JPH01192823A - Production of formed article of modified polyester - Google Patents

Abstract

PURPOSE:To enable the melt-forming of a fine fiber or thin film in high formability, by adding a polyoxyalkylene glycol, etc., and a specific organic sulfonic acid metal salt to a specific polyester copolymer dyeable with a cationic dye. CONSTITUTION:A polyoxyalkylene glycol and/or its derivative and an organic sulfonic acid metal salt of formula II (R is >=6C alkyl, aryl or aralkyl; M is alkali metal or alkaline-earth metal; n is 1 or 2) are added to a copolymer composed of (A) a bifunctional carboxylic acid composed mainly of terephthalic acid or its derivative, (B) one or more alkylene glycols or their derivatives and (C) a sulfonic acid phosphonium salt expressed by formula I (A is aromatic or aliphatic group; X1 is ester-forming functional group; X2 is H or ester-forming functional group; R1-R4 are alkyl or aryl; n is positive integer). The amounts of the polyoxyalkylene glycol, etc., and the organic sulfonic acid metal salt are 0.05-10wt.% each based on the copolymer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a cationic dye-dyeable modified polyester molded product, and more specifically, a method for producing a cationic dye-dyeable modified polyester molded product. The present invention relates to a method for producing molded products with stable moldability by adding alkylene glycol and/or its derivatives and organic sulfonic acid metal salts.

(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 such method is to copolymerize polyester with an isophthalic acid component containing a sulfonic acid metal base, such as a 5-sodium sulfoisophthalic acid component, thereby making it dyeable with a cationic dye (Tokuko Showa). 3
(See Publication No. 4-10497).

(Problems to be Solved by the Invention) However, in this method, due to the thickening effect of the isophthalic acid component containing the sulfonic acid metal base, the melt viscosity of the polymerization reaction product increases significantly, leading to a high degree of polymerization. In addition, when molded into fibers or films, the moldability is extremely poor, which is a major cause of cost increases due to lower yields.

An object of the present invention is to provide a method that can solve the problems of the prior art and produce molded products with stable moldability.

(Means to Solve the Problem) As a result of intensive studies to achieve the above object, the present inventors found that the deterioration of moldability was caused by a modification made by copolymerizing an isophthalic acid component containing a sulfonic acid metal base. We found that this was due to the thickening effect of quality polyester and the generation of static electricity during melt molding, and we copolymerized a sulfonic acid phosphonium salt compound instead of a modified polyester that was copolymerized with an isophthalic acid component containing a sulfonic acid metal base. The present invention was achieved by discovering that moldability is dramatically improved by using a modified polyester and containing a polyoxyalkylene glycol and/or its derivative and an organic sulfonic acid metal salt.

That is, the present invention provides a bifunctional carboxylic acid mainly including terephthalic acid or an ester-forming derivative thereof, at least one alkylene glycol or an ester-forming derivative thereof, and a sulfonic acid phosbonium salt represented by the following general formula (I). When melt-molding the modified polyester, at any stage before melt-molding, polyoxyalkylene glycol and/or its derivatives are added to the modified polyester in an amount of 0.05 to 10% by weight according to the following general formula (n). This is a method for producing a modified polyester molded article, characterized in that 0.05 to 10% by weight of an organic sulfonic acid metal salt represented by the formula is added to the modified polyester.

(RS ()+)l1M (II) The polyester used in the present invention has terephthalic acid as the main acid component and at least one type of glycol, preferably ethylene glycol, trimethylene glycol, terephthalic acid, etc. The main target is polyester whose main glycol component is at least one alkylene glycol selected from methylene glycol.

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.

The difunctional carboxylic acid other than terephthalic acid used here is, for example, isophthalic acid. Naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, , diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid,
P-oxybenzoic acid, adipic acid, sebacic acid, 1,4
- aromatic, aliphatic, such as cyclobexanedicarboxylic acid,
Examples include alicyclic difunctional carboxylic acids. Furthermore, isophthalic acid having a sulfonic acid metal base such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component within a range where the effects of the present invention can be substantially achieved.

In addition, as diol compounds other than the above glycols,
Examples include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimecnol, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols.

Additionally, polycarboxylic acids such as trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane to the extent that the polyester is substantially linear.

Polyols such as pentaerythritol 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. 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 sulfonic acid phosphonium salt used as a copolymerization component in the method of 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. X represents an ester-forming functional group,
Specific examples include 10-C-R', -C-OH, -C-OR'.

II II IIo
0 0+Ci(z)-r-O
H.

-○+CH277go0 (CHz) b7'0■(C
1,000 (CHz) b J a-〇H.

etc. can be given. X2 represents an ester-forming functional group or a hydrogen atom that is the same as or different from X, and is preferably an ester-forming functional group. R1,
It represents the same or different groups selected from the group consisting of R2, R3 and R4 or alkyl groups and aryl groups. n is an integer.

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 sulfonic acid phosphonium salts include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, and 315-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt. salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid tetraphenylphosphonium salt,
3゜5-dicarboxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3.5-dicarboxybenzenesulfonic acid butyltriphenylphosphonium salt, 31
5-dicarboxybenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylbosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid ethyltributylphosphonium salt, 3゜5 -Dicarbomethoxyhenzenesulfonic acid hensyltributylphosphonium salt, 3,5-dicarbomethoxybenzenesulfonic acid phenyltributylphosphonium salt, 3.5-dicarbomethoxyhenzenesulfonic acid tetraphenylphosphonium salt, 3.5- Dicarbomethoxyhenzenesulfonic acid ethyltriphenylphosphonium salt, 3,5-dicarbomethoxyhenzenesulfonic acid butyltriphenylbosubonium salt, 3,5-dicarbomethoxybenzenesulfonic acid-\endyltriphenylphosphonium salt sponium salt.

3-carboxybenzenesulfonic acid tetrabutylbosphonium salt, 3-carboxybenzenesulfonic acid tetraphenylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carpomethoxyhenzenesulfonic acid tetraphenylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetrabutylphosphonium salt, 3.5
-Di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetrabutylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetraphenylphosphonium salt salt, 4-hydroxyethoxyhenzenesulfonic acid tetrabutylphosphonium salt, 2,6-dicarpoxynaphthalene-4-sulfonic acid tetrabutylphosphonium salt, α-tetrabutylphosphonium sulfosuccinic acid, and the like. 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, it may be added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed. The proportion of the sulfonic acid phosphonium salt copolymerized with the polyester is preferably in the range of 0.01 to 20 mol% based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.

If the copolymerization ratio is less than 0.01 mol%, the resulting copolymerized polyester tends to have insufficient dyeability with cationic dyes, and if it exceeds 20 mol%, the physical properties of the polyester tend to deteriorate.

The polyoxyalkylene glycol may be a single polyoxyalkylene glycol or a copolymerized polyoxyalkylene glycol of two or more types, and even if the terminal thereof is a 10H group, ester formation is possible. It may be blocked with an organic group having no properties, or may be bonded to another organic group having ester-forming properties via an ester bond, an ether bond, or a carbonate bond. A preferred specific example is a molecular weight of 4,000 to 200,00.
0 polyoxyethylene glycol, molecular weight 1,00
0-150.000 polyoxypropylene glycol, polyoxytetramethylene glycol, molecular weight 2.0
00-200.000 1=1 copolymer of ethylene oxide and propylene oxide, molecular weight 4,000-1
Examples include trimethylolethylene oxide adducts with a molecular weight of 50,000 and nonylphenol ethylene oxide adducts with a molecular weight of 3,000 to 150,000. Particularly preferred are polyoxyethylene glycols having a molecular i of 10,000 to 20,000, molecular weights 10,000 to 20,
000 is a random copolymer of ethylene oxide and propylene oxide in a ratio of 1=3 to 3:1. Examples of polyoxyalkylene glycol derivatives include polyetheramide and polyether ester.

The amount of the polyoxyalkylene glycol and/or its derivative added is 0.1 to 0.1 to the modified polyester.
It is necessary that the content be in the range of 10% by weight. Added amount is 0
．． If it is less than 1% by weight, there will be no effect of improving molding stability, and if it is more than 10% by weight, the physical properties such as strength and fibril resistance of the polyester fiber will be insufficient.

The amount added is preferably in the range of 0.5 to 7% by weight.

Further, in the present invention, it is important to add an organic sulfonic acid metal salt represented by the following general formula (n).

(RS 03 ) nM ・=-(II) Examples of such organic sulfonic acid metal salts include sodium toluenesulfonate, lithium toluenesulfonate, lithium dodecylbenzenesulfonate, lithium dodecylbenzenesulfonate, and carbon atoms of 8 to 20. Examples include alkali metal salts of alkylsulfonic acids and mixtures thereof. The amount of such organic sulfonic acid metal salt added is 0.05 to 10% by weight based on the modified polynistyl. If it is less than 0.05% by weight, good antistatic performance cannot be obtained, and if it exceeds 10% by weight, no improvement in the antistatic effect is observed, and the physical properties of the resulting polyester deteriorate instead. death,
Problems occur frequently during molding.

The above-mentioned polyoxyalkylene glycol and/or its derivative and organic sulfonic acid metal salt may be added at any stage before melt molding, and it is especially preferable to add the polyoxyalkylene glycol and/or its derivative and organic sulfonic acid metal salt at any stage before the completion of the first stage reaction of the polyester synthesis reaction. preferable. Further, the sulfonic acid phosbonium salt may be added simultaneously or separately in any order.

Note that the polyester copolymerized with the bosphonium sulfonate salt used in the present invention has poor heat resistance as a component of the copolymer, so it does not decompose by itself under high heat conditions during the polymerization reaction process of the modified polyester or the melt molding process. or accelerate the decomposition of the polymer, coloring the produced polyester and molded articles yellowish-brown, and significantly lowering the degree of polymerization of the polyester, furthermore, this coloring worsens the color tone when dyed.

Therefore, in order to improve the heat resistance of this modified polyester, tetramethylphosphonium chloride, tetramethylbosbonium bromide 1:, and tetramethylphosphonium iodide were added.

Tetramethylphosphonium hydroxide.

Tetraethylphosphonium chloride, tetrapropylphosphonium chloride IS, tetraisopropylphosphonium chlorite, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium hydroxide, butyltriphenylphosphonium chloride, ethyltrioctylphosphonium chloride .

Hexadecyltributylphosphonium chloride.

Ethyltrihexylphosphonium chloride, cyclohexyltributylphosphonium chloride.

Hensyltributylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium high F oxide, octyltrimethylphosphonium chloride, octyldimethylbenzylphosphonium chloride, lauryldimethylhensylphosphonium chloride.

lauryldimethylbenzylphosphonium hydroxide, stearyltrimethylphosphonium chloride,
Lauryltrimethylphosphonium ethosulfate, laurylhenzentrimethylphosphonium methosulfate, lauryldimethyl-0-chlorohensylphosphonium chloride.

Stearylethyldihydroxyethylphosphonium ethosulfate, tetrabutylphosphonium acetate,
Tetrabutylphosphonium dodecylhenzenesulfonate, tetrabutylphosphonium tosylate, tetrabutylphosphonium stearate, tetrabutylphosphonium acetate.

Tetrabutylphosphonium phosphate, tetrabutylphosphonium phosphite ethyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonylam bromide, hensyltriphenylphosphonium chloride, tributylallylphosphonium Quaternary phosphonium compounds such as ethylene bistris(2-cyanoethyl)phosphonium bromide, tris-2-cyanoethylallylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, tetrakis(hydroxymethyl)phosphonium chloride, or tetrahydroxide Methyl ammonium, tetramethyl ammonium chloride, tetraethylammonium hydroxide, tetraethylammonium chloride.

Tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetraisopropylammonium hydroxide, tetraisopropylammonium chloride,
It is preferable to add quaternary ammonium salts such as tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetraphenylammonium hydroxide, and tetraphenylammonium chloride.

Furthermore, the modified polyester used in the present invention preferably contains an oxidation-resistant agent such as a sterically hindered phenol compound or a triazole compound, and further contains an ether bond formation inhibitor, such as an organic sodium metal salt such as sodium acetate. It is also desirable to add heat resistance improvers such as onium salt compounds such as tetraethylammonium hydroxide and tetrabutylphosphonium hydroxide. In addition, optional additives as necessary, such as catalyst 2 color inhibitor 5 heat resistant agent,
Flame retardants, antioxidants, matting agents, colorants, inorganic fine particles, etc. may be included.

Any molding conditions can be employed to mold the above-mentioned modified polyester. For example, when spinning yarn,
A method of spinning at a speed of 500 to 2500 m/min, stretching and heat treatment, a method of spinning at a speed of 1500 to 5000 m/min,
Method of performing stretching and false twisting simultaneously or successively, 5000
Any spinning conditions may be employed, such as spinning at a high speed of m/min or higher and omitting the stretching step depending on the application.

Further, it is preferable to heat-treat the obtained fiber or woven or knitted fabric at a temperature of 100° C. or higher because it stabilizes the structure and promotes the migration of the blended polyoxyalkylene glycol to the vicinity of the surface. Furthermore, relaxation heat treatment or the like may be used in combination, if necessary.

Furthermore, when using the film or sheet for any purpose, arbitrary molding conditions can be adopted. For example, any conditions may be employed, such as a method of applying tension in only one direction after film formation to give it anisotropy, a method of stretching in two directions simultaneously or in an arbitrary order, a method of multi-stage stretching of two or more stages, etc. Further, it is preferable to heat-treat the film, sheet, etc. at a temperature of 100° C. or higher for the reasons mentioned above.

(Function) According to the method of the present invention, the moldability is improved, and the antistatic properties and antifouling properties of the molded product are also improved, but the reason for this is not yet clear.

Probably, a modified polyester copolymerized with a phosphonium sulfonate salt has a small thickening effect, and furthermore, a modified polyester copolymerized with a phosphonium sulfonate salt, a polyoxyalkylene glycol or its derivative, and a metal organic sulfonate. It is thought that the interaction with the salt significantly suppresses the generation of static electricity, and these results combined to significantly reduce breakage during molding, roller wrapping, etc.

(Example) Next, the present invention will be explained in further detail by giving examples. Parts and % in the examples indicate parts by weight and % by weight, respectively, and the intrinsic viscosity [η] of the polymer was determined from the value measured in an orthochlorophenol solution at 35°C. The spinning property is determined by the number of yarn breaks during spinning (times/106m) and the ramp rate during drawing (
It is expressed as the number of roller windings due to single yarn breakage when drawing 100 2.5 kg bobbins.

In addition, the antistatic property was tested by scouring and air-drying the stockinette fabric knitted with the obtained drawn yarn using a conventional method, presetting it at 160°C for 1 minute, and measuring the IKV voltage using a status meter. applied, relative humidity 50%, temperature 25℃
Its half-life (seconds) was measured at .

Furthermore, dyeability with cationic dyes is determined by dyeing knitted fabrics knitted with the obtained drawn yarns with cationic dyes.
n CD-FRLII/Cathilon Blue
Dye bath containing 2% owf of CD-F B L H-■=1 (manufactured by Hodogaya Chemical Co., Ltd.) (3 g/l of Glauber's salt as an auxiliary agent)
, containing 0.3 g/R of acetic acid) at 120 °C for 60 minutes and visually evaluated.

Examples 1-10, Comparative Examples 1-2 100 parts of dimethyl terephthalate, 6 ethylene glycol
0 parts, 0.03 parts of manganese acetate tetrahydrate (0.024 mol % based on dimethyl terephthalate) and 0.009 parts of cobalt acetate tetrahydrate (0.007 mol based on dimethyl terephthalate) as a coloring agent. %) was placed in a replacement can and heated from 140°C to 22°C for 3 hours under nitrogen gas atmosphere.
The temperature was raised to 0°C, and the resulting methanol was distilled out of the system to carry out the transesterification reaction.

Subsequently, 1.5 mol% of 3,5-dicarboxyhenzenesulfonic acid tetra-n-butylphosphonium salt was added to the obtained product in the form of a 20% heated ethylene glycol solution, and then stirred at 220°C for 20 minutes. After that, 0.03 part of a 56% aqueous solution of orthophosphoric acid (0.033 mol % based on dimethyl terephthalate) was added as a stabilizer, and at the same time, expulsion of excess ethylene glycol by increasing the temperature was started. 10
After the minute, 0.04 part of antimony trioxide (0.027 mol % based on dimethyl terephthalate) was added as a polycondensation catalyst. When the internal temperature reached 240°C, expulsion of ethylene glycol was completed, and the reaction product was transferred to a polymerization vessel. Next, without raising the temperature, the reaction was carried out at normal pressure until the internal temperature reached 260°C, and then the temperature was increased from 760 imHg to lm over 1 hour.
Reduce the pressure to mHg, and at the same time reduce the internal temperature to 2.0 mHg over 1 hour and 30 minutes.
The temperature was raised to 80°C. Polyoxyalkylene glycol and organic sulfonic acid metal salt shown in Table 1 were added after polymerization was further carried out for 1.5 hours under reduced pressure of 14ml or less at a polymerization temperature of 280°C, and the intrinsic viscosity [η] was approximately 0.64. I continued to react until I got it. This polymer was chipped according to a conventional method, dried, and melt-spun at 285°C using a spinneret having 24 circular spinning holes with a hole diameter of 0.31. Next, the obtained undrawn yarn was stretched and heat treated using a supply roller at 84°C and a plate heater at 180°C at a stretching ratio such that the elongation of the finally obtained drawn yarn was 30%. A drawn yarn of denier/24 filament was obtained. The yarn spinning properties, antistatic properties and cationic dye dyeability of the obtained drawn yarn were as shown in Table 2.

Example 11 Tetra-n 3,5-dicarboxyhenzenesulfonic acid used as a cationic dye staining agent in Example 2
The same procedure as in Example 2 was carried out except that 3,5-dicarboxyhenzenesulfonic acid butyltriphenylphosphonium salt was used in place of the -butylphosphonium salt. The results are shown in Table 2.

Example 12 In place of the 3,5-dicarboxyhenzenesulfonic acid tetra-n-butylphosphonium salt used as the cationic dye staining agent in Example 2, 3,5-dicarbomethoxyhenzenesulfonic acid tetra- Example 2 was carried out in the same manner as in Example 2, except that n-butylphosbonium salt was used and the timing of its addition was changed to before the start of the transesterification reaction. The results were as shown in Table 2. In the polyoxyalkylene glycols shown in Table 1, PEG is polyoxyethylene glycol, MM-PEG is polyoxyethylene glycol with both ends capped with methoxy groups, and MP-PEG is polyoxyethylene glycol with both ends capped with phenoxy groups or polyoxyethylene glycol. P-PEG refers to polyoxyethylene glycol with only one end blocked with a phenoxy group.
The numbers in ) represent average molecular weights.

In addition, mixed alkyl sulfonic acid soda is a carbon number of 8 to 2.
It represents a mixture of sodium alkylsulfonates having 0 alkyl groups (average carbon number 14).

(Next summer, blank space below) Table 2 Examples 13 to 18 Comparative Examples 3 to 4 In Example 2, the type and amount of the organic sulfonic acid metal salt were variously changed as shown in Table 3. An experiment was conducted in the same manner as in Example 2. The results are shown in Table 4.

(Next summer, below are blanks) Table 4 (Effects of the invention) According to the present invention, phosphonium sulfonate salt copolymerized polyester, which can be made into high-strength cationic dye-dyeable polyester fiber, can be molded in a stable state. The resulting molded product has good antistatic properties and dyeability.

Claims (1)

[Scope of Claims] 1. Difunctional carboxylic acid mainly including terephthalic acid or its ester-forming derivative, at least one alkylene glycol or its ester-forming derivative, and phosphonium sulfonate represented by the following general formula (I) When melt-molding a modified polyester consisting of a salt, at any stage before melt-molding, zero amount of polyoxyalkylene glycol and/or its derivatives is added to the modified polyester.
．． 05 to 10% by weight of the organic sulfonic acid metal salt represented by the following general formula (II) based on the modified polyester.
1. A method for producing a modified polyester molded article, characterized by adding 05 to 10% by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) [In the formula, A is an aromatic group or an aliphatic group, X_1 is an ester-forming functional group, X_2 is an ester-forming functional group that is the same as or different from X_1, or hydrogen atoms R_1, R_2, R_3 and R_4 are an alkyl group or an aryl group. The same or different groups selected from the groups, n represents a positive integer. ] (RSO_3)_nM...(II) [In the formula, R is an alkyl group, aryl group, or aralkyl group having 6 or more carbon atoms, M is an alkali metal or alkaline earth metal, and n is an alkali group. In the case of a metal, 1 is shown, and in the case of an alkaline earth metal, 2 is shown. ]