JPH04149269A - Modified polyester composition - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for clearly colored sport clothings when used as the fibers having high antistatic properties and excellent dyeability in cationic dyes by mixing a modified polyester together with a specific polyoxyethylene-based polyether and an organic metallic salt. CONSTITUTION:(A) 100 pts.wt. modified polyester copolymerized with 0.1-10mol% phosphonium sulfonate expressed by formula I (A is aromatic, etc.; X1 is ester- forming functional group; X2 is H, etc.; R1 to R4 are alkyl or aryl; (n) is positive integer) is mixed with (B) 0.2-30 pts.wt., especially 0.5-5 pts.wt. water-insoluble type non-random copolymer of polyoxyethylene-based polyether expressed by formula II (z) is an organic compound having <300 molecular weight and 1-6 active hydrogens; R<1> is >=6C alkylene; R<2> is H, etc.; (k) is 1-6; (l) is a number so as kXl to be >=70; m>=1) having 500-16000 averaged molecular weight and (C) 0.05-10 pts.wt., especially 0.1-7 pts.wt. organic metallic salt (preferably metallic salt of sulfonic acid).

Description

Detailed Description of the Invention <Industrial Application Field> The present invention provides a modified polyester composition, more specifically suitable for melt molding, especially melt spinning, and having high antistatic properties and excellent cationic dye dyeability. The present invention relates to modified polyester compositions.

<Prior Art> Polyester has many excellent properties and is therefore widely used as a molding material for fibers, films, sheets, and the like. However, since polyester is hydrophobic, it is prone to static electricity, and for example, polyester fibers can cause a crackling discharge phenomenon when putting on and taking off clothes, and a phenomenon that clings to the body while wearing it, which can cause discomfort to people. Furthermore, it has the disadvantage that it attracts dust and spoils the appearance of clothes, which limits its use in fields where static electricity prevention is required.

Many attempts have been made to add antistatic properties to polyester in an attempt to overcome the second drawback.
For example, a method of mixing polyester with a polyoxyalkylene glycol polyamide pro-I copolymer or a polyoxyalkylene glycol polyester block copolymer which is substantially incompatible therewith; A method of adding an organic or inorganic ionic compound to this has been proposed (for example, Japanese Patent Publication No. 44-3i828, Japanese Patent Publication No. 60-11944, Japanese Unexamined Patent Publication No. 5F-81). 1986-
39413).

- Since polyoxyethylene glycol, which is specifically used in this method, is water-soluble and has poor water resistance, polyoxyethylene glycol/polyamide block copolymer, polyoxyethylene glycol・Polyester pro-sita copolymer and polyoxyethylene glycol-polynisdel-hoba amide copolymer, etc., decrease in hydrophilicity as their insolubility increases, so water resistance can be improved by this method. It is difficult to obtain a polyester molded product that has both excellent electrostatic properties and electrostatic properties at the same time.Therefore, the name of the present invention focuses on this antinomic tendency of hydrophilicity and water insolubility, and aims to overcome these antinomic properties. We attempted to solve the above problems by using a new polyoxyethylene polyether.Based on this research concept, we repeatedly tested a large number of compounds and found that polyoxyethylene glycol Polyoxyethylene-based polyether, which is block-copolymerized with a specific amount of a specific higher olefin oxide at both ends of the cool, has excellent water insolubility and, surprisingly,
It was found that improved hydrophilicity was exhibited, i.e.
Although the polyoxyethylene polyneedle is water-insoluble, it exhibits higher hygroscopicity than water-soluble polyoxyethylene glycol with an average molecular weight of 120,000; for example, at a temperature of 20°C and a relative humidity of 86%, the latter's equilibrium moisture absorption While the rate is 20%, the former's rate is 60%, which is about three times higher.

Knowing that a polyester composition blended with such a special polyoxyethylene polyether exhibits outstanding initial performance and durability as well as antistatic properties, sweat absorption properties, and antifouling properties, I would like to propose this to you. A molded article made of such a composition has outstanding features in that it exhibits excellent antistatic properties and durability even under low temperature F of less than about 20° C. and low humidity of less than 40% relative humidity.

However, in an attempt to obtain an antistatic, cationic dyeable polyester composition by applying such polyoxyethylene polyether to a cationic dyeable polyester, it has been widely used industrially as a cationic dyeable polyester. When the above-mentioned polyoxyethylene-based polyether is blended with a polyester copolymerized with another metal sulfoisophthalic acid compound, which is commonly used as a cationic dye, the dyeability with cationic dyes is unexpectedly impaired. It became clear that it would turn out like this.

<Object of the Invention> As is clear from the above, an object of the present invention is to provide a polyester composition that has both high antistatic properties and excellent dyeability with cationic dyes.

<Structure of the Invention> In view of the above-mentioned problems, the inventor has made extensive studies and has found that
It has been found that the above-mentioned problems can be solved by using a 5-phosphonium sulfoisophthalic acid compound instead of a 5-metal sulfoisophthalic acid compound as a cationic dye dye-enabling agent, and the object of the present invention can be achieved. The present invention was completed as a result of further studies based on this knowledge.

That is, the present invention provides (a) the following general formula (1) [wherein A is an aromatic group or an aliphatic group, Xl is an ester-forming functional group, and X2 is an ester-forming functional group that is the same as or different from Xl. or a hydrogen atom, R1゜R2, R3 and R3 are the same or different groups selected from alkyl groups and aryl groups,
n indicates a positive integer. ] 0.1 to 10 sulfonic acid phosphonium salt represented by
(b) 0.2 to 30 parts by weight of a water-insoluble polyoxyethylene polyether that satisfies the following (i) and (ii) at the same time to 100 parts by weight of the modified polyester copolymerized in mol%
A modified polyester composition containing parts by weight and (C) 0.05 to 10 parts by weight of an organic metal salt.

(i) It is a non-random copolymerizable polyoxyethylene polyether represented by the following general formula (n).

Z −f (CH2C)←[20)＊+R” ○+
-R2]k-(II)1 In the formula, Z is an organic compound residue having a molecular weight of 300 or more and having 1 to 6 active hydrogens,
R1 is an unsubstituted or substituted alkylene group having 6 or more carbon atoms, R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent acyl group having 2 to 40 carbon atoms, k
is an integer from 1 to 6, ρ is an integer such that kXρ is 70 or more, m
represents an integer greater than or equal to 1. ] fii) The average molecular weight is 5,000 to 16,000.

The polyester used in the present invention is a polyester having terephthalic acid as the main acid component and at least one type of glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol as the glycol component. The main target is

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

Examples of the difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, and diphenyl dicarboxylic acid.

Aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. can be mentioned.

In addition, as diol compounds other than 5 above glycols,
For example, cyclohexane-1,4-dimetatool, neopentyl glycol, bisphenol 4, aliphatic, ring group, aromatic diol compounds such as bisphenol S, and polyoxyalkylene glycol can be mentioned.

Historically, polycarboxylic acids such as trimellitic acid and pyromellitic acid, glycerin, and trimethylolpropane are used as long as the polyester is actually linear.

Polyols such as petaerythritol can be used.

Such polyesters can 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 alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a transesterification reaction between terephthalic acid and ethylene glycol. 1. A first step reaction in which a glycol ester of terephthalic acid and/or a low polymer thereof is produced by reacting with an oxide; It is produced by a second step reaction in which the reaction product of the first step is heated under reduced pressure and subjected to a polycondensation reaction until a desired degree of polymerization is achieved.

The sulfonic acid phosphonium salt used as a copolymerization component in the present invention is represented by the following general formula (I). In the formula, A represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. Xl represents an ester-forming functional group, and a specific example is -C H -OR +C.

H 0moCR2), -10000 (CR2H “+a OJ(.

CfOmoCH2) lower-7]"-d(,) I- (where R' is a lower alkyl group or phenyl group, a and d are an integer of 1 or more, b is an integer of 2 or more), etc. X2 represents an ester-forming functional group or a hydrogen atom that is the same as or different from Xl, and is preferably an ester-forming functional group.R+, R2, Ra
and indicate the same or different groups consisting of alkyl groups and aryl groups. n is a positive integer.

Such a sulfonic acid phosphonium salt can be easily synthesized by a reaction between a sulfonic acid corresponding to -4 and a phosphine, or a reaction between a corresponding sulfonic acid metal salt and a phosphonium halide.

Preferred specific examples of the sulfonic acid phosphonium salts include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, and 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt.
Dicarboxybenzenesulfonic acid benzyltributylphosphonium salt, 3.5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3.5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt, 35-dicarboxybenzenesulfonic acid butyltriphenyl Phosphonium salt, 3,5-dicarboxybenzecysulfonic acid henzyltriphenylphosphonium salt,
3,5-Dicarpomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyltributylphosphonium salt, 3,
5-Dicarbomethoxypenzene sulfo〉・acid henge l retributyl rephosphonium salt.

3.5-dicarphomethoxybenzenesulfonic acid phenyltributylphosphonium salt, 3.5-dicarpomethoxybenzenesulfonic acid tetraphenylphosphonium salt,
3.5-dicarbomethoxybenzenesulfonate ethyltriphenylphosphonium salt, 35-dicarbo'methoxybenzene Ilephonic acid butyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonate hensyltriphenylphosphonium salt salt, 3-carboxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carboxybenzenesulfonic acid tetraphenylphosphonium salt, 3-carboxybenzenesulfonic acid tetra-
butylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetraphenylphosphonium salt +]5-di(
β-hydroxyethoxycarbonate) benzenesuflephonate tetrabutylphosphonium salt, 3,5-di(β-
Hydroxyethoxycarbonyl)henzenesulfonic acid detraphenylphosphoniuno\ salt 13-(β-hydroxyethoxycarbonyl)ben7en7llephonic acid tetrabutylphosphonium salt, 3-<β-hydroxy ethoxybenzenesulfonic acid tetraphenylphosphonium salt 14-hydroxyethoxybenzenesulfonic acid tetrabutylphosphonium salt, 2,6-dicarpoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt 1α-tetrabutylphosphonium sulfosuccinate Examples include acids. The above sulfonic acid phosphonium salts may be used alone or in combination of two or more.

In order to copolymerize the sulfonic acid phosphonium salt into a polyester, it may be added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the beginning of the second stage reaction. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is in the range of 0.1 to 10 mol % based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.
A range of 5 to 5 mol% is preferred. If the copolymerization ratio is less than 0.1 mol%, the resulting modified polyester fiber will have insufficient dyeing properties with cationic dyes, and the amount of 10 mol%
If the amount exceeds that level, the cationic dyeability no longer shows any significant improvement, and the physical properties of the polyester deteriorate on the contrary, making it difficult to achieve the object of the present invention.

In the modified polyester composition of the present invention, a water-insoluble polyoxyethylene polyether is blended with the above-mentioned modified polyester. In the present invention, water insolubility means that 5 g of a sample is added to 100 g of pure water and heated to 60°C at 100°C.
After heat treatment for a minute, the solid content obtained by cooling to room temperature and then centrifuging the obtained transparent supernatant liquid to dryness is 10% by weight or less.

Such polyoxyethylene-based polyether has a polyoxyethylene block represented by the following general formula <I[) as a main chain component, and the polyoxyethylene molecular chain terminal is 1
Or it is a non-random copolymerizable polyoxyethylene polyether blocked by two or more specific oxyalkylene units.

Z -dry--+ C, R2CR20)-r-+RI O
+m R2] k , , ([) in the above formula,
Z is a residue of an organic compound having a molecular weight of 300 or less and having 1 to 6 active hydrogen atoms, such as methanol propatool butanol, phenol ethylene glycol, bisphenol A, propylene glycol, butylene glycol,
Neopentyl glycol, glycerin, trimethylolpropane triethanolamine, diglycerin.

Examples include residues of droxyl group-containing compounds such as pentaerythritol and sorbitol, and residues of primary and secondary amines such as ethylenediamine, hexamethylenediamine and diethylenetriamine, among which hydroxyl group-containing compounds are preferred. R1 is an unsubstituted alkylene group or substituted alkylene group having 6 or more carbon atoms, preferably a monosubstituted alkylene group having 6 to 50 carbon atoms, and more preferably an alkylethylene group having 6 to 50 carbon atoms. . Preferred specific examples of R1 include cyclohexylene group, phenylethylene group, hexylethylene group, methyl-pentylethylene group,
Examples include heptylethylene group and methyl-hexylethylene group. Moreover, R1 may be a mixture of two or more of the above.

R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent acyl group having 2 to 40 carbon atoms,
The hydrocarbon group is preferably an argyl group, an argenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or a hydroxyalkyl group. Further, the acyl group is an alkanoyl group.

Argenoyl group, cycloalkylcarbonyl group.

An arylcarbonyl group or an alkylarylcarbonyl group is preferred. k is an integer of 1 to 6 corresponding to the number of active hydrogen atoms that the organic compound that is the basis of Z has. g
It is necessary that kX and Q are integers of 70 or more, and they may be the same or different between or within molecules. When the value of kXρ is less than 70, the initial antistatic performance, hot water durability, and washing durability of the ultimately obtained modified polyester composition molded product will be insufficient. In addition, as the value of 1(), Teρ increases, the antistatic property and its durability improve, but when this value exceeds 300, it becomes difficult to notice any significant improvement in the antistatic property and its durability. On the contrary, it tends to be difficult to make the polyoxyethylene polyether water insolubilized, so ρ is k
It is preferable that the value of Xρ is an integer of 300 or less.

kXJl) is more preferably in the range of 80 to 200. m is an integer of 1 or more, and may be the same or different between or within molecules, but all m within the branches bonded to Z must be an integer of 1 or more.
If a branch with rrl of 0 exists, the antistatic durability of the polyester composition molded product finally obtained will be insufficient. The arrangement of CH2CH2O units and RIO units constituting this polyoxyethylene polyether is as follows:
A polyoxyethylene block consisting of C, H2CH20 units constitutes the main chain, and it is necessary to take a localized arrangement by forming a block of R10 units or one unit or two or more units at the end of the polyoxyethylene molecular chain. be. By adopting such a specific structure, by introducing a small amount of R10 units, it is possible to make the polyoxyethylene polyether highly insolubilizable in water and highly improve its hygroscopicity,
A high degree of antistatic property and its durability can be achieved.5 If the H2CH20 units and the RI O4 position are arranged randomly, the object of the present invention cannot be achieved.7 The above-mentioned water-insoluble polyoxyethylene system The molecular weight of polyneedle ranges from 5,000 to 16,000, ranging from 0 to 5,000.
When there is no groove, no matter how many RIO units you increase, the heat of the polyoxyethylene polyether! In addition, it is difficult to prevent it from falling into hot alkali, washing water, etc., and the antistatic properties and durability of the polyester composition molded product ultimately obtained are insufficient.

When the molecular weight exceeds 16,000, the melt miscibility of the polyoxyethylene polyether in the modified polyester deteriorates rapidly (1), resulting in poor dispersibility, making melt molding difficult, and reducing antistatic properties. The physical properties of the molded product such as mechanical strength and mechanical strength will be deteriorated, making it virtually impossible to implement. Furthermore, as the molecular weight increases, the antistatic properties under low temperature and low humidity conditions also become poor. This is because the thermal movement of the polyoxyethylene-based polyether in the modified polyester matrix becomes smaller. This is presumed to be because the antistatic performance due to ion conduction deteriorates, especially at low temperatures.

Among these, the preferred molecular weight range of the polyoxyethylene polyether is 5,500 to 1.4,000.

Such a non-random copolymerizable polyoxyethylene polyether is produced by an 11th stage reaction in which an active hydrogen compound is reacted with ethylene oxide, then a 2nd stage reaction in which the product is reacted with an olefin oxide having 6 or more carbon atoms, and If necessary, the product can be synthesized by a third step reaction in which the hydroxyl terminal group of the product is capped with a hydrocarbon group or an acyl group. Among these olefin oxides, nonene oxide, cyclohexene oxide, and α-olefin oxide having 12 to 40 carbon atoms are particularly preferred.

Particularly preferred specific examples of the above polyoxyethylene polyethers are shown in Table 1.

Specific examples of R2 other than H in the compounds shown in Table 1 include R2= CH3, C6R5, CH2C6H9+
Cl2H25, Cx5Hsr, Cx5H35゜Cx5H3CO, Cx7H33CO, Cs□Hi5CO
- etc. are preferred. Such polyoxyethylene polyethers may be used alone or in combination of two or more.

The amount of water-insoluble polyoxyethylene polyether added is 0 to 100 parts by weight of the modified polyester.
．． It is in the range of 2 to 30 parts by weight. Preferably 0.3-1
The range is 0 parts by weight, and the range of 0.5 to 5 parts by weight is particularly preferable. When the amount is less than 0.2 parts by weight, hydrophilicity is insufficient and sufficient antistatic properties cannot be exhibited. Moreover, even if the amount is more than 30 parts by weight, no further improvement in antistatic properties is observed, and the mechanical properties and heat resistance of the resulting composition are deteriorated.

Lightfastness will be impaired.

In the modified polyester composition of the present invention, an organic metal salt is blended in combination with the water-insoluble polyoxyethylene polyether described above. What is the organometallic salt mentioned here?
Dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid.

Alkali metal salts of sulfonic acids formed from sulfonic acids such as hexadecylsulfonic acid and dodecylsulfonic acid and alkali metals such as sodium, potassium, and lithium;
Examples include alkali metal salts of phosphate esters such as sodium distearyl phosphate, and alkali metal salts of other organic carboxylic acids.

Furthermore, preferred examples of sulfonic acid metal salts include those represented by the following general formula.

R' 0 (R' O), <CH2)
t, SO3M [wherein R1' is a monovalent hydrocarbon group, R' is an alkylene group having 2 to 4 carbon atoms, and a is 1 to 1
00 integer, b is an integer from 2 to 4, M is Na, K, L
Alkali metal salts such as i. ] Among such organometallic salts, sodium dodecylbenzenesulfonate, a mixture of sodium alkylsulfonates having an average number of carbon atoms of 14, C12) 1250 (
CH2CH2O) 3 CH2CH2SO3Na.

C,,6H330(CH2CH2O) 2. cHzcH
Particularly preferred are metal salts of sulfonic acids such as zcHzsO3Na.

The above organic metal salts may be used alone or in combination of two or more.

The appropriate amount is 0.05 to 10 parts by weight per 100 parts by weight of the modified polyester.

If it is less than 0.05 parts by weight, the antistatic properties will be insufficient, and if it exceeds 10 parts by weight, the mechanical properties of the final composition molded product will be impaired. Among these, a range of 0.1 to 7 parts by weight is preferred.

Any method can be used to blend the water-insoluble polyoxyethylene polyether and organic metal salt,
Moreover, both can be blended into the modified polyester simultaneously or in any order.

That is, at any stage until the molding of the modified polyester is completed, for example, before the start of the polycondensation reaction of the modified polyester, during the double condensation reaction, at the end of the single polycondensation reaction, and when the modified polyester is in a molten state, , in the molding stage, etc., even if they are added after melt-mixing in advance, or added in two or more divided doses, both may be added separately in advance to the modified or unmodified polyester, and then before molding, etc. May be mixed. Furthermore, when added before the middle stage of the polycondensation reaction, it may be added after being dissolved or dispersed in a solvent such as glycol.

The modified polyester composition of the present invention may also contain antioxidants such as hindered phenol, sulfide, and phosphite, and/or ultraviolet absorbers such as benzophenone and benzotriazole. , it is preferable to do so. In addition, flame retardants, optical brighteners, colorants, and other additives may be added as necessary.

When producing fibers from the polyester composition of the present invention, any spinning conditions can be employed without any problems. For example, a method of melt spinning at a speed of 500 to 2,500 m/min, stretching, and heat treatment;
A method of melt spinning at a speed of 5,000 m/min and performing drawing and false twisting simultaneously or sequentially, a method of melt spinning at a high speed of 5,000 m/min or more and omitting the drawing step depending on the application, etc. Can be adopted. In addition, the obtained fiber or the woven or knitted fabric manufactured from this fiber is
The heat treatment is preferably carried out at a temperature of 00°C or higher, thereby stabilizing the structure of the polyoxyethylene polyether, organic metal salt, and various additives contained as necessary in the composition. Migration to the vicinity of the surface can be encouraged. Furthermore, relaxation heat treatment or the like can be used in combination, if necessary.

The composition of the present invention can also be used to produce films and sheets. Furthermore, any molding conditions can be adopted in this molding process without any problems.

For example, a method of manufacturing an anisotropic film by applying tension in only one direction after film formation, a method of stretching the film in two directions simultaneously or in an arbitrary order, and a method of multi-stage stretching of the film in two or more stages. , etc. can be adopted under any conditions. Also Phil 11. It is preferable to heat-treat the sheet or the like at a temperature of 100° C. or higher for the reasons mentioned above.

Furthermore, the composition of the present invention can also be used as a masterbatch. This masterbatch can also be diluted with conventional polyester and the mixture can be melt-molded into final molded articles such as fibers, films, sheets, etc.

The compositions of the present invention are particularly useful for forming antistatic cationic dyeable polyester fibers.

That is, the fiber formed from the composition of the present invention may be a solid fiber without a hollow part or a hollow fiber with a hollow part, and the fiber may have a shape in a cross section or a hollow part. The shape may be circular or irregular. Furthermore, even if it is a core-sheath type composite fiber having the composition of the present invention as a core component and a normal polyester as a sheath component, it may also be a core-sheath type composite fiber having a composition of the present invention as a sheath component and a normal polyester as a core component. It may be a sheath-type conjugate fiber, or it may be a multilayer conjugate fiber with two or more layers of the above-mentioned composition and ordinary polyester in a side-pie-side type.

Note that the molded article of the modified polyester composition of the present invention may be subjected to appropriate post-hydrophilization processing, etc., if necessary. After this hydrophilization, for example, the polyester fibers are treated with an aqueous polyester polyether block copolymer consisting of terephthalic acid and/or isophthalic acid or their lower alkyl esters, lower alkylene glycol, and polyalkylene glycol. Preferably, a method of treating with a dispersion liquid or a method of graft polymerizing a hydrophilic monomer such as acrylic acid or methacrylic acid and then converting this into a sodium salt can be preferably employed.

<Effects of the Invention> Molded articles such as fibers obtained from the modified polyester composition of the present invention can be dyed with cationic dyes, so they can obtain the vivid colors characteristic of cationic dyes, and can also be dyed under low temperature and low humidity conditions. It has sufficient antistatic properties, and this excellent cationic dye dyeability and high antistatic properties are suitable for processing such as false twisting and hard twisting, dyeing processing, and alkali weight loss treatment.

This has an extremely useful effect in practice, in that it will not be lost due to harsh post-processing treatments that require heat resistance and hydrolysis resistance, such as resin coating treatment, and even harsh washing treatments.

Therefore, the fibers obtained from the modified polyester composition of the present invention are particularly useful in sports clothing applications where vivid colors are required, as they provide excellent color development and high antistatic properties. In addition, it can be made into a blended yarn with regular polyester fibers, or mixed with regular polyester yarns to make woven or knitted fabrics, and dyed with cationic dyes and disperse dyes to create high-quality marbling effects and unique color dyeing effects. It is very useful in the field of application where it is desired to express a unique dyeing effect, since it is possible to impart a high degree of antistatic property.

In addition, the film made of the composition of the present invention does not generate static electricity even under low humidity conditions, so during the film forming process and slitting process, the films do not get twisted around each other or wrap around the roll, and the discharge sparks are prevented. It is also preferable from a safety standpoint, as there is no need to worry. The above films are dyed with cationic dyes in various vivid hues and can be usefully used for colored steel plates and gold and silver threads. Since such products do not attract dust due to charging, they can maintain their beautiful colors for a long time.

<Examples> In order to explain the present invention more specifically, five examples will be given below, but the present invention is not limited to these examples. Note that parts and % in Examples and Comparative Examples indicate parts by weight and % by weight, respectively. In addition, the frictional charging voltage of the obtained polyester fiber and the visual dyeability of the dyed cloth were measured using the following methods.

(1) Frictional charging voltage i) Apparatus and materials Rotating drum type frictional charging voltage measuring device (rotary static tester), oscilloscope, friction cloth 2-cotton broadcloth 30/- scouring, bleaching, glue-free finishing jj) Adjustment of test piece Winding type: 3 .8(1)\'30CO1 Gold frame type: 4
, 0σ\8.0α Take 3 sheets of friction cloth lengthwise.Furthermore, take 3 pieces of friction cloth cotton broad (30'-) 2.5cm x 14, 0cm lengthwise. 1ii) Test operation■ Humidity control: 40= 29δRH Manaha 30=2°oR1(0
(20±2
°(:), 3072°oR11<10=2°C> ■Sample: Number of stacked sheets: 1 ■Drum rotation speed: 700r, p, m (4I Charging equilibrium time: 1 minute ■Contact pressure load: 600g Test piece 1 Attach the sheet face up to the rotating drum of the rotary static tester, and then attach one piece of friction cloth to the clips at both ends of the bottom in a balanced manner at the position where it contacts the test piece.
Apply a load of 00g. Operate the recorder (5 (2) minutes) for one rotation of the drum and the oscilloscope in this order, and when charging equilibrium is reached, read the frictional charging voltage <V> and the extreme value, -).
Expressed as the average value of 3 sheets (up to 10th integer value).

The relationship between the antistatic effect and the frictional charging voltage indicates that the antistatic effect is good if the frictional charging voltage is 1500V or less.

(2) Congratulatory dyeing of dyed fabric The L° value, a° value, and b° value of the dyed fabric were measured using a Minolta color difference meter CR-200 <Minolta Camera Sales@).

Examples 1-3 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts, 0.03 parts of manganese acetate tetrahydrate (0.024 mol % based on dimethyl terephthalate), 0.009 parts of cobalt acetate tetrahydrate as a coloring agent, 0.007 mol based on dimethyl terephthalate %), 3.5-dicarboxybenzenesulfonic acid Detra n-butylphosphonium salt in an amount of 1.5 mol % relative to dimethyl terephthalate and 0.050 mol % tetraethylammonium hydroxide relative to dimethyl terephthalate. was charged into a transesterification reactor, and the temperature was raised from 140° C. to 220° C. over a period of 13 hours in a nitrogen gas atmosphere, and the transesterification reaction was carried out while the generated methanol and ethanol were distilled out of the system. The product obtained was then treated with 0.03% of a 56% aqueous solution of orthophosphoric acid as a stabilizer.
parts (0.033 mol% based on dimethyl terephthalate)
was added, and at the same time, expulsion of excess ethylene glycol was started at elevated temperature. After 10 minutes, 0.04 part of antimony dioxide (0.027 mol % based on terephthalic acid) was added as a polycondensation catalyst. When the temperature of the inner bath reached 240°C, expulsion of ethylene glycol was completed, and the reaction product was transferred to a polymerization vessel.

Next, the reaction was carried out at normal pressure without raising the temperature until the internal temperature reached 260°C, and then the temperature was increased from 760 mmftg to 1-
Reduce the pressure to mmHg and at the same time raise the temperature of the indoor bath to 280℃ over 1 hour and 30 minutes. Two hours after the start of decompression, the chemical formula below is HOMOCHCH20+-1-(-CBOCBOCBOCHOCH).

C) H2J+1 Mo CH2CHO+, HC, H2J+1 (where, j is an integer from 18 to 28 with an average of 21, ρ is an average value of about 115, and m is an average value of 3), and has an average molecular weight of 7106. The amount of insoluble polyoxyethylene〉' polyether listed in Table 2 is added in a molten state,
The amounts listed in Table 2 of sodium dodecylbenzenesulfonate were made into 50% ethylene glycol solutions and added under reduced pressure. Subsequently, polymerization was continued for 1 hour under reduced pressure of 1 mmHg or less with stirring, and then Cyanox 1790 (manufactured by American Cyanamid Company) 0,
1 part and 0.3 parts of Mark AO-4128 (manufactured by Adeka Argus Chemical Co., Ltd.) were added under reduced pressure, followed by further polymerization for 20 minutes to give an intrinsic viscosity of 0.630 to 0.650. A polymer composition with a softening point of 254-256°C was obtained.

This polymer composition was melted at 280'C and a diameter of 0.3
mgn, was spun using a spinneret with 24 spinning holes with a length of 0.6n+m, and passed through a godet roller to
It was once wound up at a speed of 0 m/min. Next, the preheating temperature was 8 at a stretching ratio such that the elongation of the spun yarn after stretching was 35%.
A drawn yarn of 75 denier/24 filaments was obtained by drawing heat treatment using a heating roller at 0°C and a plate heater at 130°C.

The obtained drawn yarn was made into a knitted fabric, and after scouring and presetting (<180°C x 45 seconds) by a conventional method,
lon Blue CD-PRLH/Cathilon
Blue CD-FBLH (manufactured by Hodogaya Chemical) = 1
/1, 2% owf, mirabilite 3g/fJ, acetic acid 0.3g/
After dyeing for 60 minutes at 120°C in a dyebath containing fJ, soaping and final set 1 according to the usual method.
60℃ x 60 seconds to obtain a clear blue cloth. The coloring property of this blue cloth was as shown in Table 2.

Furthermore, using this fabric, the frictional charging voltage was measured after 0 washes (referred to as LO) and 30 washes (referred to as Li2), and the results shown in Table 2 were obtained.

In addition, the washing method was as follows.

(Wash i! Processing) Using a household washing machine, add 2 g of New Enzyme Sub (manufactured by Kao) at 30 ρ (bath ratio 1.:30), add the sample, and wash.
Wash at 0'C for 10 minutes with self-winding water flow.

After that, dehydrate and 30 fl of 40°C warm water (bath ratio 1:3
0> for 5 minutes and dehydration, then overflow water washing for 10 minutes and dehydration. The above washing is treated as one time,
This was repeated as many times as necessary.

Example 4 3 and 5 used as cationic dye dyeable agents in Example]
-Dicarbomethoxybenzenesulfonic acid tetra-rl-
3.5dicarboxybenzenesulfonic acid tetraphenylphosphonium salt is used in place of the butylphosphonium salt in an amount of 2.5 mol% based on dimethyl terephthalate;
The same procedure as in Example 1 was carried out except that the addition timing was after the end of the transesterification reaction and before the addition of pressurized phosphoric acid. The results were as shown in Table 2.

Example 5 In place of the polyoxyethylene polyether used in Example 1, the following chemical formula % formula % is used. However, j is an integer from 10 to 12 with an average of 11, ρ is an average value of about 180, and m is an average value. Example 1 was carried out in the same manner as in Example 1, except that a water-insoluble polyoxyethylene polyether having an average molecular weight of 111,898 and having an average molecular weight of 111,898 was used. The results were as shown in Table 2.

Example 6 Same as Example 1 except that 0.8 part of a sulfonic acid metal salt represented by the following chemical formula % was added in a molten state in place of the sodium dodecylbenzenesulfonate used as the organic metal salt in Example 1. I did the same. The results are shown in Table 2.

Comparative Example Tetra-3,5-dicarbomethoxybenzenesulfonic acid used as a cationic dye dyeing agent in Example 1
3.5-dicarbomethoxybenzenesulfonic acid sodium salt and terephthalic acid in an amount of 2.5 mol % based on dimethyl terephthalate instead of the n-butylphosphonium salt and tetraethylammonium hydroxide used as diethylene glycol formation inhibitor. The same procedure as in Example 1 was carried out except that sodium acetate trihydrate was used in an amount of 0.160 mol % based on dimethyl. As shown in Table 2, only a dull, whitish blue cloth was obtained.

Claims (1)

[Claims] (a) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, A is an aromatic group or an aliphatic group, and X_1 is an ester-forming group. Functional group, X_2 is the same or different ester-forming functional group or hydrogen atom as X_1, R_1, R_2, R_3
and R_4 are the same or different groups selected from alkyl groups and aryl groups, and n is a positive integer. ] 0.1 to 10 sulfonic acid phosphonium salt represented by
(b) 0.2 to 30 parts by weight of a water-insoluble polyoxyethylene polyether that simultaneously satisfies (i) and (ii) below and (c) an organic metal salt to 100 parts by weight of the modified polyester copolymerized with mol% A modified polyester composition containing 0.05 to 10 parts by weight. (i) It is a non-random copolymerizable polyoxyethylene polyether represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, Z is the residue of an organic compound with a molecular weight of 300 or less and has 1 to 6 active hydrogen atoms, and R^1 is a residue with a carbon number of 6 or more. Substituted or substituted alkylene group, R^2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms or 2 to 4 carbon atoms
0 monovalent acyl group, k represents an integer of 1 to 6, l represents an integer such that k×l is 70 or more, and m represents an integer of 1 or more. ] (ii) The average molecular weight is 5,000 to 16,000.