JP3345173B2 - Modified polyester and modified polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyester and a modified polyester fiber, and more particularly, to a modified polyester capable of dyeing cationic dyes (hereinafter referred to as a modified polyester) having remarkably improved light fastness. A) and modified polyester fibers.

[0002]

2. Description of the Related Art Polyesters, especially polyethylene terephthalate, are widely used as molding materials for fibers, films, sheets, etc. because of their many excellent properties. Dyes other than poor disperse dyes are difficult to dye, and therefore have the disadvantage of inferior clear color development upon dyeing, and improvements have been demanded.

Conventional methods for improving dyeing properties include, for example, 5-sodium sulfoisophthalic acid and 5-tetrabutyric acid.
A method is known in which a dye can be dyed with a cationic dye by copolymerizing an aromatic sulfonic acid metal base such as ruphosphonium sulfoisophthalic acid or an isophthalic acid component having an aromatic sulfonic acid phosphonium base (Japanese Patent Publication No. 34-34). No. 10497, Japanese Patent Publication No. 3-61766, etc.). According to these methods, a cationic dye having a larger molecular extinction coefficient than that of a disperse dye can be used, so that the sharp coloring of a dyed product is significantly improved as compared with a disperse dye. However, these modified polyesters have the disadvantage that the lightfastness of the dyed product is considerably inferior to ordinary polyesters dyed with a disperse dye or acrylics that can be dyed with a cationic dye like the modified polyester. . For example, when used in textiles, especially when used in sports applications such as ski wear, wind breakers, marine wear, etc., taking advantage of its vivid color development, the cationic dye is easily decomposed and discolored by ultraviolet rays contained in sunlight. There are disadvantages, and improvements have been required.

Furthermore, in these methods, the melt viscosity of the polymerization reaction product is remarkably increased due to the thickening action of the isophthalic acid component containing the metal sulfonate group, making it difficult to sufficiently increase the degree of polymerization. Spinning was also difficult. Accordingly, in order to lower the melt viscosity of the modified polyester obtained by copolymerizing the isophthalic acid component containing the sulfonic acid metal base to a range where the polymerization is easy and the melt spinning can be performed, the polymerization degree of the modified polyester is lowered. Need to be kept. As a result, the strength of the resulting yarn is reduced, and when forming into a fiber, even if an attempt is made to produce an ultrafine yarn having a single-filament fineness of 1.0 denier or less by high-speed spinning, the modified polyester has extremely poor spinnability. Even if single yarn breakage occurs frequently during spinning and spinning is impossible, or if spinning is possible, the obtained yarn is not actually used because it has extremely low mechanical properties and cannot be used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the light discoloration resistance of cationic dyeable polyester dyed products to the level of cationic dye dyed products of acrylic fibers, and to further expand the uses thereof.

Still another object of the present invention is to provide a spinning method for ultrafine fibers having a fineness of single denier of 1.0 denier or less, which is equivalent to the strength and elongation properties of ordinary unmodified polyester and spinning properties of ultrafine fibers. An object of the present invention is to provide a modified polyester which is also used.

[0007]

The above-mentioned problems have been solved in the following manner. Cationic dyes with excellent lightfastness In dyeable acrylic fibers, aliphatic sulfonates such as sodium allylsulfonate and sodium methallylsulfonate are used as copolymerization components that serve as cationic dyeing seats. On the other hand, in the cationic dye-dyeable modified polyester fiber, the aromatic ring is activated by absorbing ultraviolet light because the aromatic sulfonate is used as described above. As a result, a mechanism for decomposing a cationic dye formed into a salt with a sulfonic acid group directly bonded to the aromatic ring was investigated.

On the basis of the above findings, the present inventors have conducted intensive studies on aliphatic or alicyclic sulfonates which are transparent to ultraviolet rays as cationic dye dyeing agents to be copolymerized into polyester. However, aliphatic sulfonates do not have the effect of improving light resistance, probably because of insufficient heat resistance, and are specifically disclosed in US Pat. No. 3,682,866 and US Pat. No. 4,579,936. Light-fastness even with dyeable polyesters of cationic dyes copolymerized with selected metal salts of alicyclic sulfonic acids such as 3,5-dicarboxycyclohexanesulfonic acid sodium salt and 3,5-dicarbomethoxycyclohexanesulfonic acid sodium salt The improvement effect was small.

[0009] However, surprisingly, the dyeability modification of a cationic dye obtained by copolymerizing a phosphonium salt of 3,5-dicarboxycyclohexanesulfonic acid, which is a reaction product of the metal salt of alicyclic sulfonic acid and phosphonium halides, is performed. Polyester has good heat resistance, and at the same time, the light resistance when dyeing a fiber made of the polyester with a cationic dye is remarkably improved. Was found to be no different from the high quality polyester. The present inventors have made further studies based on these findings and completed the present invention.

That is, the present invention relates to a cationic dye dyeing-modified polyester which is represented by the following general formula (I) as a cationic dye dyeing agent:

[0011]

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The alicyclic sulfonic acid phosphonium salt represented by the formula (1) is used in an amount of 0.1 to 20 mol% based on all acid components except the alicyclic sulfonic acid compound, which constitutes the modified polyester.
A modified polyester characterized by being copolymerized,
And a modified polyester fiber obtained by melt-spinning the modified polyester.

The polyester (polyester before copolymerizing the compound represented by the above general formula (I)) in the present invention is a polyester comprising at least one difunctional carboxylic acid and at least one glycol.

The bifunctional carboxylic acids include, for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxy benzoic acid, p-oxybenzoic acid, adipic acid, Aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as sebacic acid and 1,4-cyclohexanedicarboxylic acid can be mentioned, and terephthalic acid or, preferably, terephthalic acid is the main acid component.

Meanwhile as glycols, e.g., ethylene glycol, trimethylene glycol, at least one alkylene <br/> glycolic, cyclo-hexane-1,4-dimethanol selected from tetramethylene glycol,
Examples thereof include aliphatic, alicyclic, aromatic diol compounds such as neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols, and among them, ethylene glycol or a main diol component is preferred. .

Further, within the range in which the effects of the present invention are substantially exerted, aromatic and aliphatic substances such as 5-sodium sulfoisofurtalic acid, m-sodium sulfobenzoic acid, and sodium 3,5-dicarboxycyclohexanesulfonate; A compound having an alicyclic sulfonic acid metal base may be used as a copolymer component.

Further, as long as the polyester is substantially linear, polycarboxylic acids such as trimellitic acid and pyromellitic acid, glycerin, trimethylolpropane,
Polyols such as pentaerythritol can be used.

Such a polyester is synthesized by any method. For example, in the case of polyethylene terephthalate, for example, terephthalic acid and ethylene glycol are usually directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are used. A first-step reaction of reacting with an oxide to form a glycol ester of terephthalic acid and / or a low polymer thereof, and heating the reaction product of the first step under reduced pressure until a desired degree of polymerization is obtained. It is produced by a second stage reaction of a polycondensation reaction.

The alicyclic sulfonic acid phosphonium salt copolymerized with the above polyester as a cationic dye dyeing agent must be a sulfonic acid phosphonium salt represented by the above general formula (I).

In the above general formula (I),

[0021]

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Is a cyclohexane ring, which may be either trans or cis, or a mixture of both. X ₁ represents an ester-forming functional group, and as a specific example,

[0023]

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(Provided that R 'is a lower alkyl group or a phenyl group, a and d are integers of 1 or more, and b is an integer of 2 or more).

[0025]

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It is preferred that X ₂ is the same as or different from X ₁ and represents an ester-forming functional group or a hydrogen atom, and is preferably an ester-forming functional group. R ₁ , R ₂ , R ₃ and R ₄ represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n is a positive integer. The above-mentioned alicyclic sulfonic acid phosphonium salt can be easily synthesized by generally reacting a corresponding alicyclic sulfonic acid with a phosphine, or reacting a reactive sulfonic acid metal salt with a phosphonium halide.

Preferred specific examples of the alicyclic phosphonium phosphonium salt include tetrabutylphosphonium 3,5-dicarboxycyclohexanesulfonate, 3,5
-Ethyl tributyl phosphonium dicarboxycyclohexanesulfonate, benzyltributyl phosphonium 3,5-dicarboxycyclohexanesulfonate,
3,5-dicarboxycyclohexanesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxycyclohexanesulfonic acid tetraphenylphosphonium salt, 3,5-dicarboxycyclohexanesulfonic acid butyltriphenylphosphonium salt, 3,5-dicarboxycyclohexane Benzyl triphenyl phosphonium sulfonate, tetrabutyl phosphonium 3,5-dicarboxycyclohexane sulfonate, ethyl tributyl phosphonium 3,5-dicarboxycyclohexane sulfonate, benzyl tributyl phosphonium 3,5-dicarboxycyclohexane sulfonate, 3,5-dicarboxycyclohexanesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxycyclohexanesulfonic acid tetraf Niruhosuhoniumu salts, 3,5-di-carboxy cyclohexane sulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarboxylate-cyclohexane sulfonic acid butyl triphenyl phosphonium salt, 3,
5-dicarboxycyclohexanesulfonic acid benzyltriphenylphosphonium salt, 3-carboxycyclohexanesulfonic acid tetrabutylphosphonium salt, 3-carboxycyclohexanesulfonic acid tetraphenylphosphonium salt, 3-carbomethoxycyclohexanesulfonic acid tetrabutylphosphonium salt, 3-carbo Methoxycyclohexanesulfonic acid tetraphenylphosphonium salt, 3,5-di (β-hydroxyethoxycarbonyl)
Cyclohexanesulfonic acid tetrabutylphosphonium salt, 3,5-di (β-hydroxyethoxycarbonyl)
Cyclohexanesulfonic acid tetraphenylphosphonium salt, 2,5-dicarboxycyclohexanesulfonic acid tetrabutylphosphonium salt, 3- (β-hydroxyethoxycarbonyl) cyclohexanesulfonic acid tetrabutylphosphonium salt, 3- (β-hydroxyethoxycarbonyl) cyclohexanesulfone Acid tetraphenylphosphonium salt, 4-hydroxyethoxycyclohexanesulfonic acid tetrabutylphosphonium salt, and the like. The alicyclic sulfonic acid phosphonium salt may be used alone or in combination of two or more.

In order to copolymerize the alicyclic sulfonic acid phosphonium salt with the polyester, it may be added at a stage before the completion of the above-mentioned synthesis of the polyester, preferably at an arbitrary stage before the initial stage of the second stage reaction. I just need. The proportion of the alicyclic sulfonic acid phosphonium salt copolymerized with the polyester excludes the alicyclic sulfonic acid phosphonium salt constituting the cationic dye dyeability-modified polyester in which the alicyclic sulfonic acid phosphonium salt is copolymerized. It is in the range of 0.1 to 20 mol%, especially 0.5 to 10 mol% based on the total acid component.
A mole% range is preferred. Here, the copolymerization ratio is 0.1
If the amount is less than 20 mol%, the sharpness of the resulting modified polyester obtained by dyeing with a cationic dye becomes insufficient, while if the amount exceeds 20 mol%, the sharpness does not show any remarkable improvement. , Physical properties such as abrasion resistance, moldability and the like are reduced.

The use of the alicyclic phosphonium phosphonium salt described above may deteriorate the heat resistance of the polymer. This disadvantage is caused by the quaternary onium disclosed in Japanese Patent Publication No. 3-61766. This can be avoided by the addition of salts.

The composition of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent brightener, a matting agent, a coloring agent, and other additives.

In the case of producing fibers from the modified polyester of the present invention, any yarn forming conditions can be adopted without any trouble. For example, a method of melt-spinning at a speed of 500 to 2500 m / min, stretching and heat treatment, 1500 to 50
A method of melt spinning at a high speed of 00 m / min and simultaneous or subsequent stretching and false twisting, a method of melt spinning at a high speed of 5000 m / min or more, and a method of omitting the stretching depending on the application. Conditions can be adopted. On this occasion,
The cross-sectional shape and fineness of the obtained fiber may be set as desired.

The modified polyester of the present invention can be used for the production of films and sheets, in which case any molding conditions can be adopted without any hindrance.
For example, a method of producing an anisotropic film by applying tension in only one direction after film formation, a method of stretching a film in two directions simultaneously or in any order, and a method of stretching a film in two or more stages in multiple stages, etc. It can be adopted under any conditions.

[0033]

According to the present invention, especially in spinning of ultrafine fibers having a single yarn fineness of 1.0 denier or less, the same high elongation properties and ultrafine fiber spinning properties as those of ordinary unmodified polyester are combined. A modified polyester is provided. In addition, when the fiber obtained from the polyester is dyed with a cationic dye, the dyed material has excellent vivid color development and dramatically improved light fastness (discoloration degree), so that skiwear, windbreakers, marine It is very useful because it can be applied to outdoor sports textiles such as clothing.

Films and sheets obtained from the modified polyester of the present invention are extremely useful because they have excellent properties such as strength and light resistance, and also have excellent antistatic properties, water absorption, printing properties, adhesive properties and the like. is there.

The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Parts and% in Examples are parts by weight and% by weight, respectively. The intrinsic viscosity [η] of the polymer was determined from the value measured with an orthochlorophenol solution at 35 ° C. In addition, the visual infectious color and the light discoloration resistance of the dyed cloth were measured by the following methods.

(1) Visual Infectivity of Dyeing Cloth L ^* , a ^* , and b ^* values of the dyed cloth were measured using a Minolta Colorimeter CR-200 (Minolta Camera Sales Co., Ltd.), and the lightness was measured. Index (L ^* ) and saturation ｛(a ^{* 2} + b ^{* 2} )
^{The darkness} and clear color development were determined by ^{1/2 1/2} . The smaller the lightness index, the greater the deep color, and the greater the saturation, the greater the vivid color development.

(2) Light discoloration resistance of the dyed cloth According to JIS L0842-71, the dyed cloth is exposed to ultraviolet light.
63 with a tofade meter (Suga Test Machine Co., Ltd.)
C for 20 hours, and L of dyed cloth before and after light irradiation ^*value,
a^*Value, b^*The value was measured in the same manner as in (1) above,
In accordance with Z8730-1980, the light discoloration resistance ΔE is obtained from
^*Is calculated.

[0038]

ΔE ^* = ｛(ΔL ^* ) ² + (Δa ^* ) ² + (Δ
b ^* ) The smaller the ² ｝ ^1/2 light fastness ΔE ^* , the smaller the discoloration and fading, and the better the light fastness. Also, JIS L084
The grade of the blue scale showing the same level of discoloration as the sample is shown by comparing and judging the discoloration with the blue scale based on 1-66. Practically grade 4 or higher is passed.

Example 1 Dimethyl terephthalate 100
Parts, ethylene glycol 60 parts, manganese acetate tetrahydrate 0.03 part (0.024 parts based on dimethyl terephthalate)
Mol%), cobalt acetate tetrahydrate 0.009 as a color-matching agent
Parts (0.007 mol% based on dimethyl terephthalate) and 2.5 mol% based on dimethyl terephthalate as a cationic dye dyeing agent in an amount of 3,5-dicarbomethoxycyclohexanesulfonate tetrabutylphosphonium Tetraethylammonium hydroxide in an amount of 0.080 mol% based on dimethyl terephthalate as a salt and a stabilizer is charged into a transesterification vessel, and the temperature is increased from 140 ° C. to 220 ° C. over 4 hours in a nitrogen gas atmosphere. The transesterification reaction was carried out while distilling off methanol from the system. The resulting product was then added with 5
0.036 parts of a 6% aqueous solution (0.040 mol% with respect to dimethyl terephthalate) was added, and at the same time, the temperature was raised to remove excess ethylene glycol. After 10 minutes, 0.04 parts of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added as a polycondensation catalyst. When the internal temperature reached 240 ° C., the expulsion of ethylene glycol was terminated, and the reaction product was transferred to a polymerization vessel. Then, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and the internal temperature was raised from 240 ° C to 280 ° C over 1 hour and 30 minutes. Polymerization was further performed under a reduced pressure of 1 mmHg or less at a polymerization temperature of 280 ° C. until the stirring power reached a predetermined value. After completion of the reaction, the polymer was formed into chips according to a conventional method. The intrinsic viscosity [η] of the obtained polymer was as shown in Table 1.

The obtained polymer is dried by a conventional method, spun at 285 ° C. at a spinning speed of 1100 m / min using a spinneret having 24 circular spinning holes having a diameter of 0.3 mm, and then obtained. At a draw ratio of elongation of the drawn yarn of 30%, drawing and heat treatment are carried out at a drawing speed of 1200 m / min by using a heating roller at 84 ° C. and a plate heater at 180 ° C. to obtain 75 denier / 24 filaments. A drawn yarn was obtained. Table 1 shows the strength of the obtained drawn yarn.

The obtained drawn yarn is knitted into a knitted fabric according to a conventional method, scoured and preset by a conventional method, and
ilon Blue CD-FRLH / Cathilon Blue CD-FBLH = 1/1
(Manufactured by Hodogaya Chemical Co., Ltd.) Dyeing is performed at 130 ° C. for 60 minutes in a dye bath containing 2% owf, sodium sulfate 3 g / L and acetic acid 0.3 g / L, and then soaped according to a conventional method to obtain a blue cloth. Was. Table 1 shows the visual infection colorability and the light discoloration resistance of the obtained dyed fabric.

Example 2 Tetraphenyl 3,5-dicarbomethoxycyclohexanesulfonate was used in place of the tetrabutylphosphonium 3,5-dicarbomethoxycyclohexanesulfonate used as a dye dyeing agent in Example 1. Polymerization, melt spinning, drawing heat treatment, knitting and cationic dyeing were carried out in the same manner as in Example 1 except that the phosphonium salt was used in an amount of 2.5 mol% based on dimethyl terephthalate. The results are shown in Table 1.

Comparative Example 1 Tetrabutyl 3,5-dicarbomethoxybenzenesulfonate was used in place of tetrabutylphosphonium 3,5-dicarbomethoxycyclohexanesulfonate used as a dye dyeing agent in Example 1. Polymerization, melt spinning, drawing heat treatment, knitting and cationic dyeing were carried out in the same manner as in Example 1 except that the phosphonium salt was used in an amount of 2.5 mol% based on dimethyl terephthalate. Table 1 shows the results.

Comparative Example 2 Tetraphenyl 3,5-dicarbomethoxybenzenesulfonate was used in place of tetraphenylphosphonium 3,5-dicarbomethoxycyclohexanesulfonate used as a dye dyeing agent in Example 2. Polymerization, melt spinning, drawing heat treatment, knitting and cationic dyeing were carried out in the same manner as in Example 2 except that the phosphonium salt was used in an amount of 2.5 mol% based on dimethyl terephthalate. The results were as shown in Table 1.

Comparative Example 3 Sodium 3,5-dicarbomethoxycyclohexanesulfonate instead of 3,5-dicarbomethoxycyclohexanesulfonate tetrabutylphosphonium used as a cationic dye dyeing agent in Example 1 Is used in an amount of 2.5 mol% based on dimethyl terephthalate, and sodium acetate trihydrate as an ether formation inhibitor is added in an amount of 0.1 to dimethyl terephthalate in place of tetraethylammonium hydroxide used as a stabilizer. The procedure was performed in the same manner as in Example 1 except that the amount used was 150 mol%. The results are shown in Table 1.

Reference Example 1 Using an acrylic fiber cloth,
Cationic dyeing was performed in the same manner as in Example 1 except that the dyeing temperature was changed to 100 ° C. The results were as shown in Table 1.

[0047]

[Table 1]

Reference Example 2 Unmodified polyethylene terephthalate having an intrinsic viscosity of 0.640 was vacuum-dried at 120 ° C. for 6 hours, and the maximum was obtained by using a spinneret having 72 circular ejection holes having a diameter of 0.15 mm. 3
It was melted at 10 ° C. and spun at a high take-off speed of 4300 m / min to obtain an ultrafine yarn of 36 denier / 72 filaments (single yarn 0.5 denier). At this time, the yarn traveling distance from the spinneret to the first take-up roller (godet roller) was 3 m. Table 2 shows the spinning condition and the physical properties of the obtained ultrafine yarn at this time.

Example 3 The same as Reference Example 2 except that the cationic dye dyeable polyester used in Example 1 was used instead of the unmodified polyethylene terephthalate having an intrinsic viscosity of 0.640 used in Reference Example 2. I went to. The results are shown in Table 2.

Comparative Example 4 The procedure of Reference Example 2 was repeated except that the cationic dyeable polyester used in Comparative Example 3 was used instead of the unmodified polyethylene terephthalate having an intrinsic viscosity of 0.640 used in Reference Example 2. Performed similarly. The results were as shown in Table 2.

[0051]

[Table 2]

Example 4 The copolymerization amount of 3,5-dicarbomethoxycyclohexanesulfonic acid tetrabutylphosphonium salt used as a cationic dye dyeing agent in Example 1 was 10.0 mol based on dimethyl terephthalate. %, Transesterification reaction, polycondensation reaction, drying, melt spinning, drawing heat treatment, knitting, scouring,
Preset, staining and soaping were performed.

The intrinsic viscosity ([η]) of the obtained polymer chip was 0.652, the single yarn fineness of the drawn yarn was 3.0 denier, the strength was 4.2 g / de, and the lightness index (L) at the time of dyeing was ^* ) Was 25.8, and the chroma was 48.9. Light fastness (ΔE ^* )
Was 2.3 and the blue scale was 4-5.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-287174 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (6)

(57) [Claims] 1. The cationic dye-dyed modified polyester as a cationic dye-dying agent represented by the following general formula (I): Wherein the alicyclic sulfonic acid phosphonium salt represented by the formula (1) is copolymerized in an amount of 0.1 to 20 mol% with respect to all acid components excluding the alicyclic sulfonic acid compound constituting the modified polyester. Modified polyester. 2. The modified polyester according to claim 1, wherein the main acid component is terephthalic acid. 3. The modified polyester according to claim 1, wherein the modified polyester is a modified polyethylene terephthalate. 4. The modified product according to claim 1, wherein the alicyclic phosphonium phosphonium salt represented by the general formula (I) is a 3,5-dicarbomethoxycyclohexanesulfonic acid tetrabutyl phosphonium salt. polyester. 5. The modified polyester according to claim 1, wherein the alicyclic phosphonium sulfonate represented by the general formula (I) is 3,5-dicarboxycyclohexanesulfonic acid tetrabutyl phosphonium salt. . 6. A modified polyester fiber obtained by melt-spinning the modified polyester according to claim 1.