. The method according to claim 1, wherein the third component is 1.2 to 2.5 mol% of an ester-forming sulfonate compound.
Polyester fiber as described. 4. The method according to claim 1, wherein the ester-forming sulfonate compound is 5
The polyester fiber according to claim 1, wherein the polyester fiber is sodium sulfoisophthalic acid or / and a tetraalkylphosphonium salt of 3,5-dicarboxylic acid benzenesulfonic acid, and the copolymerization ratio is 1.2 to 2.5 mol%. (Here, the alkyl group indicates an alkyl group having 1 to 10 carbon atoms.) 5. A fiber comprising a polyester obtained by copolymerizing a third component with polytrimethylene terephthalate, wherein the third component or (1) the copolymerization ratio of 1.5 to 12% by weight has 4 carbon atoms.
Aliphatic or alicyclic glycol up to 12; (2) copolymerization ratio of 3 to 9% by weight of aliphatic or alicyclic dicarboxylic acid having 2 to 14 carbon atoms or isophthalic acid; (3) copolymerization ratio At least one selected from 3 to 10% by weight of a polyalkylene delicol, the fiber has a peak loss tangent temperature of 85 to 102 ° C., and an elastic modulus Q (g
/ d) and the elastic recovery ratio R (%) satisfy the following formula (1): 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, and (2) a 2 to 2 carbon atom. 14
(3) a polytrimethylene terephthalate fiber obtained by copolymerizing at least one member selected from aliphatic or alicyclic dicarboxylic acids or isophthalic acid and (3) polyalkylene glycol in an amount of 3 to 7% by weight, The tangent peak temperature is 85 to 115 ° C, and the elastic modulus Q (g / d) of the fiber
A polyester fiber, wherein the relationship between the modulus and the elastic recovery rate R (%) satisfies the following formula (1). 0.18 ≦ Q / R ≦ 0.45 ・ ・ ・ Equation (1) 7. The polyester fiber according to claim 1, wherein the b value is -2 to 10. 8. A fabric characterized in that the polyester fiber according to claim 1 is partially or entirely used. 9. A mixed fabric, wherein the polyester fiber and the stretch fiber according to claim 1 are mixed. 10. A fabric using the polyester fiber of claim 1 or 7 partially or entirely, wherein the fabric is dyed with a cationic dye and / or a disperse dye.