JPS5921720A - Preparation of polyester fiber dyeable in bright color - Google Patents

Abstract

PURPOSE:To obtain the titled fibers having special micropores and depth of colors and brightness in coloring, by incorporating into a raw material containing an alkali-soluble metallic compound previously with a specific organic compound, spinning the resultant mixture, and treating the resultant fibers with an aqueous solution of an alkali to subject the fibers to the treatment for reducing the weight by a specific amount. CONSTITUTION:Polyester fibers containing an alkali-soluble or alkali-decomposable compound containing a metal, e.g. calcium salt of phosphoric acid diester, are treated with an aqueous solution of an alkali compound to reduce the weight thereof by a specific amount and give polyester fibers dyeable in bright colors. In the process, an organic compound, substantially stable under the melting conditions of the polyester which is a base material for the polyester fibers, unreactive and compatible with the polyester, without causing the phase separation from the polyester on cooling and solidifying the melt mixture thereof with the polyester, and having >=100 deg.C melting point and <=1,000 molecular weight, e.g. N-methylphthalimide, is previously incorporated with the polyester fibers, and the weight reduction ratio in the treatment of the fibers with the aqueous solution of the alkali compound is set at 2wt% or more to give the aimed fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing vividly dyeable polyester fibers. More particularly, the present invention relates to a method for producing polyester fibers that have special pores cured and exhibit improved color depth and clarity when colored.

Polyester is widely used as a synthetic fiber due to its excellent polyester properties.However, polyester fibers can also be used in natural fibers such as wool and silk, cellulose fibers such as rayon and acetate, acrylic fibers, etc. Compared to , the color lacks depth when colored, so it has the disadvantage of inferior color development -2 sharpness.

Up until now, attempts have been made to improve dyes and chemically modify polyester in an attempt to overcome this drawback, but none of these efforts have been able to produce sufficient effects (...Also, transparent thin films on the surface of polyester fibers have not been effective. 8 on the surface of woven or knitted fabrics.
Methods have been proposed in which fine irregularities are formed on the fiber surface by applying plasma irradiation of 0 to 500 mA-sec/(yl).However, even with these methods, the effect of improving color depth is insufficient. Moreover, the transparent thin film formed on the fiber surface easily comes off when washed, etc.
Its rigidity is also insufficient, and the method of applying plasma irradiation does not create unevenness on the fiber interface in the fiber part that is in the shadow of the irradiated area, so it becomes smooth due to the rolling of threads within the fiber structure that occurs during wear. It has the disadvantage that the fiber surface appears on the p-plane and becomes dark colored.

On the other hand, as a method for imparting irregularities to the surface of polyester fibers, polyester fibers containing polyoxyethylene glycol or hapholyoxyethylene glycol and a sulfonic acid compound are treated with an alkaline aqueous solution to form wrinkles arranged in the fiber axis direction. A method for producing hygroscopic fibers in which microscopic pores are formed on the fiber surface, and polyester rods and fibers containing fine particles of inert inorganic substances such as zinc monoxide and calcium phosphate are treated with an alkaline aqueous solution to form inorganic fine particles. A method for producing vibration-absorbing fibers in which fine pores are formed by elution has been proposed. However, the fibers obtained by these methods do not have the effect of improving the depth of color, and instead show a decrease in visual density. That is, in these methods, when the treatment with the alkaline aqueous solution is not sufficient, no effect of improving the color depth is exhibited at all, and when the treatment with the alkaline aqueous solution is sufficient, the effect of improving the color depth is not shown at all. Perhaps due to the diffuse reflection of light by the micropores, the visual density decreases, and even when dyed in a deep color, it appears whitish.Furthermore, the strength of the resulting fibers is significantly reduced, and they easily become fibrillated. This makes it impractical for practical use.

In addition, polyester fibers containing inorganic fine particles such as silica sol with a particle diameter of 80 mμ or less are subjected to alkali weight loss treatment to provide irregular irregularities of 0.2 to 0.7 μm on the fiber surface, and 50 to 50 μm in diameter within these irregularities. A method of improving the depth of color by creating minute irregularities of 200 mμ, and blending dry process silica containing aluminum oxide with a particle size of 100 mμ or less, or dry process silica with a particle size of 100 mμ or less that blocks silanol groups on the particle surface. A method has been proposed for improving the color development by subjecting pre-treated polyester fibers to an alkali dissolution treatment to impart a specific surface morphology to the fibers.

However, even with this method, the effect of improving the depth of color is insufficient, and in addition, perhaps due to the extremely complex shape of the unevenness, the unevenness is destroyed by external physical effects such as friction, and the destroyed parts However, there are disadvantages in that the color changes significantly compared to other undestructed parts, there is a difference in gloss, and furthermore, it easily fibrils.

The inventor of the present invention has conducted extensive research in an effort to provide a polyester fiber that does not have the above-mentioned drawbacks and has excellent color depth and clarity by adding micropores to the polyester fiber, and as a result, the inventors have discovered that a specific phosphorus compound and this phosphorus From a polyester obtained by adding a specific amount of alkaline earth metal compound to the compound to the polyester reaction system without reacting in advance, and allowing the two to react inside the cough reaction system to generate a small amount of insoluble fine particles. By treating the melt-spun fibers with alkali, it is possible to form many irregularities on the fiber surface that are smaller than the wavelength of visible light, which results in excellent color depth and clarity when colored. It was discovered that polyester fibers with sufficiently small discoloration due to friction and excellent fibril resistance can be obtained, and the method was proposed earlier.

However, the polyester fibers obtained in this manner are also limited in their use in fields where more vivid dyeability is required, and therefore further improvement in stirrup dyeability is desired.

The present inventor has found that the depth and clarity of the color when dyed is better,
As a result of extensive research in an attempt to provide a polyester fiber that has sufficiently low discoloration due to friction and sufficient fibril resistance for practical use, in addition to the internal precipitated particles consisting of the phosphorus compound and alkaline earth metal compound mentioned above, specific It has been discovered that the above object can be achieved by treating polyester fibers blended with an imide compound of the following with an alkaline aqueous solution. Moreover, the color improvement effect obtained by using the imide compound in combination was also observed when it was used in combination with the above-mentioned silica sol or dry process silica. It is not clear why the color is synergistically improved by using such an imide compound in combination, but in addition to the effect of the fine irregularities on the fiber surface, the imide compound is compatible with polyester.
It is thought that the effects of ultrafine pore formation caused by this are complicatedly superimposed. The present invention was completed after further studies based on these findings.

That is, in the present invention, when manufacturing brightly dyeable polyester fibers by reducing the amount of polyester fibers containing metal-containing compounds that are soluble or decomposable in alkali with an aqueous solution of an alkali compound, the polyester fibers are preliminarily treated with the following: Condition (1
This is a method for producing vividly dyeable polyester fibers, which is characterized in that an organic compound that satisfies (4) is blended therein, and the weight loss rate of the polyester fibers when treated with an aqueous alkali compound solution is 2i or more.

(ll) It is substantially stable under the melting conditions of the polyester that is the base of the polyester fiber, is non-reactive with the polyester, and is compatible with the polyester.

(2) No phase separation occurs when the molten mixture with the polyester is cooled and solidified.

(3) The melting point is 100°C or higher.

(4) Molecular weight is 1000 or less.

The polyester used in the present invention contains terephthal as a main acid component and contains at least 1 ffl of glycol, preferably ethylene glycol, trimethylene glycol, or tetramethylene glycol.

The main target is polyester whose main glycol component is at least one alkyne glycol selected from pentamethylene glycol and hexamethylene glycol.

It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which a part of the glycol component is replaced with the above-mentioned glycol other than the main component or another diol component.

The difunctional carboxylic acid other than terephthalic acid used here includes, for example, inphthalic acid.

Naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, rubonic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, 1.4-
Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as cyclohexanedicarboxylic acid. Examples of diol compounds other than the above-mentioned glycols include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimetatool, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyanolekylene gelyl alcohols. can be given.

Furthermore, polycarboxylic acids such as trimellitic acid, pyromellitic acid, etc., polyols such as glycerin, trimethylolpropane, pentaerythritol, etc. are copolymerized within a range where the polyester is substantially linear (usually 1 mol tre or less). There is no problem even if it is.

Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, it is usually a direct esterification reaction between terephthalic acid and ethylene glycol, a transesterification reaction between a lower fulkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a transesterification reaction between terephthalic acid and ethylene glycol. The first stage reaction is to react with terephthalic acid to produce a glycol ester and/or its low polymer, and the first stage reaction product is heated under reduced pressure until the desired degree of polymerization is achieved. It is produced by a second step of polycondensation reaction.

In the present invention, the alkali-soluble or decomposable metal-containing compound contained in the above-mentioned polyester fiber can be obtained by treating the polyester fiber containing the metal-containing compound with an alkali, by the method described later.
There is no particular restriction as long as the measured "depth of color" can be substantially improved;
) A phosphorus compound represented by the following general formula (1) in an amount of 0.3 to 3 mol based on the acid component constituting the polyester, and (
b) Without reacting the alkaline earth metal compound with (,) and (b) in advance, and the total amount of the equivalent number of metals of C,) and (b) is relative to the number of moles of the phosphorus compound of (,). te 2.0
By adding so as to increase the amount by ~3.2 times, insoluble fine particles precipitated by the reaction between (,) and (b) inside the polyester reaction system can be raised.

In the above formula (1) representing a phosphorus compound, R1 and R2 are a hydrogen atom or a monovalent organic group. Specifically, this monovalent organic group is a furkyl group or an aryl group.

75 alkyl group or ha(-(cH,)70)kR'' (where R'' is a hydrogen atom, an alkyl group, a 7-aryl group or an aralkyl group, l is an integer of 2 or more, k is an integer of 1 or more), etc. Preferably, R1 and R1 may be the same or different. X is a hydrogen atom, a monovalent organic group, or a metal; (Also, as metals, alkali metals and alkaline earth metals are particularly preferred, and among them, Ll * ” +
Kl “gl”2 + C81/2+ 8rH+”1%
is particularly preferred. m is an integer of 0 or 1.

Examples of such phosphorus compounds include orthophosphoric acid.

Phosphate triester such as trimethyl phosphate, triester phosphate, tributyl phosphate, triphenyl phosphate, methyl acid phosphate, ethyl 7-side phosphate,
Phosphoric acid mono- and diesters such as butyl acid bosphate, phosphorous acid mono- and diesters such as sulfurous acid, trimethyl phosphite, triethyl phosphate, tributyl phosphite, triphenyl phosphite, methyl acid phosphite. Phosphite mono- and diesters such as ethyl acid phosphite and butyl acid phosphite. Compounds of alkali metals such as , Na, Ni, etc. or Mg
One or more phosphorus compounds selected from phosphorus compounds obtained by reacting with compounds of alkaline earth metals such as , Ca, Sr, Ba, etc. can be used.

The alkaline earth metal compound to be used in combination with the phosphorus compound is not particularly limited as long as it reacts with the phosphorus compound to form a salt insoluble in polyester, and alkaline earth metal acetates can be used.

Organic carboxylates such as cypentarate, benzoate, phthalate, stearate, inorganic acid salts such as borates, sulfates, silicates, carbonates, bicarbonates, chlorides etc. Examples include halides, chelate compounds such as ethylenediaminetetraacetic acid complex, hydroxides, oxides, phenolates such as methylates, ethylates, and glycolates, and phenolates. organic carboxylic acid salts, halides, chelate compounds, which are particularly soluble in ethylene glycol;
Alcolades are preferred, and organic carboxylic acid salts are particularly preferred.

The above alkaline earth metal compounds may be used alone or in combination of two or more.

When adding the above-mentioned phosphorus (Is metal and alkaline earth metal compound), in order to give the final polyester fiber excellent color depth and friction durability, the amount of phosphorus compound to be used and the core phosphorus It is necessary to specify the ratio of the amount of the alkaline earth metal compound used to the amount of the compound used.In other words, if the amount of the phosphorus compound used in the present invention is too small, the color depth of the final polyester fiber will deteriorate. The depth of the color increases as the amount increases, but if the amount is increased too much, the depth of the color no longer shows any significant improvement, and on the contrary, the abrasion resistance and durability worsen, and in addition, the degree of polymerization and softening are insufficient. It becomes difficult to obtain a polyester having dots, and furthermore, trouble occurs in that fiber breakage occurs frequently during spinning.For this reason, the amount of the phosphorus compound added is 0.3 to 3 mol tsp based on the total acid components constituting the polyester. It should be in the range of 0.5 to 2 molty, particularly preferably 0.5 to 2 molt.

In addition, if the combined number of metals contained in the phosphorus compound and the alkaline earth metal compound is less than 2.0 times the number of moles of the phosphorus compound, the depth of color of the resulting polyester fiber will increase. is insufficient, and the polycondensation rate is low.
"It became difficult to obtain polyester with a high degree of polymerization,"
Furthermore, the softening point of the polyester produced is significantly lowered. On the other hand, if this amount exceeds 3.2 times, not only will the depth of the color become saturated, but also the strength and fibril resistance of the fiber will decrease. (For this reason, the total number of moles of the metals in the phosphorus compound and the alkaline earth metal compound should be adjusted to an amount in the range of 2.0 to 3.2 times the number of moles of the phosphorus compound. The range of 2.0 to 3.0 is particularly desirable.

The above-mentioned phosphorus compound and alkaline earth metal compound can be added in any order at any stage until the sugar content of the polyester is completed. However, if only the phosphorus compound is added before the first stage reaction is completed, the completion of the first stage reaction may be inhibited, and if only the alkaline earth metal compound is added to the first stage reaction, the completion of the first stage reaction may be inhibited. If it is added before the end of the reaction, when this reaction is an esterification reaction, coarse particles may be generated in the center of Fj.
During the transesterification reaction, the reaction may proceed abnormally quickly and cause bumping, so in this case,
It is preferable to keep it below about 0 weight percent. The timing of addition of at least 80 gk% by weight of the alkaline earth metal compound and the total amount of the phosphorus compound is preferably at the stage when the first stage reaction of polyester synthesis has substantially completed. In addition, when the phosphorus compound and the alkaline earth metal compound are added at the second stage σ), when the reaction has progressed too much, particles agglomerate.

Because blockage tends to occur and the color depth of the final polyester fibers obtained tends to be insufficient, it is difficult to react before the intrinsic viscosity of the reaction mixture in the second stage reaction reaches 0.3. I like that.

The above phosphorus compound and alkaline earth metal compound may be added all at once or in two or more divided doses.
Alternatively, it may be added continuously.

The above-mentioned phosphorus compound and alkaline earth metal compound need to be added to the polyester reaction system without reacting in advance. By doing so, the insoluble particles can be produced in the polyester in the form of uniform ultrafine particles.

If the phosphorus compound and the alkaline earth metal compound are reacted with the alkaline earth metal compound externally in advance to form insoluble particles and then added to the polyester reaction system, the dispersibility of the insoluble particles in the polyester becomes poor and coarse agglomerated particles are formed. This is not preferable because the effect of improving the depth of color of the finally obtained polyester fiber is no longer recognized.

In the present invention, any catalyst can be used for the first stage reaction, but among the above alkaline earth metal compounds, there are some that have the ability to catalyze the first stage reaction, particularly the transesterification reaction. When such a compound is used, it is not necessary to use a separate catalyst, and the alkaline earth metal compound can be added before or during the first stage reaction to also serve as a catalyst. As mentioned above, this may cause bumping phenomenon.

Preferably, the amount used is less than 20% by weight of the total amount of alkaline earth metal compound added.

In addition, in the present invention, the alkali-soluble or decomposable metal-containing compounds to be contained in the polyester fibers include:
In addition to the above, select from silica sol, dry process silica containing aluminum oxide, dry process silica with blocked silanol groups on the particle surface, alumina sol, fine particulate alumina, ultrafine titanium oxide, calcium carbonate sol, and fine particulate calcium carbonate. Inert inorganic fine particles having an average primary particle size of 100 mμ or less and consisting of at least Jt species can also be preferably mentioned.

The average primary particle diameter of the above inert inorganic fine particles is 100 mμ
Below, preferably 6 to 75 mμ, more preferably 10 to 75 mμ
A range of 50 tlμ is desirable.

In addition, the content of inert inorganic fine particles in polyester fibers is significantly higher than that of polyester fibers. 3-10 weight i
% range is preferred, and a range of 0.5 to 5% by weight is particularly preferred.

The above-mentioned inert inorganic fine particles are prepared as a dispersion slurry or sol of glycol, alcohol, water, etc.For example, in the case of silica sol, 1) aqueous silica sol that has been published by removing alkali from water glass, 2) adds glycol to this aqueous silica sol. and/or mixed with alcohol,
(2) It is preferable to replace the water in this aqueous silica sol with glycol and/or alcohol and add it at any stage until the polyester synthesis reaction is completed.

In the present invention, the organic compound used in combination with the alkali-soluble or decomposable metal-containing compound described above is substantially stable under the melting conditions of the polyester that is the base material of the polyester fiber (11), for example, at a temperature of the melting point of the polyester + 20°C. It must be non-reactive with polyester and uniformly compatible with polyester without causing phase separation when mixed with polyester.Here, 6. Substantially stable and non-reactive with polyester. ” means that it does not decompose itself (and does not decompose the polyester or react with the polyester).

Furthermore, (2) the organic compound is one that can maintain a homogeneous state of compatibility with the polyester without causing phase separation even when the homogeneous melt obtained by melt-mixing with the polyester is cooled and solidified. It is necessary that there be. This is for example −
When the above-mentioned uniform transparent melt is cooled at a sufficient cooling rate to obtain a non-quality solid, whether a uniform transparent solid is obtained or phase separation occurs to produce an opaque solid. You can easily judge by looking at it.

Further, the organic compound must have (3) a temperature of 100° C. or higher at 1% 1 point, and (4) a molecular weight of 1000 or less. If the melting point of the organic compound is lower than 100° C., when melt-mixed with polyester, the secondary transition point of the polyester will be significantly lowered, making handling during melt spinning difficult.

The organic compound used in the present invention is under the above condition T1.1.
It is acceptable as long as it satisfies (4), but in addition, from the viewpoint of preventing volatilization during melt-mixing, the boiling point at normal pressure is 250°C or higher,
In particular, temperatures of SOO°C or higher are preferably used.

Such organic compounds used in the method of the present invention include:
Any compound that satisfies the above conditions may be used, but for example, an imide compound represented by the following formula (II), the following formula (m) 0 111 [The imide rings are 5 or 6 members. Examples include imide compounds represented by the following.

Examples of the compound of the above formula (II) include a compound in which at least one of AI and R4 in the above formula (II) is an optionally substituted aromatic residue;
Preferably, compounds are used which are aromatic, optionally substituted, residues.

Further, as the compound of the above formula (m), a compound in which G in the above formula (m) is a monovalent, optionally substituted aliphatic residue is preferably used.

In the above general formula (■), the divalent aromatic residue representing AI is, for example, a 1.2-7 enylene group, 1
．． Mention may be made of 2+, 2.3- or 1.8-naphthylene groups; examples of divalent aliphatic residues include linear alkylene groups such as ethylene or trimethylene;
Mention may be made of Schiff 1 alkylene groups such as 2-Schiff 1 hexylene groups. These groups may be substituted with substituents that are non-reactive with polyester. Examples of such substituents include lower alkyl groups such as methyl and ethyl, lower alkoxy groups such as methoxy and ethoxy,
Examples include a cyclohexyl group which may be substituted with a halogen atom such as chlorine or bromine, a nido group, a phenyl group, a phenoxy group, or a methyl group.

Examples of the n-valent (n=or 2) aromatic residue representing R4 include a phenyl group and a 7-tyl group.

A monovalent aromatic residue such as a group of formula CXz84 (where z is 10-1-8o, - or -0H, -), 1.2-
7 enylene group, 1.2-, 2.3- or 1.
8-naphthylene group, formula 0←”Q (where 2 is 10−+
Examples of divalent aromatic residues include n-valent (n=1 or 2) aliphatic residues, such as methyl, ethyl, butyl, etc. ,
Chain fulkyl groups having 1 to 18 carbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, dodecyl, myridityl, stearyl, 5- or 6-membered cyclic alkyl groups such as cyclohexyl, cyclopentyl, ethylene, trimethylene, tetramethylene, Hexamethylene, octamethylene, decamethylene.

These groups representing a linear alkylene group having 2 to 12 carbon atoms such as dodecamethylene and 1,3- or 1,4-cyclohexyl R4 may be substituted with the same substituents as described for A1.

In the above formula (m), the tetravalent aromatic residue representing At is preferably a monocyclic, fused ring, or polycyclic tetravalent aromatic group represented by (2 is the same as the above definition). -You can give it as a gift.

The monovalent chain or cyclic aliphatic residue representing R5 includes the same chain alkyl group having 1 to 18 carbon atoms as exemplified for R4 in formula (II) above, or a 5- or 6-membered cyclic alkyl group. I can give you the basics.

The groups exemplified for A2 and R5 above may be substituted with the same substituents as described for AI.

As the imide compound represented by the above formula (If), for example, as a compound when n=1 in the formula (II), N
-Methylphthalimide, N-ethylphthalimide,
N-butylphthalimide.

N-ethyl-1,8-phthalimide, N-butyl-1
, 8-naphthalimide, N, N'-ethylenebisphthalimide, N as a compound when n = 2
, N'-tetramethylene bisphthalimito, N, N'
-Hexamethylene bisphthalimide.

N,N'-occumethylene bisphthalimide.

N,N'-decamethylene bisphthalimito, N,N'
-totecamethylene bisphthalimide, N, N'
-neopentylene bisphthalimide, N,N'-tetramethylene bis(1,S-naphthalimide).

N,Nj-hexamethylenebis(1,8-naphthalimide), N,N'-octamethylenebis(t,s-su7thalimide)',), N,N'-decamethylenebis(1,8-naphthalimide) -caftalimide), N,N'-dodecamethylenebis(1,8-naphthalimide), N
, N'-dodecamethylene bissuccinimide, N,
N'-dodecamethylenebishexahydrophthalimide, N,N'-1,4-cyclohexylenebisphthalimide, ■-7 coolimide 3-7 tarimidomethyl-3.5.5-)limethylcyclohexane , 4.
4'-bisphthalimide diphenyl ether, 3
．． 4'-bisphthalimide diphenyl ether,
3.3'-bisphthalimido diphenyl sulfone
4.4′ ~ bisphthalimido diphenyl sulfone,
4.4'-bisphthalimidodiphenylmethane and the like can be mentioned.

An example of the imide compound represented by the above formula (m) is N,N'-diethyl bilmeritimide.

N,N'-dibutylvilmeritimide, N,N'-
Didecylpyromellitimide, N,N'-dioctylpyromellitimide, N,N'-didecylpyromellitimide, N,N'-dicyclohexy♂ rubyromellitimide, N,N'-bis(3,3 ,5-)
(limethylcyclohexyl) pyromellitimide,
Examples include N,N'-diethyl-1,4,5,8-naphthalenetetracarboxylic acid 1.8-, 4.5-diimide.

The imide compounds represented by the above formulas (n) and (m) can be easily produced from the corresponding acid anhydrides and organic amines by known methods.

The above organic compounds may be used alone or in combination of two or more. It may be added to the polyester at any stage before the end of the spinning process of melt-spinning the polyester into fibers. For example, it may be added to the polyester raw materials, added during the synthesis of the polyester, or It may be added between the time of completion of synthesis and the time of melt spinning. In any case, it is preferable to mix the components in a molten state after addition.

If the amount of the above organic compound added is too small, the effect of improving the depth and clarity of the color of the polyester fiber ultimately obtained will be insufficient; on the other hand, if it is too large, the depth and clarity of the color will no longer be improved. The effect of this method does not show any significant improvement, and on the contrary, the abrasion resistance and durability deteriorate, and the melt viscosity of the polyester composition decreases significantly, making melt spinning difficult.

Therefore, the amount of the organic compound added to the polyester is preferably in the range of 0.1 to 30% by weight, particularly preferably in the range of 0.5 to 20% by weight, based on the polyester fiber.

In order to melt-spun the thus obtained polyester blended with an alkali-soluble or decomposable metal-containing compound and an organic compound into warp fibers, there is no need to adopt any special method, and ordinary methods can be used. A method of melt spinning polyester fibers is optionally employed. The fibers spun here may be solid fibers having no hollow portions, or may be hollow fibers having hollow portions. Further, the outer shape and the shape of the hollow portion in the cross section of the fiber to be spun may be circular or irregular.

In order to remove a part of the polyester fiber obtained in this way, after subjecting it to stretching heat treatment or false twisting as necessary, or further heating it in an aqueous solution of an alkaline compound after making it into a fabric, or This can be easily carried out by pad/steam treatment of an aqueous solution of an alkaline compound.

Examples of the alkali compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, and the like.

Among them, sodium hydroxide and potassium hydroxide are particularly preferred.
L. Further, alkaline dissolution promoters such as cetyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride, etc. can be used as appropriate.

The amount of alkaline compound eluted and removed by treatment with an aqueous solution should be in the range of 2 weight or more based on the weight of the fiber. By treating the fiber with an aqueous solution of an alkaline compound in this manner, a large number of special micropores can be formed on the fiber surface and its vicinity, resulting in excellent color depth when dyed.

Note that the polyester fiber obtained by the method of the present invention can be appropriately subjected to a known post-deepening process. Such post-deepening processing includes a method of coating the surface of the polyester fiber with a polymer having a refractive index lower than that of the polyester, such as dimethylpolysiloxane, tetrafluoroethylene-propylene copolymer, etc. can be preferably adopted.

In addition, the polyester fiber obtained by the method of the present invention may contain optional additives, such as catalyst 1 coloring inhibitor, heat resistant agent, '8 flame agent, fluorescent whitening agent, matting agent 2 coloring agent, etc. Even if it includes (゛.

Further explanation will be given below with reference to Examples. Parts and % in Examples indicate parts by weight and weight %, and the depth of color and resistance to friction discoloration when the resulting polyester fibers were dyed were measured by the following method.

(The bathochromic degree (K/s) was used as a measure to indicate the depth of the 11 deep colors. This value is the spectral reflectance (R) of the sample cloth.
It was measured using a -330 type self-recording spectrophotometer and calculated from the Kubelka-Munk equation shown below. The larger this value is, the greater the deep color effect is.

K/S=-Niriji 1y-(Measurement wavelength: 5oomμ)R In addition, K shows an absorption coefficient, and S shows the number of scattering images.

(1) Friction discoloration resistance Using a Gakushin type flat abrasion machine for friction fastness testing, a georgette made of 100% polyethylene terephthalate was used as the friction cloth, and the test cloth was abraded a specified number of times under a load of 5ooy. The degree of discoloration was determined using a gray scale for discoloration and fading. 1 for extremely low wear resistance
If it is extremely high, it is classified as grade 5. For practical purposes, a level 4 or above is required.

Examples 1-6 Dimethyl terephthalate loo moiety, ethylene glyfur 6
0 parts and 0.06 parts of calcium acetate hydrate (0.066 mol% based on dimethyl terephthalate) were charged into a transesterification tank, and the temperature was raised from 140°C to 230°C over 14 hours in a nitrogen gas atmosphere. The transesterification reaction was carried out while the methanol produced was distilled out of the system.Subsequently, 0.5 part of trimethyl phosphate (0.693 mol% based on dimethyl terephthalate) was added to the obtained reaction product. and 0.3
Phosphoric acid prepared by reacting 1 part of calcium acetate monohydrate (1 part, 2 times the mole relative to trimethyl phosphate) in 8.5 parts of ethylene glycol at a temperature of 120'C for 60 minutes under total reflux. Diester calcium salt phosphate obtained by dissolving 0.57 parts of calcium acetate monohydrate (0.9 times mole relative to trimethyl phosphate) at room temperature in 9.31 parts of a clear solution of diester calcium salt and acetic acid. 9.88 parts of a clear mixed solution with calcium were added, followed by 0.04 parts of antimony trioxide (transferred to a night tin).

Then, over 1 hour, 760 pieces H9 to 11. , Hg, and simultaneously heated from 230°C to 28°C over 1 hour and 30 minutes.
The temperature was raised to 5°C. 1) Under reduced pressure of 1 g or less, polymerization was carried out at a polymerization temperature of 285°C for an additional 3 hours, for a total of 4 hours and 30 minutes, to obtain a polymer having an intrinsic viscosity of 0.641 and a softening point of 259°C. After the reaction was completed, the polymer was formed into a φ tube according to a conventional method.

A predetermined amount of the organic compound shown in Table 1 was triblended to 100 parts of this chip, and then the resulting mixture was mixed with a pore size of 0.
Melt spinning was carried out at 275°C using a spinneret with 36 circular spinning holes, and then the drawing ratio was 3 according to a conventional method.
．． A raw yarn of 75 denier/36 filaments was obtained by drawing at a factor of 5.

S twist 2500T/m and 2 twist 2500T/m on this yarn
The highly twisted yarn was then heated at 80'C for 30 minutes to heat it up.

The high-twisted yarn has a warp density of 47 pieces/am + weft density of 32
A satin georgette fabric was woven by alternately arranging two S and Z twists in book/crrL.

The obtained gray fabric was heated to boiling temperature in a p-tally washer for 2 hours.
The cloth was subjected to a relaxing treatment for 0 minutes, subjected to grain raising, preset by a conventional method, and then treated with a 3.5-inch aqueous sodium hydroxide solution at boiling temperature to obtain a cloth with a weight loss rate of 10%.

DianlxBlac fabrics after these alkali treatments
k HG-FS (Mitsubishi Chemical Industries ■Product) 15%owf
After staining at 130°C for 60 minutes, sodium hydroxide 11/
A black dyed cloth was obtained by reduction washing at 70° C. for 20 minutes with an aqueous solution containing F1/l and hydrozulfite I Fl/1. The color depth and friction discoloration resistance of these black cloths after 200 wears were shown in the first grade.

Example 7 10 ( ) parts of dimethyl terephthalate, 60 parts of Kosenshingelirol, and 0.06 parts of calcium acetate monohydrate (0.066 mol % based on dimethyl terephthalate) were charged into a transesterification tank, and a nitrogen gas atmosphere was placed. 140°C for 4 hours
The transesterification reaction was carried out while the temperature was raised from 230°C to 230°C and the methanol produced was distilled out of the system. 30 minutes after the start of the transesterification reaction, a silica sol with an average primary particle diameter of 30 mμ and a concentration of 20 mμ using ethylene glycol as a dispersion medium was added to the polymer.
It was added so that the amount was 0% by weight. After the transesterification reaction was completed, 0.06 parts (0.083 mole based on dimethyl terephthalate) of trimethyl phosphate and 0.04 parts of antimony trioxide were added to the reaction product, and the mixture was transferred to a polymerization reactor. did. Next, it takes 1 hour (from 760 dragon Hg to 1w
Reduce the pressure to 11g and simultaneously reduce the pressure to 23g over 1 hour and 30 minutes.
From 0°C to 285°C! ! It was warm. 1. Under reduced pressure of H9 or less, at a polymerization temperature of 285°C for an additional 3 hours, a total of 4 hours 30
After partial polymerization, the intrinsic viscosity was 0.636.

Po9-q- with a softening point of 262°C was obtained. After the reaction was completed, the polymer was made into chips according to a conventional method.

Hereinafter, using this chip, in the same manner as in Example 1, triblending with 1-phthalimido-3-phthalimidomethyl-3,5,5-)limethylcyclohexane, melt spinning,
Stretched 1 strong twist, no twist.

Performs weaving, grain raising, alkali weight reduction treatment, beam coloring, and reduction cleaning. The results were as shown in Table 1.

Comparative Examples 1 to 2 Examples 1 and 7, respectively, except that the organic compound (imide compound) used in Examples 1 and 7 was not used.
I did the same thing. The results are shown in Table 1.

Procedural amendments to the Commissioner of the Japan Patent Office 1, Indication of the case, Patent Application No. 1987-126766, 2, Name of the invention, Method for producing brightly dyeable polyester fibers 3. Person making the amendment, Relationship to the case, Special r: Applicant: Minami Higashi-ku, Osaka City Honmachi 1-11 (300') Teijin Ltd. Representative Tomio Tokusue 6 Contents of amendment Ryu-X Esha Neri (1) In the 5th line of page 16 of the specification, the word ``total'' has been replaced with ``composite''. ” he corrected.

(2) On page 17, line 3, the text “1l111 dogification” was replaced with “
I am corrected by saying, ``coarseness''.

(3) Same g24N 9th line K r(1>-z -0-
J Correct "tosuru" as rQ-Z-QJ.

(4) Same No. 25 @lp; IQ-- on line 12)
It says, ``Correct it as ``gutsu-z, C, t J.''

(5) Same page 26, line 11 K. Correct "-1,8-7 tarimide" to "1-1,8-naphthalimide."

(6) On page 33, line 14, the phrase 1 under total reflux is corrected to read ``under total reflux.''

LL top 121

Claims (1)

[Scope of Claims] 1. In producing brightly dyeable polyester fibers by reducing the amount of polyester fibers containing a metal-containing compound that is soluble in alkali or can be used in aqueous solution of alkaline compounds, The following conditions (11 to (4)) are applied to polyester fibers in advance.
Contains an organic compound that satisfies U 7P! A method for producing vividly dyeable polyester fibers, characterized in that the weight loss rate of J ester fibers by treatment with an aqueous alkali compound solution is 2% by weight or more. (1) It is substantially stable under the melting conditions of the H-type polyester that serves as the base of the polyester fiber, does not react with the polyester, and is compatible with the polyester polyester. (2) No phase separation occurs when the molten mixture with the polyester is cooled and solidified. (3) The melting point is 100°C or higher. (4) The molecular weight is 1000 or less.