JPH01192822A - 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., to a specific polyester copolymer dyeable with a cationic dye. CONSTITUTION:A polyoxyalkylene glycol having an average molecular weight of 300-100,000 and/or its derivative 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) 0.5-10mol% (based on the carboxylic acid component) of a sulfonic acid phosphonium salt expressed by formula (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 amount of the polyoxyalkylene glycol, etc., is 0.1-10wt.% 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 articles with stable moldability by adding alkylene glycol and/or its derivatives.

(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 known method is to copolymerize a sulfonic acid phosphonium salt with a polyester to make it dyeable with a cationic dye (Japanese Patent Publication No. 47-22334, U.S. 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 the range that can normally be melt-molded. This makes it possible to obtain high-strength cationic dye-dyeable polyester fibers.

(Problem to be solved by the invention) However, with this method, static electricity is generated during molding, causing breakage of the spun yarn and formed film, and furthermore, roller wrapping during the stretching process, etc., resulting in unstable It is difficult to mold the product in a closed state.

An object of the present invention is to provide a method capable of solving the problems of the prior art and producing molded products with stable moldability.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have found that moldability is significantly improved by the presence of polyoxyalkylene glycol and/or its derivatives. This discovery led to the present invention.

That is, the present invention provides a difunctional carboxylic acid mainly including terephthalic acid or its ester-forming derivative, at least one alkylene glycol or its ester-forming derivative, and the difunctional carboxylic acid component. 10.
When melt-molding a modified polyester consisting of 0 mol% of a sulfonic acid phosphonium salt represented by the following general formula,
At any stage before melt molding, the average molecular weight is 300 to 1.
0.00,000 polyoxyalkylene glycol and/or its derivatives to the modified polyester.
This is a method for producing a modified polyester molded article characterized by adding 1 to 10% by weight.

X+ A X2 □ [same or different group, n represents a positive integer. J The polyester used in the present invention has terephthalic acid as the main acid component and at least one 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 polyester.

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

Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and adipic acid. Examples include aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as sebacic acid and 1,4-cyclohexanedicarboxylic acid. 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-dimetatool, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols.

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 can 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 sulfonic acid phosphonium salt used as a copolymerization component in the method of the present invention is represented by the following general formula.

X, -A-X2 ■ (SO+ -P "R+ R2R3R4)nIn 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, specific examples of which are -0-C-R', -C-〇H, and -C-OR'.

II II IIo 0
0 A CI-(z:h-OH.

0-(CH2 catty-HO(CHzh-hydOH.

Examples include -C-+O (CHzhF, ○H, etc.). ,
R2, R3 and R4 represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n is a positive 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-dicarboxyhenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxyhenzenesulfonic acid ethyltributylphosphonium salt, and 3,5-dicarboxyhenzenesulfonic acid ethyltributylphosphonium salt. Benzenesulfonic acid benzyltributylphosphonium salt, 3.5-dicarboxyhenzenesulfonic acid phenyltributylphosphonium salt, 3.5-dicarboxyhenzenesulfonic acid tetraphenylphosphonium salt, 3.5-dicarboxyhenzenesulfonic acid ethyltri Phenylphosphonium salt, 3,5-dicarboxyhenzenesulfonic acid butyltriphenylbosphonium salt, 3.
5-dicarboxybenzenesulfonic acid hensyltriphenylphosphonium salt, 3,5-dicarbomethoxyhenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt, 3.5 -Hensyl dicarpomethoxyhenzenesulfonate 1 to butylphosphonium salt, 3,5
-Dicarbomethoxyhenzenesulfonic acid phenyltributylphosphonium salt, 3,5-dicarboxylic acid tetraphenylbosphonium salt, 3,5
-Dicarbomethoxyhenzenesulfonic acid ethyltriphenylphosphonium salt, 3.5-dicarbomethoxyhenzenesulfonic acid butyltriphenylphosphonium salt, 3゜5-dicarboxylene 1-xybenzenesulfonic acid henzyltriphenylphosphonium salt, 3 -Carboxybenzenesulfonic acid tetrabutylphosphonium salt, 3-carboxybenzenesulfonic acid tetraphenylbosbonium salt, 3
-Carbomethoxyhenzenesulfone old tetrabutylphosphonium salt, 3-carbomethoxybenzenesulfonic acid tetraphenylphosphonium salt, 3,5-di(β-hydroxyethoxycarbonyl)benzenesulfonic acid tetrabutylphosphonium salt, 3.5- Di(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetraphenylphosphonium salt, 3-(β-hydroxyethoxycarbonyl)henzenesulfonic acid tetrabutylphosphonium salt,
3-(β-hydroxyl-oxycarbonyl)henzenesulfonic acid tetraphenylphosphonium salt, 4-hydroxyethoxybenzenesulfonic acid tetrabutylphosphonium salt, 2,6-dicarpoxynaphucrene-4-sulfonic acid tetrabutylbosphonium 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 suitably in the range of 0.5 to 10 mol % based on the bifunctional carboxylic acid component (excluding the sulfonate) constituting the polyester.

If the copolymerization ratio is less than 0.5 mol %, the resulting copolymerized polyester will have insufficient dyeability with cationic dyes, and if it exceeds 10 mol %, the physical properties of the polyester will deteriorate.

The polyoxyalkylene glycol and/or its derivatives added to the modified polyester used in the present invention are:
Average molecular weight is 300-100,000, preferably 6
00 to 20,000. Average molecular weight is 30
If it is less than 0, it is difficult to prevent the generation of static electricity during molding, and moldability cannot be improved.

On the other hand, if the average molecular weight exceeds 100,000, it is again difficult to prevent the generation of static electricity, and not only is the moldability not improved, but the physical properties and performance of the resulting molded product are deteriorated, which is unsuitable.

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 10 H group, a fragment thereof may be used. The terminal or both terminals may be blocked with an organic group that does not have ester-forming properties, and may also be bonded to another organic group that has ester-forming properties via an ester bond, ether bond, or carbonate bond. Preferred specific examples include polyoxyethylene glycol with a molecular weight of 600 to 20,000, polyoxypropylene glycol with a molecular weight of 600 to 20,000, polyoxytetramethylene glycol,
1:1 copolymer of ethylene oxide and propylene oxide with a molecular weight of 600 to 20,000, a molecular weight of 600 to 20,000
20,000 phenol ethylene oxide adducts, etc. Particularly preferred is a molecular weight of 2°OOOO~2
0.000 polyoxyethylene glycol, molecule ff
It is a random copolymer of 12,000 to 20,000 ethylene oxide and propylene oxide in a ratio of 1=3 to 3:1.

Furthermore, the polyoxyalkylene glycol derivatives referred to in the present invention also include block polyether amides and block polyether esters. Preferred specific examples of such block polyetheramides include block copolymers of poly ε-capramide and polyoxyethylene glycol diammonium adipamide, polyhexamethylene adipamide/ε-capramide and polyoxyethylene glycol diammonium Examples include block copolymers with adipamide, and preferred specific examples of block polyether esters include polyethylene terephthalate copolyesters made by copolymerizing polyoxyethylene glycol and 5-sodium sulfoisophthalic acid components. I can give you something.

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.

The polyoxyalkylene glycol and/or its derivative may be added at any stage before melt molding,
In particular, it is preferably added before the first stage reaction is completed. Further, the phosphonium sulfonate salts may be added simultaneously or separately in any order.

In addition, the polyester copolymerized with the sulfonic acid phosphonium 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 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,
Tetramethylphosphonium bromide, Tetramethylphosphonium iodide, Tetrabutylphosphonium hydroxide, Tetraethylphosphonium chloride, Tetrapropylphosphonium chloride, Tetraisopropylphosphonium chloride, Tetrabutylphosphonium bromide, Tetrabutylphosphonium bromide, Tetrabutylphosphonium iodide, Tetra Butylphosphonium hydroxide, butyltriphenylphosphonium chloride, ethyltrioctylphosphonium chloride, hexadecyltributylphosphonium chloride, ethyltrioctylphosphonium chloride, cyclohexyl 1-butylphosphonium chloride, hensyltributylphosphonium chloride, tedraphenylphosphonium Chloride, tetraphenylphosphonium hydroxide, octyltrimethylphosphonium chloride, octyldimethylhendylphosphonium chloride, lauryldimethylbenzylphosphonium chloride, lauryldimethylbenzylphosphonium hydroxide, stearyltrimethylphosphonium chloride, lauryltrimethylphosphonium i-sulfate, laurylhensen Trimethylbosphonium methosulfate, lauryl dimethyl-0
- Chlorhensylphosphonium chloride, stearylethyl dihydroxyethylphosphonium ethosulfate, tetrabutylphosphonium acetate, tetrabutylphosphonium dodecylhenzensulfonate, tetrabutylphosphonium acetate, tetrabutylphosphonium stearate 1, tetrabutylphosphonium oleate, tetra Butylphosphonium phosphate, tetrabutylphosphonium phosphite, ethyltriphenylphosphonium bromide, tetramethylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, hensyltriphenylphosphonium chloride, tributyl allyl Bosphonium bromite, ethylene bistris(2-cyanoethyl)phosphonium bromide, tris-2-cyanoethylallylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, tetrakis(hydroxymethyl)phosphonium chloride, etc.
phosphonium compounds, or tetramethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium hydroxide, tetraethylammonium chloride, TeI-laethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride It is preferable to add quaternary ammonium salts such as tetraisopropylammonium water, tetraisopropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetraphenylammonium hydroxide, and tetraphenylammonium chloride.

In addition, it is preferable to blend the modified polyester used in the present invention with an oxidation-resistant agent such as a sterically hindered phenol compound or a triazole-based compound, and an ether bond formation inhibitor such as an organic sodium metal compound such as sodium acetate. It is also desirable to add salt. Other optional additives, such as catalysts, color inhibitors, heat resistant agents, flame retardants, antioxidants, matting agents, colorants, inorganic fine particles, etc., may be included as necessary.

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 2,500 m7 minutes, drawing and heat treatment, 1. A method of spinning at a speed of 500 to 5;000 m7 minutes, drawing and false twisting simultaneously or sequentially, 5,000 Any spinning conditions may be adopted, such as spinning at a high speed of m7 minutes or more and omitting the stretching step depending on the application.

In addition, heat-treating the obtained fibers or woven or knitted fabrics at a temperature of 100°C or higher helps to stabilize the structure and form and stabilize the micro and/or macro phase separation structure of the polyoxyalkylene glycol blended. Therefore, it is preferable. Furthermore, depending on the required G, relaxation heat treatment or the like can be used in combination. Moreover, when used for film or sheet applications, arbitrary molding conditions can be adopted. For example, any conditions can be adopted, such as applying tension in one direction after film formation to give it anisotropy, stretching in two directions simultaneously or in any order, or stretching in two or more stages. . Further, it is preferable to heat-treat the film, Sea I, 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.

Presumably, the interaction between the modified polyester copolymerized with sulfonic acid phosbonium salt and polyoxyalkylene glycol or its derivatives greatly suppresses the generation of static electricity, resulting in less breakage during molding, less roller wrapping, etc. It is thought that this will decrease significantly.

(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 was expressed by the number of yarn breaks during spinning (times/10'm) and the ramp rate during drawing (number of roller windings due to single yarn breakage when drawing 100 2.5 kg bobbins).

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

Furthermore, dyeability with cationic dyes can be determined by dyeing knitted fabric knitted with the obtained drawn yarn with cationic dyes.
n CD-FRLH/Cathilon Blue
CD-FBLH=1:1 (manufactured by Hodogaya Chemical) 2%ow
Dye bath containing f (3 g/7+ of Glauber's salt as auxiliaries, 0.3 g of acetic acid
/j! ) for 60 minutes at 120°C and visually evaluated.

Examples 1 to 10, Comparative Examples 1 to 4 100 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. %) for transesterification and heated from 140°C to 220°C for 3 hours under nitrogen gas atmosphere.
The transesterification reaction was carried out while raising the temperature to C and distilling the generated methanol out of the system.

Subsequently, 3,5-dicarboxy-nzenesulfonic acid tetra-n-butylphosphonium salt in the amount listed in Table 1 was added to the obtained product in the form of a 20% heated ethylene glycol solution, and then heated at 220°C for 20 After stirring for a minute, 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 heating was started. 1
After 0 minutes, 0.04 part of antimony trioxide (
0.027 mol % based on dimethyl terephthalate) 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. 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 160wHg to 1w over 1 hour.
The pressure was reduced to Hg, and the internal temperature was reduced to 2.
The temperature was raised to 80°C. After further polymerization for 1.5 hours at a polymerization temperature of 280°C under reduced pressure of luHg or less, 3% by weight of polyoxyalkylene glycol shown in Table 1 was added to the polyester, and the intrinsic viscosity [η] was approximately 0°64. The reaction continued until Intrinsic viscosity of the obtained polymer [η]
were as shown in Table 1.

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 0.3 mm. 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%. Denier/
A drawn yarn of 24 filaments 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-n was used. Example 2 was carried out in the same manner as in Example 2, except that -butylphosphonium salt was used and the timing of addition was changed to before the start of the transesterification reaction. The results were as shown in Table 2.

(Next summer, blank space below) Table 1 In the polyoxyalkylene glycols in Table 1, P
EG is polyoxyethylene glycol, MM-PEG
is polyoxyethylene glycol with both ends capped with methoxy groups, PP'-PEG is polyoxyethylene glycol with both ends capped with phenoxy groups, and P-PEC is polyoxyethylene glycol with both ends capped with phenoxy groups.
; indicates polyoxyethylene glycol with only one end blocked with a phenoxy group, and the number in parentheses indicates the average molecular weight.

(Next summer, blank space below) Table 2 Examples 13 to 16, Comparative Example 5.6 In Example 2, the amount of PEG (20,000) added was variously changed as shown in Table 3. The experiment was conducted in the same manner as in Example 2 except for this. The results are shown in Table 3.

(Next summer, below are blanks) Table 3 (Effects of the invention) According to the method of the present invention, phosphonium sulfonate salt copolyester, which can be made into high-strength cationic dye-dyeable polyester fiber, is molded in a stable state. Procedural amendment document for the obtained article January 75, 1988

Claims (1)

[Scope of Claims] 1. 0.0% for a difunctional carboxylic acid mainly consisting of terephthalic acid or its ester-forming derivative, at least one alkylene glycol or its ester-forming derivative, and the difunctional carboxylic acid component. When melt-molding a modified polyester consisting of 5 to 10.0 mol% of a sulfonic acid phosphonium salt represented by the following general formula, the average molecular weight is 300 to 100,000 at any stage before melt molding.
A method for producing a modified polyester molded article, characterized in that 0.1 to 10% by weight of polyoxyalkylene glycol and/or its derivative is added to the modified polyester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is an aromatic group or aliphatic group, X_1 is an ester-forming 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 represents a positive integer. ]