JPH0478750B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a treatment agent that imparts excellent hydrophilicity with washing resistance and a preferable texture to polyester synthetic fibers. Polyester synthetic fibers are widely used for clothing, bedding, and sanitary materials, but because they are inherently hydrophobic, they are generally subjected to hydrophilic treatment for such uses. By the way, for the above-mentioned hydrophilic treatment, a polyester-based treatment agent is applied from the point of view of affinity with the target fiber, and water-soluble or water-dispersible treatment agent for ease of treatment work. The material satisfies the following three properties at the same time: it can provide excellent hydrophilicity, it has a preferable texture based on the coefficient of friction between fibers, and it has hydrophilicity and texture that are resistant to washing. It is required that the The present invention relates to a processing agent for polyester synthetic fibers that meets these demands. <Conventional technology and its problems> Various polyether ester copolymer type treatment agents whose main raw materials are polyoxyalkylene glycol, terephthalic acid, isophthalic acid, ethylene glycol, etc. have been proposed as treatment agents for polyester synthetic fibers. has been done. However, while each of these conventional processing agents has advantages, it also has a serious problem in that it lacks at least one of the three properties mentioned above. For example, conventional oil agents using dimethyl 5-sodium sulfoisophthalate as a copolymer component have poor hydrophilicity and wash resistance in terms of texture (Japanese Patent Publication No. 40873/1983). Conventional oil agents, in which a copolymer using polytetramethylene glycol as a copolymerization component is eutectic with a nonionic surfactant and dispersed in water, are inherently poor in hydrophilicity (Tokuko Sho).
49−16774). Conventional oils that use polyethylene glycol monophenyl ether as a copolymerization component cannot improve both hydrophilicity and wash resistance and texture (e.g., prevention of slippage) (Tokuko Showa).
46−13197). Conventional three-mix oils containing copolymers using sulfonic acid metal base-containing ester-forming compounds as copolymerization components undergo gradual changes in the bath composition of the aqueous dispersion during use, eventually resulting in the desired composition. No effect is obtained (Japanese Patent Application Laid-Open No. 59-62640). <Problems to be Solved by the Invention and Means for Solving the Problems> The present invention solves the problems of conventional oil agents as described above, and provides a processing agent for polyester synthetic fibers that simultaneously satisfies the three performances described above. This is what we provide. As a result of intensive research from the above viewpoint, the inventors of the present invention discovered that a specific polyether ester is correct and suitable, and completed the present invention. That is, the present invention provides a polyether ester obtained by copolymerizing the following (A), (B), (C) and (D), in which (A)/(D)=
100/10 to 100/40 (molar ratio) and (C)/(D)=
Block type polyoxyalkylene glycol abiethyl etherified polyether ester and/or polyoxyalkylene glycol hydroformed with a residue of (D) at the end of the molecule, having a molar ratio of 100/50 to 25/100. The present invention relates to a processing agent for polyester synthetic fibers characterized by comprising abiethyl etherified polyether ester. (A): Dicarboxylic acid or lower alkyl ester thereof consisting of terephthalic acid or a lower alkyl ester of 70 mol% or more (B): Ethylene glycol (C): Polyoxyethylene glycol with an average molecular weight of 600 to 2000 (D): The following Polyoxyalkylene glycol abiethyl ether and/or polyoxyalkylene glycol hydroabiethyl ether represented by the general formula:

[However, R is an abiethyl group shown in the following (1) or a hydroabiethyl group shown in (2). R ¹ is hydrogen or methyl group. m is 0 or an integer of 1 to 20, n is an integer of 1 or more, m+n = 10 to 100. The part bounded by m and the part bounded by n are block or random copolymerized. ]

In the present invention, regarding the copolymerization component (A), dicarboxylic acids other than terephthalic acid include:
There are aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids.Specifically, there are isophthalic acid, naphthalene dicarboxylic acid, succinic acid, sebacic acid, azelaic acid, adipic acid, and cyclohexanedicarboxylic acid. Acid, adipic acid is preferred. These dicarboxylic acids may also be their lower alkyl esters. Terephthalic acid (or its lower alkyl ester, the same hereinafter)
is 70 mol% or more based on the total dicarboxylic acid (or its lower alkyl ester, the same applies hereinafter) used, and this proportion is determined by the wetting and affinity of the polyether ester of the present invention to the polyester synthetic fiber. This is important because it ultimately affects the durability. If the amount of terephthalic acid is less than 70 mol% of the total dicarboxylic acids, the affinity for the surface of the polyester synthetic fiber will decrease, and the effect of heat setting on developing the durability will be reduced. In addition, in the present invention, the above (C) which is a copolymerization component
Regarding polyoxyethylene glycol, its average molecular weight is 600 to 2000. If the average molecular weight is less than 600, the emulsion stability of the emulsion prepared from the resulting polyether ester will be poor. On the other hand, if the average molecular weight is greater than 2000, the slipperiness of the resulting polyester-based synthetic fiber to which polyether ester has been added will be promoted. Furthermore, in the present invention, the above (D) which is a copolymerization component
Regarding polyoxyalkylene glycol abiethyl ether or polyoxyalkylene glycol hydroabiethyl ether represented by the general formula shown above, alkylene oxide can be added to abietyl alcohol or hydroabethyl alcohol by a known method. It is obtained as a block-type or random-type polyglycol with a molecular weight of about 700 to 5000, both of which are blocked at one end. In this case, the alkylene oxide to be added includes ethylene oxide and propylene oxide. In the polyether ester of the present invention obtained by copolymerizing these (A), (B), (C) and (D), (A)/(D) = 100/10 to 100/40 ( molar ratio (the same applies hereinafter), and (C)/(D) = 100/50 to 25/100. If (A)/(D) is greater than 100/10, the affinity imparted by the obtained polyether ester will be insufficient. On the other hand, if (A)/(D) is smaller than 100/40, the hydrophilicity of the obtained polyetherester becomes too strong, and the imparted hydrophilicity deteriorates the washing resistance.
In addition, if (C)/(D) is larger than 100/50, if the molecular weight of (C) is large, the hydrophilic washing resistance imparted by the obtained polyether ester will be reduced, and (C)
When the molecular weight of the polyether ester is small, the emulsion stability of the emulsion prepared from the resulting polyether ester is poor. On the other hand, if (C)/(D) is smaller than 25/100, the degree of improvement in hand by the resulting polyether ester will be low. The polyether ester of the present invention can be produced by copolymerizing the above-described (A), (B), (C), and (D) according to the already known method for producing linear polyethylene terephthalate based on predetermined conditions. By doing so, it can be obtained with an average molecular weight of about 3,000 to 20,000. In this case, (D) acts as a terminal group of the polyether ester to obtain a block type polyoxyalkylene glycol abiethyl etherified polyether ester or a block type polyoxyalkylene glycol hydroabiethyl etherified polyether ester. However, since the average molecular weight of the polyether ester obtained can be controlled by the amount of (D) used, the reproducibility as a processing agent will eventually become better.
In addition, when producing the polyether ester of the present invention, crosslinking components such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, pyromellitic acid, etc., are added to an extent that does not impair water dispersibility. They may also be copolymerized. <Effects, etc.> The polyester synthetic fibers to be treated with the treatment agent according to the present invention are polyester synthetic fibers such as polyethylene terephthalate/isophthalate or polyethylene terephthalate/butylene terephthalate, and modified polyester synthetic fibers (for example, basic or Threads, cotton, woven fabrics, and knitted fabrics made of acid dye-dyable polyester, antistatic polyester, flame-retardant polyester, etc. There are no particular limitations on the means for applying the treatment agent of the present invention to these polyester synthetic fibers, the amount of application, the stage of application, etc. If necessary, other modifiers or auxiliary agents may be used in combination without impairing the effects of the present invention. <Effects of the Invention> As explained above, the processing agent of the present invention, which can be used as it is or with a small amount of emulsifier to form a uniform and stable aqueous emulsion, has the following effects. () Can provide excellent hydrophilicity. () A good texture can be imparted. Compared to polyester synthetic fibers, it does not have an excessively slippery or slimy feel, and it does not cause slips (misalignment of threads). () Hydrophilicity with wash resistance and good texture can be imparted. The polyether ester of the present invention exhibits sufficient adhesion or affinity to polyester synthetic fibers due to the above-mentioned (D) introduced at its terminal end. <Examples> Hereinafter, the configuration and effects of the present invention will be made more specific through examples. Test conditions, measurement methods, evaluation criteria, etc. are as follows. In the following description, parts refer to parts by weight, % refers to weight %, actual examples, and ratios refer to comparative examples. ● Conditions for applying to polyester synthetic fibers: Degrease polyester (100%) staple (semi-dull 1.4 denier x 38 mm cut), apply 0.3% by weight of each treatment agent by spraying, and heat at 90°C.
It was dried for 60 minutes, heat set at 150°C for 15 minutes, and used as a sample. ●Washing conditions: 1g of commercially available detergent (ZABU, manufactured by Kao Soap Co., Ltd.)
The sample was stirred in the solution at 45°C for 5 minutes, reduced to 40%, washed with water, and dried. This is one wash,
Repeated 5 times. ●Evaluation of hydrophilicity: 1 g of the sample or the sample after washing 5 times was used as a ball field with a diameter of about 4 cm, and the time (seconds) until it settled was measured by placing it gently on the water surface. The shorter this time, the better the hydrophilicity. ●Evaluation of slipperiness based on texture: The sample or its product after washing five times was handled by four experts and evaluated according to the following criteria. ×… Significantly large amount of slippage 〓… Large amount of slippage △… Slippage ○… Little slippage feeling, flexible and good ○△… No slippage, no flexibility ××… Roughness, poor texture ●Evaluation of sliding property by static friction coefficient: Sample or After washing five times, the coefficient of static friction between fibers was measured using a radar method at 20° C. and 65% RH, and evaluated based on the following criteria. ×…0.290 or less (static friction coefficient, same below) 〓…0.291~0.304 △…0.305~0.313 ○…0.314~0.332 ○△…0.333~0.345 ××…0.346 or more●Synthesis of (D) above: Derived from rosin raw material Abethyl alcohol (Avitol, manufactured by Hercules) 289
After replacing with nitrogen gas, add 4.5 parts of flaky potassium hydroxide.
1745 parts of ethylene oxide was reacted at 130 to 150° C. under a pressure of 3 to 5 kg/cm ² for 5 hours. After the catalyst was adsorbed and filtered, polyoxyethylene glycol abiethyl ether (hereinafter simply referred to as compound D) having an average molecular weight of 2000 was obtained. ●Synthesis of polyether ester and preparation of emulsion of the present invention: 310.4 parts of dimethyl terephthalate, 77.6 parts of dimethyl isophthalate, 273 parts of ethylene glycol,
200 parts of polyoxyethylene glycol with an average molecular weight of 1000 and manganese acetate tetrahydrate as a catalyst
Charge 0.8 parts of antimony trioxide and 0.19 parts of antimony trioxide into a reaction vessel, and heat to 150 to 230 parts under nitrogen gas flow according to the usual method.
After transesterifying at ℃ and distilling off a predetermined amount of methanol, 0.28 parts of phosphorous acid was added, then 480 parts of compound D was added, and the pressure was gradually reduced while raising the temperature to 270 ℃ over 2 hours. Finally, polycondensation was carried out at 270° C. for 40 minutes under a reduced pressure of 1 mmHg. The average molecular weight of the obtained polyether ester (hereinafter simply referred to as compound S) measured by GPC was 9,500. Then, 95 parts of this compound S was melted at 170 to 180°C, and 5 g of polyoxyethylene (10 mol) nonyl phenyl ether was added in advance at 30°C.
of compound S dissolved in 900 g of water was added while stirring with a homomixer, and the concentration of
A 9.5% stable aqueous emulsion (Real-1) was obtained. ●Test Category 1: Using a water-based emulsion (Example-1), samples were obtained and evaluated as described above. The results are shown in Table 1.

【table】

[Table] ●Test Category 2: Molar ratio of Compound D to the total amount of dicarboxylic acid, molar ratio of terephthalic acid to other dicarboxylic acids in the dicarboxylic acid, molar ratio of Compound D to polyoxyethylene glycol, and molar ratio of Compound D to the total amount of dicarboxylic acid. Compound S was obtained by varying the molecular weight of oxyethylene glycol. According to the above-described method, a polyether ester was prepared into an aqueous emulsion, and a polyester staple was processed to obtain a sample and evaluated. The results are shown in Tables 2 and 3.

【table】

[Table] ●Test classification: Polyoxyalkylene glycol abiethyl ether was obtained by the same reaction as in the case of obtaining compound D, and the type and number of moles of alkylene oxide used at this time were varied. Similar to the method described above, a polyether ester is produced to form an aqueous emulsion,
Processing polyester staples to obtain samples;
evaluated. The results are shown in Table 4.

[Table] From the results in Tables 1 to 4, it is clear that according to the present invention (each example), the polyester synthetic fiber maintains excellent hydrophilicity and good texture, and these properties are sufficient. It is clear that it exhibits excellent washing resistance.

Claims (1)

[Scope of Claims] 1. A polyether ester obtained by copolymerizing the following (A), (B), (C) and (D), wherein (A)/(D) in the polyether ester )=100/10~100/40
(molar ratio) and (C)/(D)=100/50 to 25/100
(molar ratio), block type polyoxyalkylene glycol abiethyl etherified polyether ester and/or polyoxyalkylene glycol hydroabiethyl etherified polyether ester with the residue (D) formed at the end of the molecule. A processing agent for polyester synthetic fibers, characterized by comprising: (A): Dicarboxylic acid or lower alkyl ester thereof consisting of terephthalic acid or a lower alkyl ester of 70 mol% or more (B): Ethylene glycol (C): Polyoxyethylene glycol with an average molecular weight of 600 to 2000 (D): The following Polyoxyalkylene glycol abiethyl ether and/or polyoxyalkylene glycol hydroabiethyl ether represented by the general formula:
[Formula] [However, R is an abiethyl group shown in the following (1) or
Hydroabiethyl group shown in (2). R ¹ is hydrogen or a methyl group. m is 0 or an integer of 1 to 20, n is an integer of 1 or more, m+n = 10 to 100. The part bounded by m and the part bounded by n are block or random copolymerized. ]