JPH0415259B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Fields> The present invention relates to a modified polyester composition, and more specifically, to the formation of physical crosslinks between sulfonates, which is inevitable in conventional cationic dyeable modified polyesters of the sulfonic acid metal salt copolymer type. Sulfonic acid that eliminates the phenomenon of significantly increased viscosity during melting due to This invention relates to a cationic dye-dyable modified polyester composition of phosphonium salt copolymerization type. <Prior Art> Polyester has many excellent properties and is therefore widely used as fibers and films, but it has low dyeability and is particularly difficult to dye with dyes other than disperse dyes. Various proposals have been made to improve this dyeability. One of the methods is to copolymerize polyester with an isophthalic acid component containing a sulfonic acid metal base, for example, a 5-sodium sulfoisophthalic acid component, thereby making it dyeable with cationic dyes (Japanese Patent Publication No. 1989-1999). -Refer to Publication No. 10497). However, in this method, when the isophthalic acid component containing the sulfonic acid metal base is copolymerized in an amount necessary to increase the dyeability to a satisfactory level, the thickening effect of the isophthalic acid component containing the sulfonic acid metal base causes However, the melt viscosity of the polymerization reaction product increases significantly, making it difficult to sufficiently increase the degree of polymerization, and at the same time making spinning difficult. Therefore,
In order to lower the melt viscosity of the modified polyester copolymerized with an isophthalic acid component containing such an amount of sulfonic acid metal base to a range where polymerization is easy and spinning is possible, the degree of polymerization of the modified polyester is lowered. It is necessary to do so. As a result, the strength of the resulting yarn is reduced, which significantly limits the uses of the resulting cationic dyeable polyester fibers. On the other hand, a method is known in which an isophthalic acid component having a sulfonate phosphonium base is used as a cationic dye dyeing agent (see Japanese Patent Publication No. 47-22334 and US Pat. No. 3,732,183). According to this method, the thickening effect during the polymerization reaction is small, so
Even if the degree of polymerization of the modified polyester is increased, the melt viscosity can be kept within a range that allows normal spinning. As a result, high-strength cationic dye-dyable polyester fibers can be easily obtained, and by taking advantage of the vivid color development of cationic dyes and the high tenacity of yarn, it is possible to expand the application to the field of sportswear, etc. There is. However, in this method, the heat resistance of the isophthalic acid component having a sulfonate phosphonium base used is inferior to that of the isophthalic acid component having a sulfonate metal base, so the heat resistance of the isophthalic acid component used is inferior to that of the isophthalic acid component having a sulfonate metal base. It has the serious disadvantage of decomposing itself under high heat conditions or accelerating the decomposition of the polymer, coloring the produced polyester and spun yarn yellowish brown, and significantly reducing the degree of polymerization of the polyester. This will worsen the color tone when dyeing. For this reason, this method has never been industrially adopted. <Problems to be Solved by the Invention> In view of the advantages of the modified polyester copolymerized with an isophthalic acid component containing a phosphonium sulfonate base, the present inventor conducted intensive studies to overcome the above-mentioned disadvantages, and was surprised to find that By blending a specific amount of a specific coumarin compound, the disadvantage of poor heat resistance mentioned above can be greatly improved, resulting in a modified cationic dye dyeable type with high whiteness, high degree of polymerization, and good heat resistance. It has been found that high quality polyester can be obtained. The present invention was completed as a result of further studies based on this knowledge. <Structure of the invention> That is, the present invention has the following general formula () (In the formula, Z is an aromatic group or an aliphatic group, A ₁ is an ester-forming functional group, A ₂ is an ester-forming functional group or a hydrogen atom, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, Indicates the same or different groups selected from the group consisting of alkyl groups, aryl groups, and hydroxyalkyl groups.) A modified polyester obtained by copolymerizing a sulfonic acid phosphonium salt represented by (In the formula, Ar represents a benzene ring, a naphthalene ring, or an acenaphthene ring, and when Ar is a benzene ring or a naphthalene ring, these rings may contain an alkyl group or an alkoxy group as a substituent.R ₅ and _R6 represent the same or different groups selected from the group consisting of alkyl groups, aryl groups, and hydrogen atoms. The invention relates to a modified polyester composition. The polyester 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 main glycol component. The main target is It may also be a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/or a part of the glycol component is replaced with the above-mentioned glycol or other diol component other than the main component. It may also be polyester. Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, 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 given. Furthermore, isophthalic acid having a sulfonic acid metal base such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component within the range where the effects of the present invention can be substantially achieved. It is desirable to suppress the amount to less than 1.8 mol% based on the components. Examples of diol compounds other than the above-mentioned glycols include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols. etc. can be given. Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear. Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, usually terephthalic acid and ethylene glycol are 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 transesterified. 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. The modified polyester used in the present invention is
The following general formula () for the above polyester It is necessary that the sulfonic acid phosphonium salt represented by is copolymerized. In the above general formula, Z
represents an aromatic group or an aliphatic group, and among them, an aromatic group is preferable. A ₁ represents an ester-forming functional group, and as a specific example:

【formula】

【formula】

[Formula] (-CH-) _a OH, -O-(-CH ₂ -) _b (-O(CH ₂ ) _b ]- _d OH, (However, R' is a lower alkyl group or a phenyl group,
(a and d are integers of 1 or more, b is an integer of 2 or more), etc. A ₂ represents an ester-forming functional group or a hydrogen atom that is the same as or different from A ₁ , and is preferably an ester-forming functional group. R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms,
Indicates the same or different groups selected from the group consisting of alkyl groups, aryl groups and hydroxyalkyl groups. Such sulfonic acid phosphonium salts can generally be easily synthesized by reacting the corresponding sulfonic acid with phosphines or by reacting the corresponding sulfonic acid metal salt with phosphonium halides. Preferred specific examples of the phosphonium sulfonate salts include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, and benzyl 3,5-dicarboxybenzenesulfonate. tributylphosphonium salt,
3,5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-
Dicarboxybenzenesulfonic acid butyltriphenylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid benzyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarbomethoxybenzenesulfone acid ethyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid benzyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5
-Dicarbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid butyltriphenylphosphonium salt,
3,5-Dicarbomethoxybenzenesulfonic acid benzyltriphenylphosphonium salt, 3-carboxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carboxybenzenesulfonic acid tetraphenylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetrabutylphosphonium salt ，
3-Carbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetrabutylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraph enylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetrabutylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 4-hydroxyethoxybenzenesulfonic acid tetrabutylphosphonium salt ,2,6-dicarboxynaphthalene-4
-Tetrabutylphosphonium sulfonate salt, α-
Examples include tetrabutylphosphonium sulfosuccinate. The above-mentioned 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, the above-mentioned phosphonium salt may be copolymerized at any stage before the synthesis of the polyester described above is completed, preferably in the first step.
It may be added at any stage before the stage reaction is completed. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is preferably in the range of 0.5 to 10 mol% based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.
When the copolymerization ratio is less than 0.5 mol%, the resulting copolymerized polyester tends to have insufficient dyeability with cationic dyes, and when it exceeds 10 mol%, the cationic dyeability no longer shows any significant improvement.
On the contrary, the physical properties of the polyester deteriorate, making it difficult to achieve the object of the present invention. The coumarin compound used in the present invention is represented by the following general formula (). In the formula, Ar represents a benzene ring, a naphthalene ring or an acenaphthene ring, and when Ar is a benzene ring or a naphthalene ring, these rings may contain an alkyl group or an alkoxy group as a substituent. R ₅ and R ₆ represent the same or different groups selected from the group consisting of an alkyl group, an aryl group and a hydrogen atom. ) Preferred specific examples of such coumarin compounds include 3-phenyl-7-(2H-naphtho[1,2-
d]-triazol-2-yl)coumarin, 7-
(2H-naphtho[1,2-d]-triazole-2
-yl)coumarin, 3-phenyl-7-(2H-benzotriazol-2-yl)coumarin, 3-ethyl-7-(2H-naphtho[1,2-d]-triazol-2-yl)coumarin, 3 -Phenyl-7
-(2H-acenaphthotriazol-2-yl)coumarin, 3-phenyl-7-(2H-6-ethoxynaphtho[1,2-d]-triazol-2-yl)
Examples include coumarin. These may be used alone or in combination of two or more. In the present invention, the above-mentioned coumarin compound may be blended into the modified polyester at any stage until the completion of melt-forming, and at any stage until the completion of the polymerization reaction of the polyester described above or after the completion of melt-forming after synthesis. It is an arbitrary stage until
In particular, since the adverse effects of the sulfonic acid phosphonium salt, such as polymer coloration and reduction in the degree of polymerization, become noticeable after the middle stage of the second stage reaction, it is preferable to add and blend the sulfonic acid phosphonium salt at a stage before the early stage of the second stage reaction. Of course, it can also be added and blended immediately before melt molding, and in that case it is effective in suppressing thermal decomposition during melt molding. If the amount of the coumarin compound is less than 0.0001% by weight based on the modified polyester, the effect of improving heat resistance will be insufficient, and if this amount exceeds 2% by weight, the effect of improving heat resistance will no longer be achieved. This results in poor process passability in the silk spinning process (spinning/drawing) and film forming process. Therefore,
The amount used is from 0.0001 to modified polyester
It should be in the range of 2% by weight, especially 0.001
A range of 1% by weight is preferred. <Effects of the Invention> According to the present invention, polymer discoloration and decrease in polymerization degree during melt molding and polymerization reaction due to the presence of phosphonium sulfonate salts are significantly suppressed, resulting in high whiteness and high polymerization degree. It becomes possible to industrially obtain cationically dyeable polyester molded articles. In addition, light resistance has also improved in response to improved heat resistance. The thus obtained modified polyester obtained by copolymerizing a phosphonium sulfonate salt has the following advantages over the conventional modified polyester obtained by copolymerizing a metal sulfonate salt. (1) Compared to the metal ion of the sulfonate metal salt, the diffusion rate of the cationic dye is higher, probably because the phosphonium salt of the sulfonate phosphonium salt is bulkier. When used, cationic dyeing properties comparable to those of sulfonic acid metal salts can be obtained. (2) Since the thickening effect inherent to sulfonic acid metal salts does not occur, melt spinning of highly polymerized polymers can be easily performed by ordinary spinning methods;
High-strength cationic dye-dyeable polyester moldings can be easily obtained. (3) Furthermore, according to the present invention, since a phosphonium salt is used instead of a metal salt, the amount of foreign matter produced as a by-product during the polycondensation reaction is small, which reduces the increase in pack pressure during molding, especially during spinning, and reduces the The effect is that the decrease in yarn quality is small. (4) In relation to (2) and (3) above, the modified polyester composition of the present invention has extremely excellent spinnability and can be drawn at ultra-high speeds of 3000 m/min or more, particularly 5000 m/min or more. Spinning is also possible in Also,
It is possible to spin ultrafine fibers of 1 denier or less. (5) Furthermore, the fibers obtained from the modified polyester composition of the present invention have excellent heat resistance, so even when false-twisting is performed at high temperatures, there is no problem of strength loss or fusion, and the fibers have excellent properties. Processed yarn can be provided. (6) Contrary to the fact that modified polyester copolymerized with sulfonic acid metal salts is extremely prone to generating static electricity,
The modified polyester composition of the present invention exhibits excellent antistatic properties. (7) Furthermore, since the modified polyester composition of the present invention contains a phosphonium salt, it has excellent flame retardancy and antibacterial properties. The modified polyester composition of the present invention may contain optional additives, such as catalysts, color inhibitors, heat resistant agents, flame retardants, antioxidants, quenching agents, colorants, inorganic fine particles, etc., as necessary. It may be <Example> Examples will be given below for further explanation. Parts and % in Examples indicate parts by weight and % by weight, respectively.
The intrinsic viscosity [η] of the polymer was determined from the value measured in an orthochlorophenol solution at 35°C, and the softening point (SP) was measured by the penetration method. The hue of the polymer was indicated by the L value and b value determined by a Hunter color difference meter. The larger the L value, the better the whiteness, and the higher the b value on the + side, the stronger the yellowness. The number of terminal carboxyl groups in the polymer was determined by heating and dissolving a sample in benzyl alcohol and titrating with a sodium hydroxide solution. The larger the number of terminal carboxyl groups, the more thermal decomposition occurs. Examples 1 to 5 and Comparative Examples 1 and 2 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.03 part of manganese acetate tetrahydrate (0.024 mol% relative to dimethyl terephthalate), and cobalt acetate tetrahydrate as a coloring agent. 0.009 part (0.007 mol% based on dimethyl terephthalate) was charged into a transesterification tank, and the mixture was heated for 3 hours under a nitrogen gas atmosphere.
The temperature was raised from 140°C to 220°C, and the resulting methanol was distilled out of the system while transesterification was carried out.
The product obtained was then treated with 3,5
- Add a 20% heated ethylene glycol solution of dicarboxybenzenesulfonic acid tetrabutylphosphonium salt and stir for 20 minutes at 220°C, then add 0.03 parts of a 56% aqueous solution of orthophosphoric acid as a stabilizer (0.033 parts relative to dimethyl terephthalate). (mol%) was added, and at the same time, expulsion of excess ethylene glycol was started at elevated temperature. Antimony trioxide as polycondensation catalyst after 10 minutes
0.04 part (0.027 mol % based on dimethyl terephthalate) was added, and after 10 minutes, 3-phenyl-7- in the amount shown in Table 1 was added as a coumarin compound.
(2H-naphtho[1,2-d]-triazole-2
−il) coumarin was added. When the internal temperature reached 240°C, expulsion of ethylene glycol was completed and the reaction product was transferred to a polymerization vessel. Then, while increasing the temperature, the internal temperature reached 260℃.
After reacting under normal pressure until the temperature reached °C, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and at the same time, the internal temperature was raised to 280 °C over 1 hour and 30 minutes. 1mmHg
The polymerization reaction was terminated after further polymerization for 2 hours at a polymerization temperature of 280° C. under the following reduced pressure. The [η], SP, color, and number of terminal carboxy groups of the obtained polymer are
Shown in the table. The polymer was made into chips according to a conventional method. These polymers were dried using a conventional method, and 285
Melt spun at °C. Then, the obtained undrawn yarn was
A drawing heat treatment was carried out using a heating roller at 84°C and a plate heater at 180°C at a drawing ratio such that the elongation of the finally obtained drawn thread was 30% to obtain a drawn thread of 75 denier/24 filaments. Table 1 shows the quality ([η] _f , strength, color tone) of the obtained drawn yarn. These drawn yarns were made into a knitted fabric using a conventional method, and then scouring and presetting were performed according to a conventional method.
FRLH/Cathilon Blue CD-FBLH = 1/1 (manufactured by Hodogaya Chemical Co., Ltd.) at 120℃ in a dye bath containing 2% owf (containing 3 g of Glauber's salt and 0.3 g of acetic acid as auxiliaries).
Stained for 60 minutes. In contrast to the dyed fabrics of the Examples which exhibited a clear deep blue color, the fabrics of the Comparative Examples were only dyed to a dull blue color. Example 6 and Comparative Example 3 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt used as a cationic dye dyeing agent in Example 1 was replaced with 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt.
Example 1 except that dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt was used and the timing of its addition was changed to before the start of the transesterification reaction.
I did the same thing. The quality of the obtained polymer was as shown in Table 1. Further, the fibers were spun, drawn, and heat treated in the same manner as in Example 1, and the quality of the obtained fibers is shown in Table 1. Further, when a fabric was dyed in the same manner as in Example 1, the dyed fabric of Example 6 exhibited a clear deep blue color, but the dyed fabric of Comparative Example 3 exhibited only a dull blue color. Example 7 and Comparative Example 4 In place of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt used as a cationic dye dyeing agent in Example 1, 3,5-
The same procedure as in Example 1 was carried out except that butyltriphenylphosphonium dicarboxybenzenesulfonate was used instead. The quality of the obtained polymer was as shown in Table 1. Further, the fibers were spun, drawn, and heat treated in the same manner as in Example 1, and the quality of the obtained fibers is shown in Table 1. Further, when a fabric was dyed in the same manner as in Example 1, the dyed fabric of Example 7 exhibited a clear deep blue color, but the dyed fabric of Comparative Example 4 exhibited only a dull blue color. Example 8 and Comparative Example 5 3-phenyl-7-(2H-naphtho[1,2-
d]-triazol-2-yl) instead of 3-phenyl-(2H-benzotriazole-2)
−il) coumarin The same procedure as in Example 1 was carried out except that . The quality of the obtained polymer was as shown in Table 1. Further, the fibers were spun, drawn, and heat treated in the same manner as in Example 1, and the quality of the obtained fibers is shown in Table 1. Furthermore, when fabric was dyed in the same manner as in Example 1,
The dyed fabric of Example 8 exhibited a clear deep blue color, but the dyed fabric of Comparative Example 5 exhibited only a dull blue color.

【table】

Claims (1)

[Claims] 1. The following general formula () (In the formula, Z is an aromatic group or an aliphatic group, A ₁ is an ester-forming functional group, A ₂ is an ester-forming functional group or a hydrogen atom, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, Indicates the same or different groups selected from the group consisting of alkyl groups, aryl groups, and hydroxyalkyl groups.) A modified polyester obtained by copolymerizing a sulfonic acid phosphonium salt represented by (In the formula, Ar represents a benzene ring, a naphthalene ring, or an acenaphthene ring, and when Ar is a benzene ring or a naphthalene ring, these rings may contain an alkyl group or an alkoxy group as a substituent.R ₅ and _R6 represent the same or different groups selected from the group consisting of alkyl groups, aryl groups, and hydrogen atoms. A modified polyester composition made of 2. The modification according to claim 1, wherein the copolymerized amount of the sulfonic acid phosphonium salt is 0.5 to 10 mol% based on the bifunctional carboxylic acid component (excluding sulfonate) constituting the modified polyester. Quality polyester composition. 3 The coumarin compound has the following formula () The modified polyester composition according to claim 1 or 2, which is a compound represented by: