JPH10158931A - Polyester yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester yarn excellent in clarity, deep colorability, wear resistance and productivity, having a handle of dry touch. SOLUTION: This polyester. yarn comprises both side parts of three parts obtained by dividing yarn width into equal three parts, hardly having observable closed pores and composed of a great number of small ridges connected in a stripe state when the whole side of the yarn is looked with a magnification of ×3,000. The polyester has irregular unevenness and 0.001-5.0μm pores different in size and depth in the direction of fiber axis and 0.001-3.0μm size and depth in the direction perpendicular to the fiber axis and 0.01-0.5μm maximum depth when the surface of the yarn is looked with a magnification of ×8,000. The yarn has 50-3,000 primary particles/μm<2> contained in the cross section of the yarn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester fiber having excellent sharpness and deep color, excellent abrasion resistance, a dry touch feeling, and excellent productivity. More specifically, it was dispersed with an extremely excellent degree of dispersion,
Polyester fibers having a specific structure and having a unique morphology on the fiber surface and having a completely new microcrater structure, obtained by reducing the weight of polyester fibers containing salts soluble in aqueous alkaline solutions by alkali. It is.

[0002]

2. Description of the Related Art Polyester fibers are the most widely used synthetic fibers because of their excellent properties, but they also have major disadvantages. In particular, the problem relating to the color development is serious. In recent years, color trends in women's outerwear have demanded sharpness, and black in formal wear and chromatic deepness in women's outerwear are also strongly desired. However, compared to natural fibers such as wool and silk, regenerated fibers such as rayon and acetate, and synthetic fibers such as acrylic fibers, polyester fibers have sharpness (characteristics in which dyed materials show vivid colors) and deep color (dying). Inferiority in the color of objects). This is because the existing polyester polymer has a high refractive index and the surface of the obtained fiber is smooth, so that incident light hardly enters the fiber and is easily reflected on the fiber surface.

[0003] In order to solve the drawback of vivid color depth, many improved techniques have been proposed. Above all, a clear deep-colored yarn having fine irregularities particularly on the fiber surface has been developed. This technology aims to reduce specularly reflected light by repeatedly reflecting light within the irregularities of the fiber surface, and at the same time to increase the amount of light absorbed by the dye, thereby improving sharpness and deep color. Things.

[0004] Further, since the polyester fiber is produced by melt spinning, the surface has a very smooth structure and has a unique waxy feeling (a slimy feel like wax).
The waxy feeling is a property that is not preferred by general consumers, compared to the texture of natural fibers such as the dry feel of silk and the silky feel of cotton and cellulose fibers.
Therefore, there is also a demand to change the waxy feeling of the polyester fiber. As one of the countermeasures, dry touch fibers have been proposed.

[0005] As described above, there have been known some proposals regarding fibers having irregularities for the purpose of improving sharp and deep color.
JP-A-55-107512 discloses that a particle size of 100
Silica sol, titanium oxide, calcium carbonate or the like having a particle size of not more than μm is added during the polymerization process, and the polyester fiber containing the obtained fine particles is alkali-reduced, so that the surface of the fiber becomes 0.1 μm.
A fiber having irregular irregularities of 2 to 0.7 μm and having fine irregularities of 50 to 200 nm inside the pores is disclosed. However, since the fibers have large fine particles, the holes are clearly and independently formed one by one, and furthermore, since there are many holes having a relatively large diameter, the effect of sharp and deep color is small. Further, there is a disadvantage that unevenness covering the surface is peeled off by external force such as friction, and the portion becomes white or fluffed. Further, the added fine particles act as an abrasive, causing a problem that the running yarn cuts the guide.

[0006] On the other hand, similar studies have been made on polyester fibers containing other fine particles. For example, JP-A-57-143523 discloses a polyester fiber containing silica in which a hydroxyl group on the silica surface is blocked with an alkyl group such as a methyl group, and has a maximum width of 0.0.
The fiber surface has pores having a length / maximum width ratio of 5 to 1.5 μm and a ratio of 1.5 or more. JP-A-3-16510 discloses a polyester fiber containing silica, kaolin and polyalkylene glycol. Also in these fibers, since the pores are substantially independent, the degree of sharp and deep color achieved is insufficient, and there is a problem that the fibers are washed out by friction. Furthermore, in these cases,
Since silica produced by the dry method is used, the silica tends to be easily aggregated and the pressure of the spinning pack tends to increase during the spinning process. If spinning is continued in a state where the pack pressure is high, the frequency of fluffing and yarn breakage increases, and there is a disadvantage that productivity is extremely reduced.

Further, an alkali metal or an alkaline earth metal used as a transesterification catalyst is reacted with a phosphate or phosphite such as trimethyl phosphate or trimethyl phosphite in a polyester polymerization system to precipitate phosphorus. A number of methods have been proposed for treating polyester fibers containing fine particles of acid ester metal salts or phosphite metal salts with alkali, for example (Japanese Patent Application Laid-Open No. 56-56).
JP-A-132039, JP-A-57-139118, JP-A-58-13717, JP-A-58-13
719, JP-A-58-104215, etc.).
The surface of the fiber obtained in this way is substantially independent,
There is a hole having a length of 0.1 to 5 μm in the fiber axis direction and a width of 0.1 to 0.3 μm in a direction perpendicular to the fiber axis. However, in the case of this fiber as well, since the pores are present substantially independently of one another, the level of vivid color depth developed is not sufficient. Further, the reaction for forming the metal salt is extremely affected by the temperature, the amount of water, the method of adjusting the reagent and the storage time after adjustment, and the reproducibility of the amount of the generated fine particles and the dispersion state is extremely poor. As a result, it was found that the polymerization reactivity and the vivid color depth changed for each batch. Also, scale tends to occur in the polymerization vessel, and if the number of polymerizations is repeated,
The phenomenon that the stain of the kettle was transferred to the polymer was observed.

Further, in order to solve the problem proposed by the above-mentioned internal precipitation method, a zirconium compound and a phosphorus compound such as trimethyl phosphate are reacted in a polyester reaction system to be precipitated. A method has been proposed in which polyester fibers containing fine particles are subjected to alkali weight reduction treatment (JP-A-61-124).
673, JP-A-61-179367). In this case, zirconium acetate is used as the zirconium compound. However, since zirconium acetate is a very unstable compound, it exists stably only in a state of being dissolved in an acid solvent represented by acetic acid or the like. When zirconium acetate is to be isolated, it is partially decomposed, and it is extremely difficult to carry out stable polymerization. It can be dissolved in a solvent such as acetic acid and added to the polymerization system.However, if an acid solvent enters the polymerization system, the polymerization rate will decrease, or diethylene glycol dimerized ethylene glycol will be copolymerized in the polymer. In addition, problems such as a decrease in heat resistance, coloring and a decrease in melting point occur. In addition, zirconium compounds are generally expensive and are not preferred in terms of production cost.

As described above, the existing fibers having irregularities have problems in the degree of achievement of clear and deep color, polymerization stability, fiber productivity and the like.

[0010]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors have found that a polyester fiber having a unique surface shape, which has not been known, has excellent clarity, It has been found that polyester fibers exhibit deep color, are excellent in abrasion resistance, have a dry touch texture, and are excellent in productivity. Succeeded in finding a polyester fiber that can solve all of the above, and reached the present invention.

[0011]

That is, the first aspect of the present invention is that, when the entire side surface of the fiber is viewed at a magnification of 3000 times, almost no independent holes are observed at both ends where the yarn width is divided into three equal parts. Instead, a large number of small ridges are connected to form a streak, and when the surface of the fiber is viewed at a magnification of 8000 times, the irregularity is 0.001 to 5.0 μm in the fiber axis direction along with the fiber axis, with irregular irregularities. 0.001-3.0 μm in the orthogonal direction, maximum depth 0.0
There are 1 to 0.5 μm pores having different sizes and depths, and the number of primary particles contained in the cross section of the fiber is 50 to 50 μm.
The ^second aspect of the present invention is a polyester fiber characterized in that the number of the primary particles is 3,000 / μm ² , the distance between both ends of the primary particles in the major axis direction is 1 to 100 nm, and the width thereof is 0.001 to 1
3. The polyester fiber according to claim 1, wherein the secondary aggregated particles formed by aggregating the primary particles are 3 nm per fiber cross section of 10 μm ² .
The polyester fiber according to claim 2, wherein the number is from 1,000 to 1,000.

The polyester referred to in the present invention is a polyester in which 85% by mole or more of the total carboxylic acid component is composed of terephthalic acid.
It is a polyester containing at least one kind of alkylene glycol selected from trimethylene glycol and tetramethylene glycol as a main glycol component. Further, a polyester in which the terephthalic acid component is substituted with another dicarboxylic acid component in a range of less than 15 mol% or a polyester in which a part of the glycol component is substituted with a glycol other than the main component may be used.

The dicarboxylic acid component other than the terephthalic acid component and the glycol component other than the main component can be appropriately selected in consideration of the properties of the obtained polymer. For example, in order to impart cationic dye dyeability, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5- (tetrabutylphosphonium) sulfoisophthalic acid, etc.
10 to 10 mol%, preferably 0.5 to 3 mol% can be copolymerized. In order to impart easy dyeability, aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dodecane diacid are copolymerized with 3 to 10 mol%, or polyethylene glycol or a diol having about 3 to 10 carbon atoms is copolymerized. can do. In order to impart high shrinkage, isophthalic acid,
Bis (oxyethyl) bisphenol A, bis (oxyethyl) bisphenol S and the like can be copolymerized in an amount of 5 to 15 mol%. In addition, cyclohexane-1,4-
Dimethanol, 1,4-cyclohexanedicarboxylic acid,
Naphthalenedicarboxylic acid, diphenyldicarboxylic acid, etc.
There is no particular limitation as long as it is a monomer copolymerizable with the polyester.

Further, various additives such as matting agents,
A heat stabilizer, an antifoaming agent, a coloring agent, a flame retardant, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, a fluorescent whitening agent, and the like may be copolymerized or mixed as necessary. . The polymerization method of the polyester used in the present invention is not particularly limited. For example, a direct esterification reaction of terephthalic acid and ethylene glycol or a transesterification reaction of terephthalic acid such as dimethyl terephthalate with an ester of a lower alcohol and ethylene glycol, bis (oxyethyl) terephthalate and its low polymerization It is produced by a first-stage reaction for forming a coalescence and a second-stage reaction in which the first-stage reaction product is heated under reduced pressure to proceed with polycondensation until a desired degree of polymerization is reached.

In the polyester fiber of the present invention, when the entire side surface of the fiber is viewed at a magnification of 3000 times, almost no independent holes are observed at both end portions where the yarn width is divided into three, and many small ridges are formed. It is streaked in a row and the surface of the fiber is 80
When viewed at a magnification of × 00, 0.001 to 5.0 μm in the fiber axis direction along with irregular irregularities, 0.001 to 3.0 μm in the direction perpendicular to the fiber axis, and a maximum depth of 0.01 to 0.1 μm. 5μ
m, pores having different sizes and depths are present, and the number of primary particles contained in the cross section of the fiber is 50 to 3000 / particle.
It is a polyester fiber characterized by μm ² .By achieving this surface structure, it exhibits excellent clarity, deep color, excellent abrasion resistance, and a dry touch texture. . It is unclear why these features are exhibited by the surface structure described above, but the structure with irregular irregularities increases the area exposed to visible light, and the presence of minute holes causes the irregularities to enter the irregularities. It is considered that the visible light is further repeatedly reflected in the pores, and the ratio of the visible light absorbed by the dye is increased to improve the sharpness and deep color. The reason for the durability against friction is estimated as follows. It is considered that the peeling of the fiber surface due to friction is caused by the fact that the end of the hole is sharpened and the frictional material is caught on the end. In the surface structure of the polyester fiber of the present invention, since there are large irregularities, the ends of the holes do not protrude to the surface, and thus it is considered that excellent abrasion resistance is exhibited.

When the entire side surface of the fiber is viewed at a magnification of 3000 times, a large number of small ridges observed at both ends where the yarn width is divided into three equal parts are not visible when the surface of the fiber is viewed at a magnification of 8000 times. This corresponds to a state in which regular irregularities are viewed obliquely, and the ridges are larger than the holes that exist together with the irregularities. The size of the holes is 0.001 to 5.0 μm in the fiber axis direction, and 0.01 to 3.0 μm in the direction orthogonal to the fiber axis. The pore size was measured by observing the surface of the fiber with a scanning electron microscope (× 8).
000), the size of the holes observed on any five 25 μm ² planes in the fiber axis direction and the direction perpendicular to the fiber axis is measured, and the average value is calculated. 0.00 in the fiber axis direction
When it is smaller than 1 μm or larger than 5.0 μm, the effect of vivid color depth is small. Preferably, from the viewpoint of vivid color depth, abrasion resistance and dry touch, 0.1 to 0.1 in the fiber axis direction.
To 3.0 μm, 0.01 to 1.0 in a direction perpendicular to the fiber axis.
0 μm.

The maximum depth of the holes is between 0.01 and 0.5 μm. The maximum depth of the hole is measured by observing the cross section of the fiber with a transmission electron microscope (the magnification is set to a value at which the size of the irregularities on the outer periphery of the fiber can be sufficiently discerned by the naked eye), and observing the outer periphery of the fiber Then, measure the depth of the deepest part. 0.01 μm
If it is shallower, sufficient clear deep color and dry touch texture cannot be achieved, and if it is deeper than 0.5 μm, the abrasion resistance is greatly reduced and fluff is generated. Preferably, clear and deep color, abrasion resistance, good balance of dry touch,
0.01 to 0.2 μm, particularly preferably 0.01 to 0.2 μm
0.1 μm.

The polyester fiber of the present invention comprises fine particles.
Method to elute fine particles by containing alkali in weight loss
It is manufactured using Fine particles are primary particles or primary particles.
It is composed of agglomerated secondary particles. The poly of the present invention
Ester fiber is the long axis direction of primary particles existing inside the fiber.
The distance between the opposite ends is 1 to 100 nm, and the width is 0.001.
１５15 nm, and the number of primary particles is 5 in the cross section of the fiber.
0-3000 pieces / μm ^TwoFine particles soluble in aqueous alkaline solution
Polyester fiber containing fibers in an aqueous alkaline solution.
Is preferably produced by a method of dissolving 2% by weight or more of
You. The size of primary particles in the major axis direction and width direction is one by one
Cross-sectional photograph of fiber enlarged enough to confirm primary particles
(With a transmission electron microscope)^Two
Longitudinal direction and width of individual primary particles observed on the surface
From the average value of Longitudinal distance between primary particles
Exceeds 100 nm or the width of primary particles exceeds 15 nm.
The polyester fiber of the present invention cannot be obtained.
No. From the viewpoint of vivid color depth, the distance between both ends in the long axis direction is
It is preferably 1 to 50 nm, and its width is preferably 0.5
１２12 nm. The number of primary particles is 50 to 30.
00 pieces / μm^TwoAnd 50 pieces / μm^TwoLess than clear deep color
Low effect of 3,000 pcs / μm^TwoIf it exceeds
During spinning, fine particles are clogged in the filter of
Spinning cannot be performed properly. View of vivid deep color and spinning stability
From the viewpoint, preferably 50 to 1000 pieces / μm^TwoIt is.
Further, the preferred form of fine particles is that secondary aggregated particles are present.
And the number of the secondary aggregated particles is 10 μm^TwoHit
3 to 1000 pieces. Particularly preferred is a fiber cross section
10 μm^TwoThe number is 20 to 700 pieces. Where
Secondary agglomerated particles are enlarged so that primary particles can be identified.
The distance between the centers of gravity of adjacent primary particles
At least 4 separations within the length of the major axis of the primary particle
Particle group. The secondary particles are produced by aggregating the primary particles.
But the size of adjacent primary particles
The distance between the centers of gravity is within the length of the long axis of the primary particle
Therefore, the maximum length of the secondary particles is 100 nm, preferably 50 n
m, which is sufficiently fine even if it is secondary particles
It is.

As described above, deep and large pores are formed by reducing the amount of fibers containing secondary particles having a certain size in the presence of alkali. At the same time, since there are fine primary particles, many shallow small holes are created,
By partially connecting the large holes and the small holes, a unique surface structure of the present invention in which the ridge-shaped unevenness and the holes coexist is formed.

The fiber serving as a precursor for producing the fiber having irregularities as described above is not particularly limited. Preferably, the phosphonate represented by the formula (1) is used in an amount of 0.01 to 0.01.
The polyester fiber contains 3% by weight, and 85% by mole or more of the total carboxylic acid component is composed of terephthalic acid. (O = PR (OR ′) (O ⁻ )) _n · M Formula (1) Here, R and R ′ represent a hydrogen atom or a carbon number of 1 to 7.
And M represents an alkali metal or an alkaline earth metal, and n is a natural number corresponding to the valence of the ion of M. The polyester fiber of the present invention is obtained by adding 2% by weight of the polyester fiber in an alkaline aqueous solution.
It can be obtained by eluting the above.

In the structure of these phosphonates,
R and R 'each represent a hydrogen atom or 1 having 1 to 7 carbon atoms.
It shows a valent organic group. Examples of the monovalent organic group having 1 to 7 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-butyl, and n- And a hydrocarbon group such as a pentyl group, an n-hexyl group, an n-heptyl group, a phenyl group, and a benzyl group. Some or all of these hydrogen atoms are halogen atoms, ester groups, ether groups, and carbonyl groups. , A sulfone group or the like. Among these R, a phenyl group and an ethyl group are most preferable in view of the degree of vivid color depth, low toxicity of phosphonic acid, and availability. For the same reason, R ′ is most preferably a hydrogen atom, a methyl group or an ethyl group. M represents an alkali metal or an alkaline earth metal, and specific examples thereof include lithium, sodium, potassium, rubidium, beryllium, magnesium, calcium, and strontium. Of these, calcium, sodium, and magnesium are most preferred from the viewpoints of the degree of vivid deep color, the low coloring property of the obtained polymer, and the thermal stability.

The content of these phosphonate polymers in the polymer must be 0.01 to 3% by weight.
If it is less than 0.01% by weight, it is not possible to form irregularities effective for enhancing sharp and deep color. Also,
If it is larger than 3% by weight, the spinning yield is reduced. The preferred range of the content is 0.1 to 1.5% by weight, more preferably 0.2 to 1.0% by weight.

The method of adding these phosphonates to the polymer is not particularly limited, such as a method of adding the phosphonate in a solid state during the polymerization process or by dissolving it in a solvent, a method of blending with a polyester chip, and the like. Preferably, a first-stage reaction for producing a dicarboxylic acid mainly composed of terephthalic acid or an ester-forming derivative thereof and at least one glycol ester and a low polymer thereof, and a second reaction for polycondensing the reaction product In producing a fiber made of the polyester synthesized by the step reaction, O = PR (OR ′) ₂ and the metal salt are completely dissolved in water or an organic solvent in any step until the synthesis of the polyester is completed. Or a solution containing the phosphonate represented by the formula (1), which is obtained by partially or partially reacting, and then the polymerization of the polyester is completed. In this method, a phosphonate obtained by completely or partially reacting O = PR (OR ′) ₂ with a metal salt in water or an organic solvent during the polymerization is in a solution state or a partial solution. Is added to the polymerization system while being precipitated from the polymer. In this case, the reaction for forming the phosphonate may be substantially completed by the end of the polymerization, or unreacted one may remain. The resulting phosphonate can be used at any stage of the polymerization process.
Alternatively, the particles are precipitated as fine particles in a form in which the polymerization is completed and the polymer is cooled and phase-separates from the polymer layer.

The organic solvent used for reacting O = PR (OR ') ₂ with a metal salt in water or an organic solvent is not particularly limited, but glycol used as a raw material of the target polyester is most preferred. As the reaction temperature,
Although there is no particular limitation, the temperature is usually from room temperature to the boiling point of the solvent, and when heat generation is severe, the reaction may be carried out while cooling. O = P
The molar ratio of R (OR ') ₂ to the metal salt is usually 1: 2 to 2: 1.
It is. If the molar ratio of O = PR (OR ′) ₂ is smaller than this range, the sharpness and color depth will decrease, and at the same time,
The polymer is colored. Conversely, when it is larger, the sharpness and deep colorability are reduced, and at the same time, the activity of the polymerization catalyst is reduced and the polymerization time is prolonged. When the polymerization time becomes longer,
The thermal degradation of the polymer becomes severe, and the productivity also decreases. Preferably it is 1: 1.3 to 1.3: 1. The metal salts used are alkali metal salts and alkaline earth metal salts, formate, acetate, oxalate, benzoate, phthalate, adipate, sebacate, sulfate, nitrate,
Examples include silicates, carbonates, borates, bicarbonates, chlorides, bromides, fluorides, methylates, ethylates, glycolates, phenolates and the like. Particularly preferred are acetate, formate and carbonate. These metal salts may be used alone or in combination of two or more.

When partially reacting, unreacted O =
PR (OR ') ₂ or a metal salt may be present, and unreacted O = PR (OR') ₂ and a metal salt react with each other at the stage of the polymerization reaction to completely form a phosphonate, or It may be partially generated. As described above, the method of producing phosphonate fine particles in the polymerization system is based on the fact that the fine particles are generated by phase separation from the polymer regardless of the phosphonate generation stage, so that the shape, particle diameter, and dispersion state of the fine particles are dispersed. Is uniquely determined according to thermodynamic laws. Therefore, fine particles having the same shape, particle diameter, and dispersion state are produced with good reproducibility. In this case, the generated fine particles are, surprisingly, generally such that primary particles present inside the fiber have a distance of 1 to 2 at both ends in the longitudinal direction.
100 nm, its width is 0.001 to 15 nm, and the number of primary particles is 50 to 3000 particles / μm ^2, which is the most preferable for achieving the object of the present invention.
When O = PR (OR ′) ₂ and a metal salt are added to a polymerization system without reacting in water or an organic solvent, the degree of sharp and deep color achieved varies or the phosphonate salt is aggregated. Or cause a sharp rise in pressure of the spinning pack. From the viewpoints of reproducibility, attainment, and aggregation of vivid deep color, the reaction rate of O = PR (OR ') ₂ and the metal salt added to the polymerization system is preferably 5 to 100%, particularly preferably 20 to 8%.
0%.

The polyester thus obtained is fiberized by a known method. The form may be a solid fiber without a hollow portion or a hollow fiber. Further, the cross-sectional structure may be used for a part of a round or other modified yarn, a sheath core yarn, or a side-by-side. As a spinning method, a normal method of stretching an undrawn yarn at a winding speed of about 1500 m / min by about 2 to 3.5 times, or
Direct-rolling method directly connected to spinning-drawing process, 5000 m / min
A high-speed spinning method with the above winding speed can be applied.

The polyester fiber of the present invention is obtained by subjecting a spun fiber to scouring, heat setting, false twisting, or the like, or forming a fabric, and then eluting 2% by weight or more thereof in an alkaline aqueous solution. . Examples of the alkali compound used in the aqueous alkali solution used herein include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium hypochlorite, and the like. Preferred are sodium hydroxide, potassium hydroxide and sodium carbonate.

The concentration of the aqueous alkali solution is usually 0.01 to 4
0% by weight, preferably 0.1 to 30% by weight. The processing temperature is preferably from room temperature to 100 ° C., and the processing time is from 1 minute to 4 hours. At the time of alkali weight reduction, it is necessary to elute at least 2% by weight in order to form the surface structure shown in the present invention. Weight loss rate is 10
When the content is more than the weight%, the softness of the fiber or the fabric is increased, and the texture is improved. However, if the weight loss rate exceeds 40% by weight, the fibers become too thin and the strength of the fabric decreases.
The preferred range is 5 to 40% by weight, and more preferably 10 to 30% by weight.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention is not limited only to Examples. The main measured values in the examples were measured by the following methods. (1) Evaluation of Sharpness (Scale for Sharpness) A single-mouth knitted fabric of the obtained polyester fiber was scoured at 70 ° C. for 20 minutes using warm water containing 2 g / L of score roll 400. Next, the scoured knitted fabric was added to a 5% by weight aqueous solution of sodium hydroxide, and the weight reduction rate was 20% in a boiling state.
%, Alkali weight loss was performed.

After weight loss, Michelon Polyester Red FL
(Manufactured by Mitsui Toatsu) and Nikka Sun Salt 7000
(Nichika Chemical Co., Ltd.) 0.5 g / L, acetic acid 0.25 mL / L
And 1 g / L of sodium acetate.
Staining was performed at 0 ° C. for 60 minutes. In this case, dyeing was performed by changing the dye concentration at four points of 2, 4, 8, and 16% owf.
After dyeing, reduction washing was performed by a conventional method, and color measurement was performed after drying.

A color computer (SM, manufactured by Suga Test Instruments Co., Ltd.)
Using -4), the color density C ^* and the sharpness B ^* of the four dyeings obtained by changing the dye density were measured. The measurement results were plotted with B ^{* on} the vertical axis and C ^* on the horizontal axis, and graphs were prepared with the scales on the vertical and horizontal axes being 2 to 6 and 9 to 15, respectively. At this time, the lengths of the vertical and horizontal axes were 12 cm and 20 cm, respectively.
The curve obtained by plotting the obtained data of four points is
The shape that is convex to the upper right is shown, and the distance (unit: cm) from this curve (scale on the vertical axis, scale on the horizontal axis) to the point (2, 9) is defined as the sharpness. The sharpness indicates that the larger the number, the higher the sharpness. The sharpness obtained in this way has a very good correlation with the sharpness seen and felt by humans. (2) Evaluation of deep color degree (scale indicating deep color property) A single-port knitted fabric that had been scoured and alkali-reduced in the same manner as (1) was used with Sumikaron Black S-BF (manufactured by Sumitomo Chemical Co., Ltd.).
Dyeing was performed using a dyeing assistant having the same formulation as in (1).
After dyeing, reduction washing was performed by a conventional method, and color measurement was performed after drying. In the present invention, this L value is defined as deep chromaticity.
The deep chromaticity indicates that the smaller the number, the higher the deep chromaticity. The deep chromaticity obtained in this way has a very good correlation with the deep chromaticity seen and felt by humans. (3) Evaluation of abrasion resistance The dyed product obtained in (2) was subjected to a Gakushin-type friction tester, and a plain fabric of polyester fiber having a call number of No. 10 described in JIS-L-0803 was used as a patch cloth. And rubbed 200 times under a load of 700 g. The degree of fading of the dyed material before and after the treatment was evaluated on a 1 to 5 grade (the higher the grade, the better). (4) Evaluation of dry touch Five fixed persons touched the dyed product of (2), and evaluated the dry touch in the 1st to 5th grades (the higher the grade, the better).

[0032]

Example 1 1294 parts of dimethyl terephthalate, 777 parts of ethylene glycol, and 1.04 part of calcium acetate monohydrate as a transesterification catalyst were gradually heated from 150 ° C. to 240 ° C., and required 3 hours. While distilling off methanol, a transesterification reaction was performed. Then, 6.32 parts of dimethyl phenylphosphonate and 2.30 parts of calcium acetate monohydrate were previously added to 90 parts of ethylene glycol,
A solution obtained by reacting at 120 ° C. for 4 hours (hereinafter, a solution obtained by reacting a phosphonic acid derivative with a metal salt with ethylene glycol is referred to as “solution A”) was added, and 0.64 g of antimony trioxide was further used as a polycondensation catalyst. Parts were added. After stirring for 30 minutes, the pressure is gradually reduced and finally 0.1 Torr
at 290 ° C for 2 hours and 40 minutes, and ηsp / c
= 0.73 modified polyester in chip form. A
When the liquid was analyzed using gas chromatography and NMR, dimethyl phenylphosphonate was charged,
78% calcium salt of monomethyl phenylphosphonate
Turned out to be included. The obtained polymer chip was dried at 160 ° C. under a nitrogen flow of 100 L / min for 20 hours, and then spun at a spinning temperature of 290 ° C. and a spinning speed of 1500 m / min using a spinner having 24 round cross-section holes. A drawn yarn was prepared. Next, the obtained unstretched yarn was twisted at a hot roll of 80 ° C., a hot plate of 160 ° C., a draw ratio of 3.2 times and a draw speed of 800 m / min.
A drawn yarn of 0d / 24f was obtained. The strength was 4.5 g / d and the elongation was 38%. According to NMR analysis of this fiber, the calcium salt of monomethyl phenylphosphonate was 0.5%
% By weight.

The sharpness and deep color of the obtained dyed product are 1
9.3 and 17.3, showing extremely excellent clear and deep color. There was almost no change in the vivid color depth even when the number of batches was increased. Further, both the rub resistance and the dry touch were grade 5. The surface of the dyed yarn and the cross section cut into a circle were observed using a scanning electron microscope and a transmission electron microscope. When the entire side surface of the fiber was viewed at a magnification of 3000 times, hardly any independent holes were observed at both end portions where the yarn width was divided into three, and many small ridges continued to form a streak. 8
When observed at 000 times, the surface of the fiber has a thickness of 0.01 to 3 μm in the fiber axis direction and 0.01 to
A continuous hole in which holes having a size of 0.4 μm and a maximum depth of 0.05 to 0.4 μm and having different sizes and depths were connected to each other without being substantially independent was observed. These holes covered almost the entire surface of the fiber. In addition, when the cross-sectional photograph was enlarged, it was confirmed that the acicular primary particles were finely dispersed. The primary particles had a length of 1 to 40 nm in the major axis direction and a width of 4.5 nm. The number of secondary aggregated particles was 123 per fiber cross section 10 (μm) ² . These are summarized in Table 1.

[0034]

Comparative Example 1 The same measurement as in Example 1 was performed using polyethylene terephthalate fiber containing no calcium salt of monomethyl phenylphosphonate. The resulting dyed product had sharpness and deep chromaticity of 17.2 and 19.7, and was poor in clear and deep color. When the entire side surface of the fiber was viewed at a magnification of 3000 times, independent holes were sparsely observed at both ends where the yarn width was divided into three equal parts, but no ridge as in Example 1 was seen. When observed at 8000 times, the surface of the fiber has a thickness of 0.2 to 2.5 μm in the fiber axis direction, 0.1 to 0.6 μm in a direction orthogonal to the fiber axis, and a maximum depth of 0.0.
3 holes / μm with different size and depth of 6 μm or less
m ² or less. The abrasion resistance was grade 5, but the dry touch was grade 1.

[0035]

Comparative Example 2 Instead of dimethyl phenylphosphonate,
A polymer was obtained in the same manner as in Example 1 using trimethyl phosphate. A polyester fiber was obtained from this polymer by the same production method as in Example 1. When measured in the same manner as in Example 1, the resulting dyed product had sharpness and deep chromaticity of 19.0 and 17.6, respectively. The abrasion resistance was grade 3 and the dry touch was grade 4. When the same experiment was repeated, there was reproducibility of the abrasion resistance, but the sharpness and the deep chromaticity were 19.3 to 18.5 and 17.3 to 17.
8, it was found that it varied in a certain range. In some cases, polymerization did not occur. The reason is presumed as follows. Trimethyl phosphate has a boiling point of 197 ° C.
It is. Usually, the temperature after completion of the transesterification reaction is 20
It is considered that because the temperature exceeds 0 ° C., unreacted trimethyl phosphate partially evaporates, and the degree of evaporation changes from batch to batch, so that the obtained dyed product changes in clear and deep color. Sharpness and deep color are 19.
In the case of 0, 17.6, when the amount of phosphorus contained in the fiber was examined by fluorescent X-ray, it was only 55% of the theoretical amount. This result supports the evaporation of trimethyl phosphate. Incidentally, the amount of phosphorus in the polymer of Example 1 was as expected. This is because evaporation does not occur because the boiling point of dimethyl phenylphosphonate is as high as 270 ° C.

When the entire side surface of the fiber was viewed at a magnification of 3000 times, independent holes were observed at both ends where the yarn width was divided into three equal parts, and many small ridges continued to form a streak. When observed at 8000 times, 0.3 to 0.3
6.0 μm, 0.1-0.5 μ in the direction perpendicular to the fiber axis
m, holes having a maximum depth of 0.08 to 0.5 μm and holes having different sizes and depths existed substantially independently. These holes covered about 50% of the entire surface of the fiber. In addition, when the cross-sectional photograph was enlarged, it was confirmed that the acicular primary particles were finely dispersed. The primary particles had a length of 5 to 120 nm in the major axis direction and a width of about 0.01 to 10 nm. Almost no secondary aggregated particles were observed, and large needle-like crystals were sparsely present as compared with Example 1.

[0037]

Comparative Example 3 A polymer was obtained in the same manner as in Example 1 except that zirconium acetate (obtained by distilling a 15% acetic acid solution) was used instead of calcium acetate. A polyester fiber was obtained from this polymer by the same manufacturing method as in Example 1, and when measured in the same manner as in Example 1, the clarity and deep color of the obtained dyed product were 18.3 and 18.3. Further, both abrasion resistance and dry touch were grade 4.

When the entire side surface of the fiber was viewed at a magnification of 3000 times, independent holes were observed at both ends where the yarn width was divided into three equal parts, and a large number of small ridges continued to form a streak. Also, when observed at 8000 times, the surface of the fiber is 0.3 to 5 μm in the fiber axis direction and 0.1 in the direction perpendicular to the fiber axis.
Holes of different sizes and depths of ~ 0.4 [mu] m with a maximum depth of 0.1-0.4 [mu] m were present substantially independently. These holes covered 60% of the entire fiber surface.

[0039]

Comparative Example 4 A polyester fiber prepared by a dry method and containing 0.5% by weight of silica having a primary particle diameter of 16 nm was prepared in the same manner as in Example 1. The sharpness and deep color of the obtained dyed product are 1
7.9 and 18.1, and both abrasion resistance and dry touch were second class. When the entire side surface of the fiber was viewed at a magnification of 3000 times, independent holes were observed at both ends where the yarn width was divided into three, and many small ridges as in Example 1 could not be observed. When observed at a magnification of 8000 times, the surface of the fiber has a surface of 0.3 to 8.0 μm in the fiber axis direction, 0.1 to 0.5 μm in a direction perpendicular to the fiber axis, and a maximum depth of 0.08 to 0.8 μm.
Shallow and large holes having a size of 2 μm and different depths were independently present. These holes covered about 50% of the entire surface of the fiber. The primary particles are agglomerated spherically and have a diameter of 5
It was as large as 0 to 100 nm.

[0040]

Examples 2 to 4 Example 1 was repeated by changing the type and amount of the fine particles. Table 1 shows the results. In each case, good vivid color depth, abrasion resistance and dry touch were exhibited. In addition, when the entire side surface of the fiber was viewed at a magnification of 3000 times, independent holes were observed at both ends where the yarn width was divided into three equal parts, and a large number of small ridges continued to form a streak.

[0041]

Example 5 In Example 1, 0.1% by weight of sodium salt of monomethyl benzylphosphonate was used instead of solution A.
The ethylene glycol solution was added after the transesterification was completed. In this case, the phosphonate is added to the polymer in an amount of 0.1.
7% by weight was added. Fibers were obtained from this polymer by the production method described in Example 1, and when measured in the same manner as in Example 1, the clarity and deep color of the obtained dyed product were 18.
8, 17.6, abrasion resistance was 5th grade, and dry touch was 4th grade.

[0042]

Example 6 1500 parts of dimethyl terephthalate, 900 parts of ethylene glycol, 0.9 parts of calcium acetate monohydrate
The transesterification reaction was carried out by a conventional method using the above-mentioned parts. 5.2 parts of dimethyl phenylphosphonate and 15.5 parts of calcium acetate monohydrate are dissolved in 200 parts of ethylene glycol, and trimethyl phosphate is used as a heat stabilizer.
Example 1 was repeated using 9 parts of the solution A.
Solution A contained 85% of a calcium salt of monomethyl phenylphosphonate. The whiteness of the obtained yarn was extremely excellent.

Fibers of 50d / 24f were prepared from the obtained polymer. When this fiber was measured in the same manner as in Example 1, the sharpness was 19.4 and the deep chromaticity was 17.0. In addition, both abrasion resistance and dry touch were grade 5. When the entire side surface of the fiber was viewed at a magnification of 3000 times, hardly any independent holes were observed at both end portions where the yarn width was divided into three, and many small ridges continued to form a streak. 8
When observed at 000 times, the surface of the fiber has a thickness of 0.01 to 3 μm in the fiber axis direction and 0.01 to 0.01 μm in the direction orthogonal to the fiber axis.
Holes having a size of 0.3 μm and a maximum depth of 0.05 to 3 μm and holes having different depths were present, and continuous irregularities in which several holes were connected to each other covered almost the entire fiber. The density of the primary particles was 120 / (μm) ² .

[0044]

Example 7 Example 1 was repeated except that 2 mol% of dimethyl terephthalate was replaced by dimethyl 5-sodium sulfoisophthalate. The resulting polymer exhibited good dyeing properties for cationic dyes. Fibers of 50d / 24f were prepared from the obtained polymer. When this fiber was measured in the same manner as in Example 1, the sharpness was 19.4 and the deep chromaticity was 17.5. In addition, both abrasion resistance and dry touch were grade 5.

When the entire side surface of the fiber was viewed at a magnification of 3000 times, hardly any independent holes were observed at both end portions where the yarn width was divided into three, and many small ridges continued to form a streak. Was. When observed at 8000 times, the surface of the fiber is 0.1-5 μm in the fiber axis direction and 0.05 μm in the direction orthogonal to the fiber axis.
There were holes of different sizes and depths of 1 to 0.3 μm and a maximum depth of 0.5 to 3 μm, and a continuous hole in which several holes were connected to each other covered almost the entire fiber. The density of the primary particles was 150 particles / μm ² . The shape of the primary particles was the same as in Example 1. Secondary agglomerated particles are fiber cross section 1
The number was 150 per 0 μm ² .

[0046]

[Table 1]

[0047]

The present invention is excellent in sharpness and deep color,
An object of the present invention is to provide a polyester fiber having a dry touch texture and excellent productivity. 100% ester,
Alternatively, it is extremely useful as a woven or knitted fabric mixed with cellulose fibers, particularly for application to the field of women's outerwear.

Claims (3)

[Claims] 1. When the entire side surface of the fiber is viewed at a magnification of 3000 times, almost no independent holes are observed at both end portions where the yarn width is divided into three equal parts, and many small ridges continue to form a streak shape. When the surface of the fiber is viewed at a magnification of 8000 times, it has 0.001 to 5.0 μm in the fiber axis direction with irregular irregularities.
There are pores of different sizes and depths of 0.001-3.0 μm and a maximum depth of 0.01-0.5 μm in the direction orthogonal to the fiber axis, and the primary particles contained in the cross section of the fiber Is 50 to 3000 / μm ² . 2. The distance between both ends of the primary particles in the major axis direction is 1 to 2.
The polyester fiber according to claim 1, wherein the polyester fiber has a thickness of 100 nm and a width of 0.001 to 15 nm. 3. The polyester fiber according to claim 2, wherein the number of secondary aggregated particles formed by aggregating the primary particles is 3 to 1000 per 10 μm ^{2 of the} fiber cross section.