JPS58149322A - Modified polyester fiber and preparation thereof - Google Patents

Abstract

PURPOSE:The titled fibers, containing a specific amount of silica having specified values or less of average primary particle diameter and number of coarse particles in undrawn yarns, capable of exhibiting improved color developing property by dissolving the surfaces thereof, and having specific surface shapes. CONSTITUTION:Modified polyester fibers prepared by drawing undrawn fibers containing 0.30-0.49wt% silica having <=100mmu average primary particle diameter and <=150 coarse particles/g undrawn yarns, and capable of exhibiting a color developing improving index of 1.4 times or more of that of regular polyester fibers having the same fineness per fiber and total fineness on dissolving the surfaces of the undrawn yarns the color developing improving index is defined as follows: Color developing improving index=(L value of a circular knitted fabric without the alkali treatment)-(L value of the circular knitted fabric with 20% reduction in weight with the alkali) .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester fiber having a unique surface morphology and improved color development, and a method for producing the same.

Polyester fibers have excellent physical and chemical properties and are therefore widely used for clothing and industrial purposes.

However, polyester fibers are inferior to other fibers such as acetate, rayon, wool, and silk in the color development of dyed fabrics (deep black or sharpness of chromatic colors). In particular, when the single yarn fineness of the polyester fiber constituting the dyed fabric was less than 1 denier, the surface reflectance of light on the fabric surface was high and the color development was poor.

As a method to improve the color development of dyed fabrics, which is a drawback of conventional polyester fibers.

(1) A polyester fiber containing inorganic fine particles such as silica sol having an average particle diameter of 100 mμ or less in an amount of 0.45 to 10% by weight is subjected to alkali dissolution treatment.

Fiber with specific surface structure (JP-A-5-10751
(2) Polyester fibers containing 0.5 to 10% by weight of inorganic fine particles such as silica sol having an average particle diameter of 100 mμ or less are subjected to alkali dissolution treatment to give a specific surface structure and have a single yarn fineness of 1. Ultra-fine fibers below denier (4?
(Kokai No. 55-1123106) have been proposed.

However, the silica particles used in the il+ and (2) color development improvement technologies, such as the silica sol and dry method sled force, have the activity of the silanol group on the 1 surface, resulting in aggregation of the silica particles, reaction between the silanol group and the polymer, etc. happens. This results in decreased productivity due to increased viscosity during polymerization, poor hydrolysis resistance due to reaction between silica particles and polymer,
There are also problems such as yarn breakage at the culm during spinning, drawing, and high-order processing due to agglomeration of silica particles, and increased P pressure due to clogging of the P layer during spinning. It was not possible to stably produce the polyester produced industrially.

In addition to the problem that if the amount of silica particles added is increased using the color development improvement techniques described in (1)B and (2) above, the amount of silica particles present in the polymer increases, which amplifies the above problems. 1. There was a problem in that after the surface elution treatment, which was not intended to improve color development, the surface became extremely rough, and 1. color development deteriorated.

Furthermore, when the extremely roughened fibers are rubbed against the fabric, the uneven parts on the surface are destroyed and the surface tends to become a mirror surface.The fibers tend to partially reflect light, which changes the color and also causes fibrillation. The problem was that it was easy.

In view of the above-mentioned problems, the present inventors aimed to improve the manufacturing technology problems in the polymerization and spinning process KM of silica particle-added polyester fibers, and to improve the fiber surface morphology and anti-frosting property after surface elution treatment.

The present invention was arrived at as a result of extensive research into improving the reduction in color development caused by friction on the fiber surface.

That is, the present invention provides (1) an average primary particle diameter of 100 m;
A polyester fiber drawn from an undrawn yarn containing 0.30 to 0.49 weight factor of silica of μ or less and having a number of undrawn yarn coarse particles of 150/& or less. The first invention is a polyester fiber characterized in that the color development improvement index during surface elution treatment is 1.4 times or more that of regular polyester fiber having the same single fiber fineness and the same total fineness, (2) Silica with an average primary particle diameter of 100 mμ or less is 030% by weight.
．． Contains 49 weight coefficient or less, Chip I target dog eagle 4 number is 20
Polyester with 0 pieces/g or less.

A second invention provides a method for producing a modified polyester fiber, which comprises melt spinning using sand having a mesh size of 80 or more and/or a metal nonwoven filter having an absolute filtration diameter of 30 microns or less, followed by drawing. It is something.

The polyester according to the present invention refers to a polyester containing ethylene dalicol or 1,4-butanediol as a main glycol component and terephthalic acid or an ester thereof as a main dicarboxylic acid component.

A portion of this dicarboxylic acid is added to a dicarboxylic acid such as a monoalkali metal salt of 5-sulfoinphthalic acid, inphthalic acid, siphenylincarboxylic acid, naphthalene dicarphonic acid, adipic acid, sebacic acid, 3-dodecanedioic acid, etc. For example, a part of ethylene glycol or 1,4-butanediol may be replaced with an oxycarboxylic acid such as p-oxybenzoic acid, p-β-oxyethoxybenzoic acid, or an ester thereof. -10 alkylene glycols, 1,4-cyclohexane dimetatool, 1,4-bis(β-oxyethoxy)benzene, and glycols other than the main glycol components of bisglycolethernato of bisphenol A may be substituted.

It is also possible to use a small proportion of a chain branching agent such as pentaerythritol, trimethylolpropane, trimellitic acid or trimesic acid, or a polymerization terminator such as monohydric polyalkylene oxide or phenylacetic acid.

To produce polyester sheets from such raw materials, for example, dimethyl terephthalate may be mixed with ethylene glycol or
, 4-butanediol, or
The most widely used method is to directly esterify terephthalic acid with the glycol or to add ethylene oxide to terephthalic acid, or to polymerize terephthalic acid with the glycol and then the product by a conventional method. be done.

Synthesis of polyester that further carries out the present invention? In this case, catalyst 1 coloring inhibitors, matting agents, ether bond by-product inhibitors, antioxidants, flame retardants, etc., which are well known in the bucket industry, can be used as appropriate. .

The silica used in the present invention is dry process silica.

Examples include wet process silica, dry process silica containing aluminum oxide, and silica organosol. Among these, aluminum oxide-containing dry process liquids are particularly preferred from the viewpoint of color development improvement effect (1) agglomeration during polymerization, #J thread, thread breakage during drawing (f^ large grains 1%).

In addition, in the present invention, silica refers to silicon oxide.
% or more.

In the present invention, the aluminum oxide-containing dry process silica is produced by the presence of aluminum halide in silicon halide when silicon oxide is produced by a dry process.The aluminum oxide content is 0.1 to 5% by weight. %, preferably 0.3 to 2% by weight.

It should be noted that if the inorganic fine particles to be contained in the polyester are fine particles other than the silica of the present invention, the effect of improving coloring properties will be poor and this is not preferred.

The average primary particle diameter of silica in this invention 1 is 100m
μ or less, preferably 50 mμ or less, especially? Preferably 2
It is 0 mμ or less.

If the average primary particle diameter exceeds 100 mμ, the effect of improving color development will be reduced, which is not preferable.

The content of silica particles in the polyester fiber of the present invention is 0
．． It is necessary to make it 49 weight downwind.

The detailed reasons will be explained below. Since silica particles tend to aggregate, the polymer tends to contain many coarse particles.

The polyester fiber of the present invention has undrawn yarn coarse particles of 150
It is necessary to keep the number of particles/g or less, so the mesh is 80
Sand B with mesh size or higher/or absolute filtration diameter of 60
Melt spinning is performed using a metal nonwoven fabric filter with a size of less than μ. In this case, if a polymer having a number of 15,000-knob enlarged particles exceeds 200 as measured by the method described below is used.

Due to clogging of the furnace layer, the pressure in one unit increased significantly, ”-:t=
'Not practical for production.

However, in the present invention, when the content of silica particles in the polymer exceeds 0.49% by weight, the coarse chip particles become 20% by weight.
This is because the above-mentioned problem occurs because the number of particles per gram is 0.

The polyester fiber of the present invention must be drawn from an undrawn yarn having a coarse particle count of 150 pieces/g or less as measured by the method described below.

The number of coarse particles in the undrawn yarn refers to the number of coarse particles in the undrawn yarn immediately after passing through the spinneret during melt spinning of polyester.If the number of coarse particles exceeds 150 pieces/g, the coarse particles are Because of the foreign matter inside, yarn breakage occurs frequently during spinning and drawing.

Furthermore, since the number of coarse particles in the polyester fiber after drawing increases, yarn breakage is more likely to occur due to tension loading, abrasion, etc. in higher-order processes such as false twisting, one-strong twisting, weaving, and weaving. Furthermore, when surface elution treatment is performed with an alkali or the like, large holes are formed in the coarse particles, which is disadvantageous in terms of strength and fuzziness of the fabric obtained.

When the deformation rate during spinning is high, such as when spinning highly oriented undrawn yarn or spinning to obtain a drawn yarn only in the spinning process, 'P6
When the single fiber denier is small or when producing a yarn with an irregular cross section, it is preferable to reduce the number of coarse particles in the undrawn yarn as much as possible.

In order to eliminate the above problem, the number of undrawn yarn coarse particles is 100.
The number of particles/g or less is particularly preferable.

Further, the polyester fiber of the present invention is drawn from an undrawn yarn in which the number of undrawn coarse particles is 150 pieces/g or less, but this drawing step may be performed in any of the following cases.

(1) A process in which the undrawn yarn and highly oriented undrawn yarn, which have been wound once as usual, are stretched or false-twisted in a separate process.

(Spinning at 4,000 to 4,500 m/set n or less in 21 spinning steps.

A direct spinning/drawing process that involves continuous drawing.

(3) 4.50 to obtain a drawn yarn only in the spinning process.
A step of spinning at 0 to 5,000 m/si+ or more.

In addition, the number of undrawn yarn coarse particles defined in the present invention is:

The number of coarse particles in the undrawn yarn immediately after the spinneret is the number of coarse particles in the undrawn yarn. In this case, the number of coarse particles is 4-. H (It is thought that the number of large particles is smaller than that of the IJ phase.

[Number of coarse particles in undrawn yarn]

When spinning polyester, about 7 g of polymer is collected on a clean stainless steel plate at a position of 5 to 10 σ on the upper hook of one nozzle, and then measured in the same manner as the coarse chip particles described below.

When the polyester used in the present invention with a siliency addition amount of more than 0.49% by weight, which has a large effect of improving color development, is polymerized by a normal method, coarse particles are generated violently due to the large amount of 1 particle added, and undesirable particles due to the coarse particles are generated. Increase in coarse particles in the drawn yarn and deterioration in spinning properties.

Problems such as decreased color development and decreased thread strength tend to occur.

In particular, the generation of coarse particles tends to gradually increase as polymerization batches are continued.

In order to reduce the production of coarse particles to 200 or less per gram of polymer, it is preferable to optimize the amount of one type of particle added and to optimize the polymerization conditions as described below.

The number of secondary particles having a diameter three times or more the average primary particle diameter in the present invention (e) is preferably 10 or more per 10 square microns. If the number is less than 10, the effect of improving color development tends to be small. The reason for this is thought to be that the shape, number, etc. of the vertically long depressions that occur when the fibers are subjected to the alkali elution treatment are different.

In addition, in the present invention, the number of secondary particles having a diameter of 3 times or more of the average primary particle diameter is determined by the number of secondary particles having a diameter of 3 times or more than the average primary particle diameter.
The cut thread sample was exposed to 50,000 yen using a Hitachi HU-12 transmission electron microscope (acceleration voltage 75 KV).
The number of secondary particles is counted around 7.3 cm x 11 crn of a photograph taken at a magnification, and the value is calculated as an average of 20 samples based on a Schiff calculated per 10 μ2 of polymer.

The ultimate viscosity [η] of the polyester fiber according to the present invention is:
Preferably it is 0.36 or more, particularly preferably 0.5
It is 3 or more. If it is less than 0.36, strength, fibrillation, etc. may become a problem depending on the application, and for this reason, a value of 0.53 or more is more preferable.

The diethylene glycol content in the present invention is preferably 2 weight ranges or less, particularly preferably 1 weight range or less.

If the amount exceeds 2 weight width, the OR of the false twisted yarn will be applied as described below.
There is a tendency for the value to decrease and the feel of the fabric to deteriorate.

Furthermore, the false twisted yarn of the present invention has a DEQ content of 2.0wt.
% or less, more preferably 1.0wt4 or less. If the content of DEG is too high, the heat setting property during false twisting will be insufficient, and the OR value will decrease, which is not preferable.

The method for producing the modified polyester fiber of the present invention will be described below.

The modified polyester fiber of the present invention contains silica having an average primary particle size of 100 mμ or less in an O:3O weight ratio or more.
Polyester polymer sand with a mesh size of 80 or more and/or sand with an absolute filtration diameter of 30 microns or less, containing 49% by weight or less, and the number of coarse particles measured by the method described below is 20 (] pieces/g or less) It is obtained by melt spinning using a metal nonwoven filter and then stretching.

In order to obtain the polyester fiber of the present invention in which the number of undrawn yarn coarse particles is 150 pieces/g or less, the polymer having the number of chip coarse particles of 200 pieces/g or less is mixed with sand and/or polyester fibers having a mesh size of 80 meshes or more. It is necessary to perform melt spinning using a metal nonwoven fabric filter with an absolute filtration diameter of 30 microns or less. Polyester containing silica particles has many coarse particles due to aggregation of silica particles, so in order to reduce undrawn yarn coarse particles, it is necessary to perform filtration using sand with a mesh of 8 [17771 or more]. There is. Since the number of coarse particles in sand of less than 80 meshes, such as 40 meshes or 60 meshes, is not less than 150 pieces/piece, problems such as yarn breakage occur in the above-mentioned spinning and higher-order processes.

In addition, if a sand made of ordinary glass beads or morundum is used for the above-mentioned filtration, the furnace pressure will increase significantly due to clogging of the furnace layer, but if a metal sand such as stainless steel is used, the increase in P pressure can be reduced. preferable. Furthermore, it is preferable to perform filtration using a metal nonwoven filter made of sand and/or stainless steel, since the rise in furnace pressure can be reduced. Absolute metal non-woven filter? The filtration diameter must be 30 microns or less, and 2
More preferably, it is 0 micron or less.

Further, although the metal nonwoven fabric filter may be used alone, it is preferable to use it in combination with sand. In this case, the sand mesh may be less than 8o mesh, but it is more preferable to use 80 mesh or more. In order to prevent an increase in P pressure and enhance the filtration effect, it is most preferable to combine metal sand and a metal nonwoven filter. Metallic sand and non-woven filters require special filtration enhancement. It is preferable to apply this method to yarns with a single fiber denier of 1.5 deniers or less, yarns with irregular cross sections, high-speed spinning, and the like.

Further, as described above, in accordance with the present invention, sand with a mesh of 80 meshes or more and/or an absolute filtration diameter of 3
Filtration during spinning is performed using a metal non-woven filter with a diameter of 0 microns or less.

Is there a way to prevent P pressure from increasing due to clogging in the furnace layer? It is necessary to use a polyester polymer in which the number of coarse chip particles is 200 pieces/g or less.

If the number of coarse chip particles exceeds 200 pieces/g, there is a problem that the P pressure rises too much, making it impractical for industrial production.

In other words, the upper limit (pack internal pressure in a normal spinning device) is 450 to 500 kg/cIi, but 1. When producing the polyester of the present invention, the undrawn yarn coarse particles are mixed at 150 pieces/cIi.
In order to make the yarn less than 80 mesh, sand with a mesh/yu ratio of 80 mesh or more and/or gold nonwoven with an absolute filtration diameter of 50 microns or less (Ii Mitsuilter is used, so the bank internal pressure at the start of spinning is 150 to 200%. /-.

Therefore, it is necessary to keep the total pack internal pressure rise within 250 to 300 m/d. On the other hand, in normal industrial production, the pack replacement cycle must be at least 15 to 20 days, and the pack internal pressure must rise by a maximum of 15 to 20 kg/d7 days. Therefore, when spinning normal 75 denier polyester fiber, the increase in P pressure is 0.3 to 0.4.
−/kLi polymer or less.

-The polyester used in the strength tree invention contains 0.50% silica.
Contains a weight factor of 0.49 or more and a weight factor of 0.49 or less.

Since the number of chip coarse particles is 200 pieces or less, 75
When spinning tenier yarn using 80 mesh sand, the P pressure increase is approximately 0.5 to 9/ly? r/kg of polymer, and can be preferably applied to the above-mentioned low pressure spinning machine.

[Number of chip coarse particles]

Vacuum dry 7g of polyester chips using a conventional method [1st, sandwich between stainless steel plates at 290°C, 100ky/cJ]
Press for 1 minute, then cool quickly.

Then, it was stretched by a conventional method to an area ratio of about 10 times.

Create a film. Cut out about 1 g of the obtained film, mark one coarse particle on a polarizing plate, measure silica particles of 50 μ or more with a stereomicroscope, and calculate the number of coarse particles per 1 g of sample.

The number of coarse particles is measured 10 times per level and is expressed as the average value.

Silica in the present invention is an aliphatic glycol.

Aliphatic alcohol or water, etc. 1. It can be added as a dispersed slurry by a known method at any stage until the polymerization of the polyester is completed, but it is particularly preferable to add it after being dispersed in glycol, which is the raw material for the polyester. .

The silica dispersion slurry in the present invention can be prepared by a conventionally known method.
, 4-butanediol is preferably dispersed in a high-wheel stirrer having a plurality of helicoids parallel to the rotating direction of the stirring blades, as disclosed in JP-A-55-125495.

Further, it is more preferable to use separation of coarse particles by a centrifugal sedimentation method, separation of coarse particles by a filtration method, etc. in combination with the present technique. Furthermore, it is particularly preferable to use dispersion by a conventionally known ultrasonic method in combination with the above method.]7.

Furthermore, conventionally known dispersants can also be used as dispersants.

Here, the use of a dispersant is effective not only in improving the dispersion of the additive particles but also in improving the color development of the dyed fabric. Although the reason for this is not clear, it is thought that by adding a dispersant to improve particle dispersibility in the polymer, the alkaline dissolution treatment system improves the yarn surface to be more favorable. In particular, tetraalkylammonium compound dispersants have a great effect on improving color development and preventing silica agglomeration.
suitable.

Here, examples of the tetraalkylammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, -tetrapropylammonium hydroxide, tetrainprohylammonium hydroxide, and tetrabutylammonium hydroxide, among which tetraethyl hydroxide Ammonium is particularly preferred.

When such a dispersant, such as a tetraalkylammonium compound, is used, the preferred amount thereof is 5 to 30% by weight relative to the silica of the present invention. Usage amount is 5% by weight
If it is less than 30% by weight, the effect of preventing agglomeration is not sufficient, and if it exceeds 30% by weight, the effect not only becomes saturated, but also causes defects such as the polymer becoming yellowish brown and deteriorating the physical properties of the polyester fiber. .

In the present invention, the silica slurry can be added at any stage until the polymerization of polyester is completed.
In particular, it is preferable to carry out the reaction before the start of transesterification of the polyester and before the start of the polymerization reaction because the number of coarse particles of the silica of the present invention is reduced.

However, if it is a so-called master patch method in which the same polyester as the polyester of the present invention is dispersed at a high concentration by changing the dispersion medium of silica.

It can be added either after completion of polymerization or during spinning. /When producing a liquefied polyester, agglomeration tends to occur, and it is important to know how to prevent aggregation. It is known that silica agglomeration does not occur at high temperatures, so it is better to add it at as low a temperature as possible. As a result of studies conducted by the present inventors, it has been found that there are other important factors in preventing aggregation. It is well known that the polyester batch f7fc synthesis process generally involves transesterification cans and polymerization cans. The coil for heating the reaction solution in the transesterification tank is usually placed directly into the transesterification tank. Polyester polymerization is normally designed so that the reaction rate in the transesterification tank and the polymerization tank is evenly balanced, but the polymerization rate is highly dependent on the amount of charge, so a polymerization catalyst with a high degree of polymerization or low reactivity is used. If it is necessary to do so, it is common practice to reduce the amount charged so that the polymerization rate is in balance with the transesterification reaction rate. However, when polymerizing silica-containing polyester, it has slightly less heat resistance than ordinary polyester. It is necessary to give some consideration to the polymerization temperature, amount of catalyst, etc. Therefore, when the charging amount was lowered, the heating coil of the ester and replacement tank was often exposed outside the reaction solution. In such cases, the silica slurry or reaction solution adhered to the exposed heating coil, causing severe agglomeration of the silica and an increase in coarse particles. In such cases, the present inventors have found that the amount of coarse particles can be significantly reduced by increasing the charging amount and immersing the heating coil in the reaction solution. However, if the amount of charge (2) is increased, the polymerization reaction rate becomes slower, so that the transesterification reaction rate and the polymerization reaction rate become unbalanced. Therefore, the present inventors have discovered that by charging the transesterification can so that the coil is buried and transferring only an appropriate amount to the polymerization can, the reaction rate can be balanced and the number of coarse particles can be significantly reduced. Ta.

In the present invention, it is particularly preferable to produce a polymer in which the number of coarse particles in the polymer is 200 particles/g or less. However, this method is for continuous production using production equipment, and in tests, trial production, etc., if continuous production is not required, the temperature rise curve of the transesterification reaction may be changed to equalize the rate. Note that even if polymerization is carried out by such a method, a polymer having the same characteristics as the above-mentioned transesterification reaction liquid storage method can be obtained.

The transesterification catalyst and polymerization catalyst used in the present invention are not particularly limited, but in the case of silica, diethylene glycol is easily generated during polymerization.

Transesterification catalysts include lithium, calcium, manganese,
Magnesium compounds are preferred, and antimony compounds are particularly preferred as the monopolymerization catalyst.

The size of the vertically long fine dents in the present invention is not particularly limited, but polyester fibers that can form dents with a maximum width of 0.05 to 1.5μ and a length/maximum width ratio of 1.5 or more This is particularly preferred in terms of color development.

Here, the maximum width of the vertically long recess refers to the maximum width of the shortest distance of the recess in the horizontal direction. For example, if the □dent is oval, it is the short axis. Further, the length of a vertically long depression refers to the maximum straight distance of the depression. For example, if the vertically elongated depression is oval, it is referred to as the major axis.

The polyester fiber of the present invention must have the effect of improving color development when the fiber is subjected to surface elution treatment with a soluble or degradable solvent.

The above-mentioned coloring property improvement effect is such that the coloring property improvement index measured by the method described below is 1 when the single fiber fineness and the total fineness are the same.
Is it more than 1.4 times the coloring property improvement finger fi of Ina regular polymer with coloring property improvement technology added? This is achieved through this. The term "regular polymer" referred to here is an improvement in which the color development property is improved by making the fiber surface finely uneven through surface elution treatment (for example, by adding inert inorganic fine particles such as silica as in the present invention). Or,
This refers to ordinary polyester that has not been subjected to techniques such as blending polymers with different solubility with solvents, alkalis, etc.). In addition, when a heat-generating additive such as a matting agent that changes the coloring property is used in the polyester fiber of the present invention, it is necessary to add the same additive to the regular polyester for comparison and evaluate it. It is preferable that the color development improvement index is 1.6 times or more that of the regular polymer.

The polyester yarn of the present invention was subjected to surface elution treatment.

When improving color development by forming fine irregularities on the surface 1. The effect of improving color development varies depending on the denier of the single fibers constituting the polyester fiber. In particular, when the denier of one single fiber is less than 2 denier, the effect of the denier of one single fiber is large compared to the effect of improving color development. Therefore, when evaluating the color development improvement index.

The single fiber fineness and total fineness of regular polyester must be the same. When the polyester fibers of the present invention, which have a color development improvement index of 1.4 times or more than regular fibers, are subjected to surface elution treatment, a moderate number of vertically elongated minute dents are present in the fiber axis direction on the fiber surface. is recognized. Furthermore, it is considered effective to have an appropriate distribution of the depth of the minute depressions, the way the irregularities are connected, the shape of the vertically long parts without depressions, etc. in order to exhibit the effect of improving color development. In order to make the color development improvement index 1.4 times or more than that of Gular, it is necessary that the silica content of the polyester fiber of the present invention is 0.5 or more by weight.

If it is less than 0.50% by weight, the number, size, depth, etc. of depressions on the fiber surface after surface elution treatment will be insufficient.

It is considered that the total color development improvement index indicated by mI is not more than 1.4 times that of regular.

Moreover, the silica content is 0.49% by weight.

After surface elution treatment, the fiber surface is extremely roughened.

The edges of the vertically long dents become sharp, and the dents become even deeper, or even more dents occur within the dents. This causes diffuse reflection of light on the fiber surface.

Although there is an effect of improving color development due to effects such as scattering.

Thread physical properties deteriorate, which is not desirable. Therefore, if it is only to impart an effect of improving color development, the amount of glue force addition is 0.
Although the amount may exceed 49% by weight, it is necessary to set the upper limit of the amount added at 0.49% by weight from the viewpoint of silk-spinning property, industrial productivity, etc.

As described above, the effect of improving the color development of the polyester fiber of the present invention is subtly influenced by the distribution of the shape of the irregularities on the surface when the polyester fiber of the present invention is subjected to the surface elution treatment, the mutual positional relationship, etc.

Therefore, in order to obtain excellent color development when using the polyester fiber of the present invention, [6] The type of silica particles used in the present invention, the particle size and the amount of particles added, as well as surface elution such as alkali treatment. Processing also needs to be optimized.

[Method of measuring color improvement index]

The filament yarn to be evaluated was passed through a 27-gauge tricot sock knitting machine (manufactured by Seishi Kikai Seisakusho) to knit two tube-knitted fabrics, and then 0.2 inches of non-ionic activator (Sandets) G was added using a conventional method. -900 (manufactured by Sanyo Chemical Co., Ltd.)] and scouring by boiling in boiling water containing 0.2 parts soda ash for 5 minutes, then washing with water and drying.

Next, dry heat treatment was performed in a non-tensioned state for 60 seconds using a baking machine (MODEL-DK-IH manufactured by Ohtsuka Kagaku Seiki Seisakusho) adjusted to 10180° C. to set the front knitted fabric. Next, one side of the tubular knitted fabric was subjected to the alkaline dissolution conditions described below to reduce the weight loss rate to 20%? Process this to reduce its weight. Both the front knitted fabric is subjected to bleaching alkali dissolution treatment, and the tube knitted fabric is not.

Disperse dye Dianix Black FB-FS i
5% Owf (or cationic dye Oat, hil
onBlack CD-BLH14Owf) Acetic acid 0.
2g dispersant (Sanunruto 1,200) 140w
After staining for 60 minutes in an aqueous solution of 1:50 at 130° C., follow the usual method.

Hydrosulfide 2g/l Caustic soda 2g/l Non-ionic activator
After staining was carried out for 60 minutes in an aqueous solution of 2 g/l (Sundead G-900) at 130 DEG C. in a bath ratio of 1:50, the usual method was followed.

Hydrosulfide 2g/j? Caustic Noda 2g/j? Reduction cleaning was carried out for 20 minutes in an aqueous solution at 80° C. containing 2 g/l of a nonionic surfactant (Sanded 0-900), followed by washing with water and drying.

To evaluate the color development, use a digital measurement color difference calculator (manufactured by Suga Test Instruments Co., Ltd.) to stack six or more sheets of the front knitted fabric and measure the L value in a state where no irradiation light is transmitted.

As for the L value, the dark color has a small value, and the light color has a large value.

The color development improvement index is determined by the following formula.

(Color development improvement index) = (Value of tubular knitted fabric without alkali treatment) = (Value of tubular knitted fabric with alkali weight loss rate of 20%) (Alkali dissolution conditions) 1 part by weight of ms fabric was dissolved in sodium hydroxide (3 parts by weight) The sample was immersed in 50 parts by weight of a boiling aqueous solution of 100% by weight, treated with stirring for a predetermined period of time, washed with water, then neutralized with a 1% acetic acid aqueous solution, further washed with water, and dried. After careful consideration, a predetermined weight loss of 4F was set.

8. To calculate the weight loss rate, dry the front knitted fabric before treatment in hot air at 100°C for 20 minutes, and then measure the weight (A).
The cylindrical knitted fabric after the weight loss D process was similarly dried at 100°C for 20 minutes, and its weight was measured (the weight at this time is referred to as (B)).

Formula A-B X100 = weight loss rate (regret) I asked for more.

In order to exhibit the effect of improving the coloring property of the polyester fiber of the present invention, it is most preferable to perform a surface elution treatment with a solvent that is soluble or decomposable for one polymer.

The elution treatment can be performed either before or after dyeing the fiber. If the elution treatment is performed after dyeing, fine irregularities can be formed more significantly on the fiber surface.

As the surface elution treatment, dissolution treatment with an alkali is most preferable because it dissolves not only the polyester but also the silica. According to the purpose, amine decomposition treatment and elution treatment using a solvent can also be carried out.

The alkali dissolution treatment applied to the polyester of the present invention includes alkali metal hydroxides such as caustic soda and caustic potash,
When dissolved in water, fibers or knitted fabrics are heated in an aqueous solution of a basic alkali metal compound, such as an alkali metal carbonate, or an aqueous solution of a basic alkali metal compound is applied to a woven or knitted fabric using a pad/steam. Processing, etc. is thus accomplished. The alkali dissolution is preferably carried out by the above-mentioned alkali dissolution treatment method so that the weight loss rate is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, based on the weight of the fiber or woven or knitted fabric. If it is less than 5% by weight, the effect of improving color development will not be sufficient, so it is not preferable, and if it exceeds 50% by weight, the strength of the yarn will decrease, which is not preferable.

Further, in the alkaline dissolution treatment, an alkaline dissolution promoter such as cetyltrimethylammonium bromide and lauryldimethylbenzylammonium chloride can be used as appropriate.

The single fiber fineness of the polyester fiber in the present invention is not particularly limited. However, in general, when the single fiber fineness of polyester fiber is 1 denier or less, the light reflectance on the fabric surface increases and the deep bed decreases. It can be particularly preferably applied to fibers.

The surface elution treatment such as alkaline dissolution treatment applied to the polyester ultrafine fiber of the present invention usually results in a weight loss rate of 10 to 50%, and in order to reduce the single fiber fineness after dyeing to 1 denier or less, the present invention The single fiber fineness of polyester fiber is 1
．． It must be 5 denier or less. In general, when producing ultrafine fibers with a single fiber fineness of 1 to 1.3 deniers or less, there are generally many fiber breakages during spinning or drawing, and filtration reinforcement during spinning is required, so there are many coarse particles in the polymer. Since it is necessary to strengthen filtration during spinning, there is a problem that the internal pressure at the start is high and the increase in P pressure during spinning is also large.

For example, the known method disclosed in JP-A No. 55-112306 certainly has a great effect of improving color development, but because of the problems mentioned above, it is difficult to stabilize ultrafine fibers of 1.5 denier or less. It was difficult to produce.

The present invention optimizes particle type, amount added, number of coarse particles, etc.
It has also been possible to stably produce ultrafine fibers of 1.3 denier or less.

The 7-liquid-added polyester fiber of the present invention can be applied not only to straight yarns but also to highly twisted yarns and false-twisted yarns, but highly twisted yarns and false-twisted yarns are particularly preferable because the coloring property is further improved.

For the strong twisting of the polyester Im fibers of the present invention, commonly used up twister, town twister, or double twister methods are adopted, but the effect of improving color development by strong twisting depends on the twist coefficient. .

The highly twisted yarn preferably has a twist coefficient (K) K=Tfl of 3,500 or more, which is calculated from the denier (D) of the fiber and the number of twists per meter of fiber (T) using the following formula. 5.5
00 or more. Here, the twist coefficient is a number related to the twist angle of the fibers, and by increasing the twist coefficient, the twist angle increases, and the length of the contact area between single fibers per unit length of the fiber bundle increases. As is well known.

Therefore, when silica-added polyester fibers are strongly twisted and subjected to alkali dissolution treatment, color development is greatly improved synergistically because the contact area between single fibers increased due to strong twisting is reduced by the alkali dissolution treatment. A void is created, and this void acts as a kind of tunnel for light.1. In addition to increasing light absorption efficiency, the roughening of the fiber surface caused by alkali dissolution treatment of polyester fibers containing silica makes the tunneling effect caused by the voids between single fibers more effective. considered to be a thing.

Therefore, when the twist coefficient of the highly twisted yarn is less than 3.500, a sufficient amount of voids between the single fibers cannot be obtained, and the effect of improving the coloring property by the highly twisted process becomes extremely small.

In addition, increasing the twist coefficient improves the color development of dyed products, but excessive twisting also reduces the strength of the fibers, which is not practical.
The upper limit is K=25,000.

As the method for false twisting the polyester fibers of the present invention, either a spindle method or a friction method using a tube or disk can be adopted.

The yarn to be subjected to the false twisting process may be an ordinary drawn yarn, and the yarn may be drawn at a general drawing speed (1,000 to 1.500 m/m1-n
) or P OY (pre-”
. The high take-up speed (rientθayarn)
It is also possible to use highly oriented, low-crystalline, undrawn yarn drawn at a speed of 2,500 to 4,000 m/m1n) to perform false twisting at the same time as drawing.

Although the direct purpose of false twisting is to impart bulkiness and elasticity, the color development of the silica-added polyester fiber of the present invention can be further improved by alkali dissolution treatment after false twisting.

When polyester fibers containing the silica of the present invention are false-twisted and subjected to alkali dissolution treatment, the synergistic improvement in color development is due to the tunnel effect due to the voids between single fibers increased by the false-twisting process, and the silica of the present invention. This is thought to be due to the roughening of the fiber surface resulting from the alkali dissolution treatment of the added polyester fibers, which makes the effect more effective.

Therefore, the degree of freedom in selecting the false twisting conditions is extremely large.

In order to improve color development, the temperature of the heater is preferably in the range from the peak crystallization temperature of the polyester supplied to a high temperature that does not cause the threads to fuse or become brittle, and in the case of polyethylene/terephthalate fibers, it is 160°C. The above is particularly preferable.

The heating number during false twisting is preferably within the range of formula (1) below from the viewpoint of improving color development, and particularly preferably within the range of formula (II) below.

Tv′I5>10,000 ・−・−・−・−(1)
! i5,000≧TS/″′Tf, 215,000
(It) [where T represents the heating number (tpm) and D represents the denier of the yarn immediately after leaving the final heating element such as a spinner, tube, or disk. ] Note that the upper limit of the heating number is set within a range that does not cause frequent yarn breakage or excessive double twisting.

Furthermore, the effects of the present invention can also be achieved by employing a so-called false-twisting improvement method in which the false-twisted yarn is heat-treated by running a dry heat heater, or is gently wound and steam-set.

The polyester fiber of the present invention can be made into a composite fiber, but in the case of a core-sheath type composite fiber, the amount of silica added in the polymer forming the sheath portion is 0.50% by weight or more, 0.4% by weight or more.
Must be less than 9% by weight, 0.40% by weight or more,
It is preferably 0.49% by weight or less.

In the case of other composite fibers, it is also possible to use the silica-free polyester of the present invention as the polymer forming the surface as long as it has the effect of improving color development.

In particular, in order to impart excellent antistatic performance to the polyester fiber of the present invention, the following composite fibers are particularly preferred.

That is, the proportion of polyalkylene ether in the block polyether amide composition to the total fibers is 0.05.
A polyester system with excellent coloring properties, whose core is a mixture of a block polyether amide composition mixed with the above-mentioned polyester at a concentration of ~5% by weight, and whose sheath is the silica-containing polyester used in the present invention. Antistatic conjugate fiber and polyester antistatic conjugate fiber with excellent color development and abrasion properties, in which the core and sheath are arranged substantially concentrically, and the ratio of the core is 5 to 50% by weight. be.

In the case of the composite fiber, the polyester forming the sheath portion contains 0.30% by weight or more and 0.49% by weight or less of silica having an average primary particle diameter of 100 mμ or less, and the sheath portion contains The number of undrawn yarn coarse particles is 150 pieces/g or less, and the color development improvement index during surface elution treatment as a composite fiber must be 1.4 times or more than when ordinary polyester is used as a sheath component. be.

Depending on the purpose of use, if the weight loss rate during elution treatment such as alkali treatment is low and the proportion of the sheath is less than 20%, the alkali weight loss rate when measuring the color development improvement index of the present invention is
It is necessary to change the weight loss rate to the desired one and perform the measurement.

The block polyether amide composition used here is a block bipolyether amide containing a predetermined amount of an organic electrolyte and a phenolic antioxidant. The organic electrolytes here include sulfonic acids such as dodecylbenzenesulfonic acid, tridecylpe/ze/sulfonic acid, nonylbenzenesulfonic acid, hexadecylsulfonic acid, and dodecylsulfonic acid, and sodium and potassium.

These include alkali metal salts of sulfonic acid formed from alkali metals such as lithium, alkali metal salts of phosphoric acid such as sodium distearyl phosphate, and alkali metal salts of other organic carboxylic acids. Metal salts of sulfonic acids such as Da are suitable.

As a phenolic antioxidant, for example, 1°3, 5
trimethyl -2,4,6-tri
(5,5-di-tθrt-phthyl-4-hydroxybenzyl) be/zene, 2.2'-methylenebis(4-methyl-6tert-butylphenol), 2.6-tert-butyl-p-cresol, 2. It is a phenol derivative containing a sterically hindered substituent at a position adjacent to a phenolic hydroxyl group, such as 2'-methylenebis(4-ethyl-6-tθrt-7'tylphenol).

Block polyether amide refers to a block copolymer of polyether and polyamide, and a mere blend of polyether and polyamide is not included in the block polyether amide.

The polyether constituting the block polyether amide is a polyalkylene ether, which is a polymerization product of ethylene oxide and/or propylene oxide such as polyethylene ether, polypropylene ether, and polyethylene propylene ether. The molecular weight of these polyethers is 1,000 or more, preferably 3.
000 to 8,000, among which polyethylene glycol is most suitable.

On the other hand, the polyamides constituting the block polyetheramide are nylon 6, nylon 8. Nylon 12. It is a homopolyamide such as nylon 66 and nylon 610, or a copolymer containing these or other copolymer components, and is a homo or copolyamide produced by a polycondensation reaction of polyamide-forming components.

A method for producing block polyether amide is, for example, by 77-noethylating both ends of polyalkylene glycol, hydrogenating it to form polyalkylene ether diamine, and reacting this with a suitable dicarboxylic acid such as adipic acid or sebacic acid. A method of synthesizing a nylon salt and polycondensing this salt with the monomer forming the polyamide, and aminating both ends of a polyalkylene glycol to form a polyalkylene ether diamine, and then polycondensing it in the same manner as described above. The method for producing these block polyetheramides is not particularly limited. The weight ratio of the polyether component to the polyamide component in the block polyether amide is suitably 50 to 70 to 70 to 6.

The method of polycondensation of block polyether amide is not particularly limited either. For example, the normal pressure polymerization method often employed for nylon 6, etc., or the pressure polymerization method employed for nylon 66, etc. Legal methods can be used regardless of batch type or continuous type.

The proportion of organometallic salt in the block polyether amide composition is preferably 1 to 10% by weight. Particularly preferred is a range of 3 to 7% by weight. When the amount is less than 1% by weight, the antistatic property improving effect is insufficient, and when it is more than 10% by weight, the antistatic property is deteriorated due to deterioration of the streak-forming ability due to a decrease in the melt viscosity of the block polyetheramide composition.

The proportion of the phenolic antioxidant in the block polyether amide composition is from 1 to 10% by weight, especially from 5 to 7% by weight.
If it is less than 1% by weight, it will be difficult to sufficiently suppress the deterioration of antistatic properties due to thermal oxidative deterioration in the spinning process, yarn processing process such as false twisting, fabric dyeing, finishing process, etc. If the amount exceeds 10% by weight, the thermal oxidation suppressing effect will be saturated even if added, and no further effect will be observed.

It should be noted that in addition to organic metal salts and phenolic antioxidants, other additives such as matting agents, anti-coloring agents, fluorescent agents, light-fastening agents, and pigments may not be added to the block polyetheramide composition. There is nothing wrong with that.

Further, the ratio of the polyalkylene ether component of the block polyether amide composition to the total fibers is 0.0.
By using a mixture of a block ether amide composition mixed with polyester at a concentration of 5 to 5% by weight as the core and a silica-containing polyester as the sheath,
It not only has excellent durability and good antistatic properties, but also has the same whitening, heat resistance, light resistance, and dyeing light fastness as regular polyester yarn, and does not cause peeling between the core and sheath. It is possible to produce polyester fibers without any deterioration in quality due to fibrillation, without the troubles encountered with conventional yarns.

If the proportion of the polyalkylene ether component in the entire fiber is less than 0.05% by weight, sufficient antistatic properties cannot be imparted, and if it exceeds 5% by weight, the effect of improving antistatic properties is saturated and further Not only is no improvement expected, but an increase in the amount added may lead to deterioration of yarn properties. The ratio of polyalkylene ether component to the entire fiber is 0.
, 1 to 1% by weight is particularly preferred.

Furthermore, when the polyester fiber of the present invention is used as the composite fiber, the block polyether composition =-, -'-+ j
J-J-J+ ,,,(,l? I-J)? ? -4
Giri 卆→も.

Therefore, since the inner pressure of the pack increases during spinning with the polyester in the sheath, it is not possible to use polymers that thicken due to glue force or cause a large increase in oven pressure. However, the polyester used in the present invention is preferable because it does not have the above problems. Can be used.

In addition, since the core strength of the composite fiber is low, the strength characteristics of the sheath polymer are important, but since the polyester fiber of the present invention has a small amount of undrawn yarn coarse particles, it does not cause problems such as yarn breakage, and does not cause problems such as yarn breakage. It can be preferably used for core-sheath type composite fibers.

The effects of the present invention will be described below.

(1) Uses a specific amount of specific 7-reforce particles, so there is less agglomeration during polymerization, and coarse particles cause less yarn breakage during spinning, increased pressure inside the pack, yarn breakage during the DTY process, and less fluff, so it is used for general purposes. It can also be applied to ultrafine fibers, false twists, strong twists, composite fibers, etc.

(2) Since the silica particles are uniformly dispersed,
The surface unevenness that contributes to improving color development is uniformly formed, and large depressions due to agglomerated particles are not formed, so the effect of improving color development is high and it is also advantageous in terms of strength properties.

(3) Normally, the smaller the silica particle size, the greater the effect of improving color development, but on the other hand, problems are likely to occur due to particle aggregation.

However, in the present invention, it is possible to use silica with a small particle size and good coloring properties because it causes less aggregation during polymerization.

(4) Since the silica particles act as a crystallization nucleating agent in the DTY process, the efficiency of DTY heat fixation can be improved.

Furthermore, since the silica particles are uniformly dispersed, the above effect is even greater.

The present invention will be specifically explained below with reference to Examples.

In addition, in the examples, parts mean parts by weight, and chi means parts by weight.

In addition, the average primary particle diameter of silica in the following Examples, diethylene glycol content, measurement method of intrinsic viscosity [η], b value, fibrillation property evaluation.

[Average primary particle diameter] Take a photograph of silica powder magnified 100,000 times with an electron microscope, measure the longest diameter of each missing particle from the obtained image,
This is the value determined as the average of 1,000 values.

[Diethylene glycol content] 25 g of monoethanolamine is added to 1 g of polymer and heated under reflux to depolymerize. After cooling, 20 ml of methyl alcohol was added, and after neutralization with acetic acid, the amount was determined by gas chromatography and expressed as the ratio (%) of diethylene glycol obtained to the polymer.

[Measurement method of intrinsic viscosity [η]] This is the value measured at 25° C. by dissolving the polymer in O-chlorophenol.

[b value]

Polymer diameter 2.5~3.5 mm, height 4.5~5.5 mm
It is molded into a cylindrical shape and measured using a direct reading type color difference meter/computer manufactured by Suga Test Instruments Co., Ltd. The larger the b value, the greater the yellowing tendency of the polymer.

[Fibrillation evaluation method]

Figure 1 shows a schematic diagram of the fibrillation tester.

The friction area between wet sample (dyed knitted fabric) 1 and friction cloth 2 is 12.5! Attach it to the head 5 using the holder 4 so that the sum of the loads 5 on it becomes 750 g.

On the other hand, a shore rubbing table 6 was attached via anti-slip sandpaper 7, eccentrically rotated at 85 rpm, and rubbed for 10 minutes, after which the sample 1 was removed and the degree of fibrillation was visually determined.

That is, when fibrillation occurs, the rubbed part looks whiter than the unrubbed part, so we observed how the rubbed part looked white and judged it in the following 5 stages.

Grade 5: Frosting is not acceptable.

Grade 4: Slight frosting is observed.

Grade 6: Some frosting is observed.

Grade 2: Frosting is quite noticeable.

Grade 1: Frosting is significantly observed.

Among the above, when used for ordinary fabrics, a grade 5 or higher is considered a passing level.

However, this does not apply in special fields of use, such as when used in applications that require building resistance.

[Electrical specific resistance]

The sample was washed in a weak alkaline aqueous solution of 0.2% anionosurfactant for 2 hours using an electric washing machine, then washed with water and dried. Then, the sample was lengthened to 'LI5crn1 fineness (D
) 1.00 [20 by pulling it into a 1 denier fiber bundle
After controlling the temperature at 40% RH for 2 days, the resistance of the sample was measured using an oscillating capacitance micropotential measuring device at an applied voltage of 500 cm and calculated using the following formula.

XD ρ: Volume resistivity (Ωφα) R: Resistance (Ω) d: Sample density (g/cIIl) D: Fineness (denier) L: Sample length (crn) [Frictional charging voltage] Kyoto University Chemical Research method Using a rotary static tester (manufactured by Koa Shokai), a plain-woven cotton Kanakin No. 3 (weighing 100 g/1
yf) in an atmosphere with a rotor rotation speed of 40 Orpm, an applied voltage of 100 V, a temperature of 20° C., and a relative humidity of 30%.

100 parts of dimethyl terephthalate, ethylene glycol (
(including the amount of inorganic fine particle slurry brought in) 60
parts, 0.09 parts of magnesium acetate tetrahydrate, various silicas shown in Table 1, a 20% aqueous solution of tetraethylammonium hydroxide, and ethylene glycol at a weight ratio of 5:
Janke & Ku 2.5:92.5 mixture
nke1 Ultra Turrax T45 DX
The slurry was dispersed for 45 minutes at 10,000 rpm, and then filtered through a nickel filter with holes of 25 μm on each side.

The temperature was raised from 140° C. to 230° C. over 6 hours under a nitrogen gas atmosphere, and the resulting methanol was continuously distilled out of the system to carry out the transesterification reaction.

However, this polymerization apparatus is designed so that when 100 parts of dimethyl terephthalate is charged, the heating coil of the transesterification can, including the ethylene glycol tube, is completely buried.

Therefore, when 100 parts of dimethyl terephthalate is charged, the polymerization time, which normally takes 5 hours, takes 6 hours, so it is necessary to reduce the temperature increase rate so that the rate of transesterification is delayed.

Subsequently, 0.05 part of trimethyl phosphate and 0.03 part of antimono trioxide were added to the obtained product. The system was then gradually depressurized from 760 mHg to lm over 1 hour.
The pressure was reduced to Hg, and at the same time the temperature was raised from 230°C to 280°C over 1 hour and 30 minutes. Polymerization was further carried out under reduced pressure of 1 tax Hg or less at a polymerization temperature of 280° C. for an appropriate time to reach the target intrinsic viscosity. After the reaction is complete, discharge into water,
Polyester chips were obtained by a conventional method.

The obtained polyethylene terephthalate was dried under reduced pressure at 160°C for 4 hours, and then spun at 300°C using 36-hole gold.
The yarn was spun at a take-up speed of 1.550 m/min, followed by a hot roll at 85°C and a hot plate at 150°C, and the stretching ratio was changed as appropriate so that the elongation of the drawn yarn was 30 to 40%. A drawn yarn of 75 denier and 36 filaments was obtained.

Note that the discharge amount during spinning was changed so that the resulting drawn yarn denier was 75 denier in accordance with the drawing ratio of each condition.

A total of approximately 9 in 300 spinning tests were performed for each polymer on a single spindle spinning machine and the furnace pressure rise was measured.

In addition, regarding yarn-spinning property, N undrawn yarns of 3 instant windings were sampled, and a drum of undrawn yarns with no yarn breakage or fuzz was drawn, and wound into 5 to 7 pirns. The yarn reeling property is expressed by the following formula (1).

A: Number of undrawn yarn drums without fluff or yarn breakage B:
The increase in furnace pressure in the number of drawn yarn pirns was expressed as the increase in pack internal pressure per polymer passing through the pack.

Using the obtained drawn yarn, a tubular knitted fabric was created by the method described above, and then it was scoured, and the L value of the one that was subjected to alkali dissolution treatment so that the weight loss rate was 20% and the one that was not subjected to alkali dissolution treatment. was measured to evaluate the effect of improving color development.

Furthermore, fibrillation properties were evaluated using a tubular knitted fabric with a weight loss rate of 20%.

Table 1 shows the polymer properties and evaluation results of the drawn yarn.

Note that the filtration conditions in Table 1 are as follows.

A, 80 mesh random sand B, metal sand C160 mesh metal sand D, 60 mesh metal sand and experiment A6, which is a comparative example of a stainless steel nonwoven fabric filter with an absolute filtration diameter of 20 microns.
Since there are many coarse particles in the polymer and there are also many coarse particles in the undrawn yarn, the spinning property is poor and the furnace pressure increases greatly.

In Experimental Arashi 4, which is also a comparative example, the number of coarse particles in the polymer is 200 particles/g or less, but since 607 particles/Usand is used, the number of coarse particles in the undrawn yarn is also large and the spinning property is poor.

Polyester with coarse particles of 200 pieces/g or less is used, and the number of coarse particles of undrawn yarn is also 150 pieces/g or less, so both P pressure increase and yarn spinnability are good, and the number of secondary particles is 1
Since zero or more are present, the effect of improving color development is also large.

Note that Experimental Flat 1 is a blank for showing the color development improvement index of regular polyester to which silica is not added.

Example 2 A small amount of polymer was polymerized and spun into a 75 denier 36 filament in the same manner as in Example 1, except that the silica particles were changed and 80 mesh metal sand was used. A drawn yarn was obtained.

Table 2 shows the polymer properties and thread properties of the obtained yarn, as well as the fibrillation and coloring properties evaluated in the same manner as in Example 1.

In Experiment & 9.16.18, which are comparative examples, the amount of silica added was small, and in Experiment A15, the warp particle size exceeded 100 mμ, so the number of secondary particles was also small and the color development improvement index was low.

Moreover, Comparative Example 17.20.27 has a large number of coarse particles in the polymer, and also has a large number of undrawn yarn coarse particles.

On the other hand, Experiment A, which is an example of the present invention, 8.10 to 15.19°2
1.22 has a large effect of improving color development.

Also, since a polymer with coarse chip particles of 200 pieces/g or less was used, and the particle size was 80 mesh metals/g or less, although a small amount of yarn was spun, no abnormality was observed in the spinning performance or furnace pressure increase.

In addition, experiment A in which the degree of polymerization [η] was changed is an example of the present invention.
Nos. 25 to 26 have few coarse chip particles and have a large effect of improving color development.

Example 3 A small amount of drawn yarn was obtained in the same manner as in Example 2, except that silica was used and the dispersant was changed.

The obtained drawn yarn was subjected to a spindle-type false twisting machine equipped with a heater length of 110°C at a heater temperature of 210°C, a false-twisting speed of 100 m/m/nt, and a heating number of 5,4501. After false twisting using pm, knitting and alkali dissolution treatment using the method described above, color development was evaluated.

Table 3 shows the expansion/contraction elongation ratio (OR value) of the obtained false twisted yarn and the fibrillation property of the tubular knitted fabric after the alkali dissolution treatment.

In Table 3, experiment 428.29 has a large amount of DEG, so the false twist yarn OR is low, but experiments A28 to A51 all had a small amount of coarse particles in the polymer and had good color development.

Moreover, as a result of false twisting the regular polymer of Experiment A1 using the above method, the color development improvement index was 0.54.

Example 4 The polymer used in Experiments 1 and 2 of Example 1 was spun using 72-hole gold at a spinning temperature of 300°C and a take-up speed of 1.300.
m/min, then 85°C hot roll, 1
Stretched at a stretching ratio of 3.15 times using a 50°C hot plate,
A drawn yarn of 5 denier 72 filaments was obtained.

The filtration conditions were as follows.

C: 60 mesh metal sand E: Combination of 80 mesh metal sand and stainless steel nonwoven fabric filter with absolute filtration diameter of 20 microns Under each filtration condition, both undrawn yarn and drawn yarn are wrapped in 2 glazes, totaling about 10
A silk spinning test was carried out at a level of 0.01'l/l to evaluate the silk spinning properties. Siltability was calculated using the formula (1) of Example 10.

Table 4 shows the evaluation results of color development and fibrillation properties using the obtained drawn yarn.

Experiment No. 52 is a blank showing the color development improvement index of regular poly star stell.

Compared to the comparative example Experiment & 54 K, Experiment Arashi 54, which had strengthened filtration (-), showed good spinning properties.

Furthermore, the fibrillation property and color development improvement index were also good.

Example 5 The raw yarn obtained in Example 1 and Experiment 5 was strongly twisted with the twist coefficient shown in Table 5, knitted, and subjected to alkali dissolution treatment so that the weight loss rate was 20%, and then color development was evaluated.

Table 5 also shows the color development evaluation results, which are expressed as the L value reduction relative to the raw silk yarn without alkali dissolution treatment.

The higher the twist coefficient, the better the color development.

Table 5 Example 6 In Example 1 Experiment A2, 5.8 parts of sodium 6.5-bis(methoxycarbonyl)benzenesulfonate was added before transesterification, and lithium acetate 2 hydrate was used instead of magnesium acetate. Polymerization was carried out in the same manner as in Example 1 except that 0.2 part was added.

A small amount of the obtained polymer was spun and stretched in the same manner as in Example 1.

The obtained drawn yarn was treated with alkali using the method described above and evaluated by dyeing with a cationic dye. As a result, the color development improvement index was 1.65, indicating good color development.

Example 7 Polymerization was carried out in the same manner as in Experiment 4 of Example 1, except that in Experiment A2 of Example 1, 4 parts of polyethylene glycol having a molecular weight of 1,000 was added after completion of the transesterification reaction.

A small amount of the obtained polymer was spun and stretched in the same manner as in Example 1.

As a result of dyeing and evaluating the obtained drawn yarn after alkali treatment using the method described above, the coloring property improvement index was 1.32.By reacting with acrylonitrile in the presence of the yarn and further carrying out a hydrogenation reaction, more than 97% of both ends were amino groups. Polyethylene glycol diamine (number average molecular weight 4,000) was synthesized, and this was subjected to a salt reaction with adipic acid in a conventional manner to obtain a 45% aqueous solution of polyethylene glycol diammonium adipate.

Capacity 2rr? 9. Add the above 45% aqueous solution of polyethylene glycol diammonium adipate to 200% in a concentration can.
85 thicaproctam aqueous solution to 120 t, 9.40 tica hexamethylene diammonium inphthalate aqueous solution 16
Kg was added and heated under normal pressure until the internal temperature reached 110°C for about 2 hours, and concentrated to a concentration of 80%. Next, the capacity is 5ool!
Transfer the above concentrated liquid to a polymerization can, and add 2.5r/ml to the polymerization can.
Heating was started while nitrogen was flowing at min.

When the internal temperature reached 120°C, add 5.2 and 1.3.5 trimethyl-2,4,6-tri(6,5 di-tert-butyl 4-
Add 5.2 kg of hydroquine benzyl)benzene (TTB), start stirring, and stir until the internal temperature reaches 245°C.
Polymerization was completed by heating for 8 hours.

After the polymerization was completed, a pressure of 7FC9/1 (G) was applied with nitrogen inside the can, and the molten polymer was rotated into a belt shape of about 15mm wide and 1.5mm thick with an endless belt (length 6m, belt material stainless steel, surface (cooled with water spray) and extruded into a plate, and after cooling was pelletized in a conventional manner.

The relative viscosity of the obtained pellets was 2.18. Using a known composite spinning device, the pellets (A) made of the block polyether amide composition produced by the above method were mixed with polyethylene terephthalate pellets (B) containing no titanium oxide obtained by a conventional method, and the ratio was changed. The mixed pellets were fed as a core component from one hopper, and the polyethylene terephthalate pellets (C) of the present invention obtained in Experimental Boil 7 of Example 1 were fed as a sheath component from the other hopper, and the composite ratio of core to sheath was A concentric composite yarn having a ratio of 20 to 80 (weight ratio) was spun at a spinning take-off speed of 1.350 m/min.

3. The obtained undrawn yarn was heated at a hot plate temperature of 140°C.
The yarn was drawn 21 times to obtain a drawn yarn of 75 denier and 5.6 filaments.

The spinnability and drawability of all samples other than Experimental Sample No. 47 were good.

The obtained drawn yarn was treated with alkali using the method described above, and its color development was evaluated. Table 6 shows the results of fibrillation property, electrical resistivity, frictional charging voltage, and color development improvement effect.

In experiment Asa, the polyalkylene ether ratio was 0.
Since it is less than 0.05% by weight, antistatic properties tend to be insufficient.

However, since the ratio of polyalkylene ether in Experimental Sample No. 45 exceeds 5.0% by weight, the yarn-spinning properties are slightly deteriorated.

All of Experimental Arashi 38 to 45 had good fibrillation properties, and the color development improvement index was also good and almost the same as that of Experimental Arashi 2, which was obtained by spinning only the polyester of the present invention.

Table 6

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an apparatus for measuring fibrillation.

Claims (1)

[Scope of Claims] (1) The undrawn yarn contains 0.30% by weight or more and 0.49% by weight or less of silica having an average primary particle diameter of 100 mμ or less, and the number of undrawn yarn coarse particles is 150 pieces/g or less. A polyester fiber drawn from a certain undrawn yarn, which has a color development improvement index upon surface elution treatment of N regular polyester fiber having the same single fiber fineness and the same total NR degree.
A modified polyester fiber characterized by being 4 times or more. (2) The modified polyester fiber according to claim (1), wherein the average primary particle diameter of the silica is 50 mμ or less. (3) The modified polyester fiber according to claim (1), wherein the average primary particle diameter of the silica is 20 mμ or less. (4) Silica content is 0.40% by weight or more 0.4
Modified polyester fiber according to claims (1) to (3+), characterized in that it has a weight factor of 9 or less. Claims (1) to (1) are produced by spinning the following polymers:
Modified polyester fiber described in section 4). (6) Claim No. (1) characterized in that there are at least 10 particles per 10 square microns whose secondary particle diameter is 6 times or more the average primary particle diameter of the silica contained therein. Modified polyester fibers according to items (5) to (5). (7) The modified polyester fiber according to claims (1) to (6), which has an intrinsic viscosity of 0.56 or more. (8) The modified polyester fiber according to claims (1) to (6), which has an intrinsic viscosity of 0.53 or more. (9) The modified polyester fiber according to claims (1) to (8), characterized in that the content of diethylene glycol is 2% by weight or less. False-twisted modified polyester fiber. 02 The modified polyester fiber subjected to the modified polyester twist process according to claims (1) to (I), wherein the single fiber fineness is 1.0 denier or less. A polyester fiber in which polyalkylene ether in an αa block polyether amide composition is mixed in an amount of 0.05 to 5% by weight based on the entire fiber. Polyester containing silica with an average primary particle size of 100 mμ or less in a weight coefficient of 0.30 or more and 0.49 weight 1 Iq6 or less, and a chip size particle number of 200 pieces/P or less, with a mesh of 80 mesh or more sandwich and/
Or a modified polyester II1 characterized in that it is melt-spun using a metal nonwoven fabric filter with an absolute filtration diameter of 30 microns or less, and then stretched. Iino manufacturing method. 071 The average primary particle size of silica is 20 mμ or less (Claim 151) Claim No. 1 (method for producing modified polyester fiber according to claim 15). A patent claim characterized in that the content of silica is 0.40% by weight or more and 0.49% by weight or less. A method for producing a modified polyester fiber according to Items 09 to 09.Ql At least 10 particles per 10 square microns in which the diameter of the secondary particles is 3 times or more the average primary particle diameter of the silica contained. Claims No. 09 and 1. A method for producing a modified polyester fiber according to section 1. ■ Claim No. 9, characterized in that the fiber has an intrinsic viscosity of 0.36 or more. Item 09 (-) The method for producing a modified polyester fiber according to Item 01. QD: The modified polyester fiber according to Items α9 to ■ of the claims, characterized in that the intrinsic viscosity is 0.53 or more. Q2 A method for producing a modified polyester fiber according to claims t1!19 to c!tt, characterized in that the content of diethylene glycol is 2% by weight or less. (c) Diethylene glycol A method for producing a modified polyester fiber as described in Claims 09 to 2(2), characterized in that the content is 1% by weight or less. The method for producing a modified polyester fiber as described in (a) the method for producing a modified polyester fiber as described in claims 9 to 9, wherein the polyester fiber is a highly twisted textured yarn. (The polyalkylene ether in the 2'0 block polyether amide composition is 0.05 to 5
Claim 0, characterized in that the core is made of polyester mixed in proportion to the weight, and composite spinning is performed.
A method for producing a modified polyester fiber according to items 9 to (a).