JPS61108768A - Treatment agent for polyester synthetic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a treatment agent that gives polyester synthetic fibers excellent hydrophilicity with wash resistance and a favorable texture.

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. ■Being able to impart excellent hydrophilicity;
■It must have a favorable texture based on the coefficient of friction between fibers, ■It must have hydrophilicity and wash resistance in its texture, and it must satisfy the above three properties at the same time. The present invention relates to a processing agent for polyester synthetic fibers that meets such 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 treatment agents has its own advantages, it also has the serious problem of lacking at least one of the three properties mentioned above. Conventional oils using dimethyl have poor hydrophilicity and wash resistance (texture).
Special Publication No. 47-40873). 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 (Japanese Patent Publication No. 49-16774). Conventional oils that use polyethylene glycol monophenyl ether as a copolymerization component cannot simultaneously improve hydrophilicity and improve their wash resistance and texture (e.g., prevention of slippage).
% Japanese Publication No. 46-13197) o Conventional three-mixed oil containing a copolymer using a sulfonic acid metal base-containing ester-forming compound as a copolymerization component has been found to cause the bath composition of the aqueous dispersion to gradually change during use. As a result, the desired effect cannot be obtained (Japanese Unexamined Patent Publication No. 59-62640).

<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention is a processing agent for polyester synthetic fibers that solves the problems of conventional oil agents as described above and simultaneously satisfies the three performances of (1) to (3) described above. It provides:

However, as a result of intensive research from the above viewpoint, the present inventor found that
It was discovered that a specific polyether ester is suitable, and the present invention was completed.

That is, the present invention provides the following (A), (B), (C) and (
(A)/(
D) = 100/1 o~Zoo/4Q (molar ratio)
And (C)/(D) = 100/60~2
(D) at the end of the molecule, which is 5/100 (molar ratio)
A treatment agent for polyester-based synthetic fibers characterized by comprising a block type polyoxyalkylene glycol abiethyl etherified polyether ester and/or a polyoxyalkylene glycol hydroabiethyl etherified polyether ester in which a residue is formed. (A): Dicarboxylic acid or lower alkyl ester thereof in which 70 or more moles are composed of terephthalic acid or its lower alkyl ester (B): Ethylene glycol (C): Polyoxyethylene glycol (D) with an average molecular weight of 600 to 2000 Polyoxyalkylene glycol abiethyl ether and/or polyoxyalkylene glycol abiethyl ether represented by the following general formula: R-0+CHZCHO CH2CH2O trench H [However, R is the following (1) An abiethyl group represented by (2) or a hydroabiethyl group represented by (2). R1 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 1000 The part bound by m and the part bound by n are block or random copolymerized 0] (1): CH2- (2): In the present invention, regarding the above (A) which is a copolymerization component,
Dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and specifically, inphthal aLt7tale dicarboxylic acid, succinic acid, sebacic acid, azelaic acid, adipic acid, Among them, cyclohexanedicarboxylic acid is preferred, and isophthalic acid and adipic acid are preferred. These dicarboxylic acids may also be their lower alkyl esters. The amount of terephthalic acid (or its lower alkyl ester, hereinafter the same) is 70 moles or more based on the total dicarboxylic acid (or its lower alkyl ester, the same hereinafter) used, and this proportion is the final amount of the polyether ester of the present invention. This is important because it affects the wettability and affinity for polyester synthetic fibers, and ultimately affects the durability. If the amount of terephthalic acid is less than 70 mmol of the total dicarboxylic acid, the affinity for the surface of polyester synthetic fiber will decrease,
Heat setting reduces the effect of developing the durability.

Further, in the present invention, regarding the copolymerization component (C), polyoxyethylene glycol has an average molecular weight of 600 to 2,000.

If the average molecular weight is smaller 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 2,000, the slipperiness of the resulting polyester-based synthetic fiber to which polyether ester has been added will be promoted.

Furthermore, in the present invention, regarding the copolymerization component (D), polyoxyalkylene glycol abiethyl ether or polyoxyalkylene glycol hydroabiethyl ether represented by the above general formula can be converted into abiethyl alcohol or polyoxyalkylene glycol abiethyl ether by a known method. By subjecting hahydroabiethyl alcohol to an addition reaction with hair alkylene oxide, it is obtained as a polyglycol having a molecular weight of about 700 to 5,000, either block type or random type, 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, same below), and (C)/(D
)=100150 to 25/100. (A)/(
If D) is larger than 100/lQ, the resulting polyetherester will not be able to impart sufficient hydrophilicity. On the other hand, if (A)/(]) is smaller than 100/40,
The hydrophilicity of the obtained polyetherester is too strong, and the wash resistance of the imparted hydrophilicity deteriorates. Also, (C
)/(D) is larger than 100,150, if the molecular weight of (C) is large, the wash resistance of the hydrophilicity imparted to the resulting polyether ester will be low. When the molecular weight of (C) is small, the emulsion stability of the emulsion prepared from the resulting polyether ester is poor. On the contrary (C)
If /(D) is smaller than 25/100, the degree of improvement in hand by the resulting polyetherester will be low.

The polyether ester of the present invention is as described above (A)
, (B), (C) and (D) under predetermined conditions according to the already known method for producing linear polyethylene terephthalate, resulting in an average molecular weight of 30.
It can be obtained as a product of about 00 to 20,000.

In this case, (D) acts as a terminal group of the polyZ-f ester, and the block-type polyoxyalkylene glycol; An ether ester is obtained, and since the average molecular weight of the obtained polyether ester can be controlled by the amount of (D) used, the reproducibility as a processing agent will eventually be improved. In addition, when producing the polyether ester of the present invention, crosslinking components such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, pyromellitic acid, etc., to an extent that does not impair water dispersibility, are added. The compounds may also be copolymerized.

Polyester synthetic fibers to be treated with the processing agent of the present invention include polyester synthetic fibers such as polyethylene terephthalate/isophthalate or polyethylene terephthalate/butyne/terephthalate, and modified polyester synthetic fibers (e.g., basic polyester synthetic fibers). or yarn, cotton, woven fabric, or knitted fabric 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 adjuvants may be used in combination within a range that does not impair 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.

1) Excellent hydrophilicity can be imparted.

11) A good texture can be imparted. Compared to polyester synthetic fibers, it does not have an excessively slippery or slimy feel, and does not cause slippage (misalignment of threads).

111) Hydrophilicity with wash resistance and good texture can be imparted. The polyether ester of the present invention exhibits sufficient adhesion or affinity for 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 explained in more detail with reference to Examples. The test conditions, measurement methods, evaluation criteria, etc. are as follows. In the following description, parts mean parts by weight, q means weight %, actual examples, and ratios mean comparative examples. 0 Polyester-based Conditions for applying to synthetic fibers: Polyester (100%) staple (semi-dull 164 denier
8m cut) was degreased and sprayed with 0.3 of each treatment agent.
% by weight, dried at 90°C for 60 minutes, and dried at 150'CX.
It was heat set for 15 minutes and used as a sample.

Washing conditions: The sample was stirred at 45° C. for 5 minutes in a 1 f/1 solution of a commercially available detergent (ZABU, manufactured by Kao Soap Co., Ltd. and reduced to 40%), washed with water, and dried. This was washed once and the edges were turned over 5 times.Evaluation of hydrophilicity: The sample or its 1f after washing 5 times was shaped into a sphere with a diameter of about 4 strokes, and was gently placed on the water surface until it settled. time (seconds)
was measured. 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 slippery and rough texture... Large slippage Δ... Slippage ○... Little slippage, flexible and good ■... No slippage, no flexibility X... Roughness 9 texture Evaluation of slipperiness based on defect/static friction coefficient: The sample or the one after washing 5 times was evaluated by radar method.
The coefficient of static friction between fibers was measured at 0°C x 6 SRH and evaluated based on the following criteria.

×...0.290 or less (static friction coefficient, same below) Todoroki
...0.291 - 0.313 0...0.3 0 5 - 0.313 0...0.314 - 0.332 ■...0.333 - 0.345 M...0. Synthesis of (D) above: 289 parts of abietyl alcohol derived from rosin raw material (Avitol, manufactured by Vercules) were charged into an autoclave, and after replacing with nitrogen gas, 4.5 parts of potassium hydroxide in the form of flakes was added. 3 to 5 at 130 to 150℃.
1,745 parts of ethylene oxide was reacted under a pressure of 9/yt for 5 hours. After adsorbing the catalyst, it was heated in a furnace to obtain polyoxyethylene glycol abiethyl ether (hereinafter simply referred to as a compound) having an average molecular weight of 2000.

e Synthesis of polyetherester of the present invention and preparation of emulsion: 310.4 parts of dimethyl teleheptatalate, 77.6 parts of dimethyl isophthalate, 273 parts of ethylene glycol, 200 parts of polyoxyethylene glycol having an average molecular weight of 1000, and a catalyst. 0.8 parts of manganese acetate tetrahydrate and 0.19 parts of antimony trioxide were charged into a reaction vessel, and transesterification was carried out at 150 to 230°C under a nitrogen gas stream according to a conventional method. After distilling off a predetermined amount of methanol, , phosphorous acid 0.28
1 part and then 480 parts of Compound D to give 270'
It took 2 hours to reach C, and the pressure was gradually reduced while raising the temperature.
Finally, polycondensation was carried out at 270° C. for 40 minutes under a reduced pressure of 11EII Hg. The average molecular weight of the obtained polyether ester (hereinafter simply referred to as compound S) measured by GPC was 9,500.

Then, 895 parts of this compound was brought to a molten state at 170 to 180°C, and 5gt of polyoxyethylene (10 mol) nonylphenyl ether - 9oof of water at 30°C was prepared.
The emulsifier was added to the solution dissolved in the solution while stirring with a homomixer to obtain a stable aqueous emulsicon (Example-1) with a concentration of Compound S of 9.5%.

- Test section: Using the water-based emulsion (Example-1), samples were obtained and evaluated as described above. The results are shown in Table 1.

Note) After washing: 5 @ After washing, - marks were not evaluated (the same applies below) 0 Ratio -1 is untreated staple.

For Ratio-2, Permalose TMC (manufactured by Imperial Chemical Industry Co., Ltd.) was used.

For ratio-3, use the following emulsion: φ-dimethyl terephthalate/dimethyl inphthalate = 80/20
(molar ratio) 150 parts in total, 1 part ethylene glycol
20 parts, average molecular weight 3100 (7), 340 parts of NIJ ethylene glycol monophenyl ether, 0.30 part of manganese acetate tetrahydrate and 0.0 part of antimony dioxide.
73 parts, and at normal pressure and 175-235°C.
After reacting for 80 minutes, the theoretical amount of methanol was distilled off.
The transesterification reaction was completed. Next, after adding 0.11 part of phosphorous acid to this, 2
20 min at 30-260°C followed by 0.8 sa
g The resulting copolymer was reacted for 40 minutes at 275° C. under a reduced pressure of Hg, and the resulting copolymer was immediately poured into water at room temperature in a homomixer with stirring to form a 10% emulsion.

-Test Category 2: Molar ratio of compound RI to the total amount of dicarboxylic acid, molar ratio of terephthalic acid to other dicarboxylic acids in the dicarboxylic acid, molar ratio of compound RI to polyoxyethylene glycol, and polyoxyethylene glycol Compound S was obtained by varying the molecular weight of polyether ester according to the above-mentioned method to prepare an aqueous emulsion, and a polyester stable was treated to obtain a sample and evaluated. The results are shown in Tables 2 and 3.

Table 2 Table 3 Note: Throughout Tables 2 and 3, on each side, ethylene glycol was used in moles 2.2 times the total amount of dicarboxylic acids. A-1 is terephthalic acid, A-2 is inphthalic acid. ,A-3
is adipic acid OC. C is polyoxyethylene glycol, and the appended value is its average molecular weight.

Ratio-4 had poor emulsion stability and could not be put to practical use.

・Test category: Polyoxyalkylene glycol abiethyl ether was obtained by the same reaction as in the case of obtaining compound S, but by varying the type of alkylene oxide used and the number of moles thereof. Similarly to the method, a polyether ester is produced to form an aqueous emulsion W/,
Samples were obtained by processing polyester stable and evaluated. The results are shown in Table 4.

Note) m, R1, and n are the same as the symbols in the general formula above.

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 has sufficient washing resistance with these properties. It is clear that he is demonstrating his sexuality.

Patent applicant: Takemoto Yushi Co., Ltd. Agent: Hiroshi Yama, Patent Attorney 1, 1 (11-

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 is )=100/1
0 to 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 with residue (D) formed at the end of the molecule A processing agent for polyester-based synthetic fibers, characterized in that it consists of a hydroabiethyl etherified polyether ester. (A): Dicarboxylic acid or lower alkyl ester thereof, of which 70 mol% or more consists of terephthalic acid or its lower alkyl ester (B): Ethylene glycol (C): Polyoxyethylene glycol having an average molecular weight of 600 to 2000 (D): The following Polyoxyalkylene glycol abiethyl ether and/or polyoxyalkylene glycol abiethyl ether represented by the general formula: ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [However, R^ is shown in the following (1) or a hydroabiethyl group represented by (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. ] (1): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼