JPS6195057A - Production of modified polyester fiber - Google Patents

Abstract

PURPOSE:To obtain the titled fiber of both persistent autistatic potential and stain absorptivity, free from strength drop even after weight reduction by alkali, by incorporating a small amount of POG in a polyester incorporated with a specific phosphorus compound and then by spinning using a cap with its single hole having a specified open area. CONSTITUTION:A polyalkylene terephthalate polyester incorporated with 150-1,000ppm, on a P-atom basis, of phosphorus (V) compound of formula [R1, R2 and R3 are each H, OH, OX, 1-20C oxyalkyl, oxyaryl, alkyl or aryl; where at least one of R1, R2 and R3 being OH, oxyalkyl or oxyaryl; X is alkalicalkaline earth) metal] is incorporated with 0.1-5wt% of a polyoxyalkylene glycol (POG) or its derivative. The resulting polyester is subjected to melt spinning using a cap with its single hole having >=0.2mm<2> of open area. Said phosphorus (V) compound may be used in combination with a metal (II) compound in an atom number ratio P/said metal=0.5-5.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing modified polyester fibers. More specifically, regarding a method for producing polyester fibers that have excellent antistatic properties and water absorption properties and have little loss of strength even after weight loss treatment with alkali, the polyester fibers obtained by the method of the present invention are As a material, of course, it can be used in combination with other different types of fibers, such as blended yarns, mixed fiber yarns, processed yarns, mixed fibers with different types of fibers or yarns made of different types of fibers, mixed knitted items, non-woven fabrics, heavy fabrics, and multilayer structure woven fabrics. It also exhibits excellent antistatic effects on knitted fabrics, etc. In addition, the fibers obtained by the present invention can be used for dress shirts, casual shirts, women's blouses, women's skirts, underwear, slacks, men's formal wear,
Rezois formal wear, knitwear, sportswear, coats, outwear in general, baby wear, children's wear in general, men's suits, jackets, blouson, general uniforms, working wear for special work, dust-free clothing, kimonos,
Japanese underwear, Japanese lining, household items (aprons, tablecloths, gloves, hats, etc.),! These include odor or sleeping clothes (futons, sheets, duvet covers, pajamas, etc.), interior ceiling and flooring materials for automobiles, interior goods, carpets, and other industrial materials.

[Conventional technology]

Hydrophobic polymeric substances, such as polyethylene terephthalate, are easily charged due to friction, peeling, etc., and this W resistance causes various problems in molded products, and during use, it may cause shock due to electrical discharge, attract dust, etc. It has the following disadvantages. In order to eliminate these drawbacks, methods have been proposed in which an antistatic agent is attached to the surface of the molded product or mixed into the molded product.

Of the nine proposals above, the method of blending an antistatic agent into a polymeric material is known as a relatively durable method. For example, a method of blending a polyoxyalkylene glycol into a thermoplastic polymer such as polyethylene terephthalate has been disclosed. ing.

[Problem that the invention seeks to solve]

However, in order to impart practically sufficient antistatic properties to polyester fibers by this method, it is necessary to contain a large amount of polyoxyalkylene glycol or its derivatives (hereinafter abbreviated as POG). This large amount of POG is added to the polyester Z-r tk woven fiber.
Polyester fibers whose antistatic properties have been improved by this method have the disadvantage that they have very little practical value. In order to improve this drawback, many proposals have been made to impart antistatic properties to polyester fibers by adding a small amount of POG. Most cases were accompanied by an extreme decrease in sex.

On the other hand, when polyester fibers containing polyoxyalkylene glycol or its derivatives are subjected to weight reduction treatment with an alkali, significant fibrillation occurs, resulting in a decrease in strength to the extent that it cannot be put to practical use.

[Means to solve the problem]

There has been a strong desire to develop polyester fibers that do not have the above-mentioned drawbacks, have practical and durable antistatic and dirt absorbing properties, and do not lose strength even after alkali weight reduction treatment. .

The present inventors have conducted intensive studies to obtain a polyester fiber that exhibits practical durable antistatic properties and excellent water absorption, has no POG addition amount, and does not lose its strength through alkali weight reduction treatment. By spinning a composition obtained by adding a small amount of FOG to the polyester obtained by adding the compound using a spinneret having a single hole with a single hole opening area of 0.2- or more. They have discovered that polyester fibers that satisfy the above objectives can be obtained, and have arrived at the present invention. That is, the present invention provides general formula (I) 0-P-1h (It (wherein R1, R1 and Rs are the same or different groups and H
loH, OX (X is an alkali metal or alkaline earth metal), 1 to 2 carbon atoms with or without substituents
0 oxyalkyl group, oxyaryl group, alkyl group, and aryl group. However, at least one of Rt, Ih and R3 is OH, OX, an oxyalkyl group or an oxyaryl group. ) with 150 to 11,000 phosphorus atoms
A composition containing 0.1 to 5% by weight of polyoxyalkylene glycol or a derivative thereof based on the total composition in polyalkylene diterephthalate polyester obtained by adding PP was prepared with a single pore opening area of 0.2- This is a method for producing a modified polyester fiber, which is characterized by performing melt spinning using a spinneret having a single hole as described above.

Examples of the pentavalent phosphorus compound represented by the general formula (I) of the present invention include phosphoric acid, sodium salt of phosphoric acid, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, phosphonic acid, phenylphosphonic acid, dimethylphenylphosphonate, 3- dimethylphosphono-methylpropionate, diethylphosphono-ethyl acetate)
, 9.10-dihydro-1O-oxy-9-oxa-I
Examples include O-phosphaphenanthrene-1O-oxide, phosphinic acid, diphenylphosphinic acid, and ethyldimethylphosphinate. These phosphorus compounds may be used alone or in combination of two or more. It can be added to the polyester at any stage from the synthesis of the polyester to the blending of polyoxyalkylene glycol or its derivatives, but it is best to add it to the reaction system before or after the transesterification or esterification reaction. Common. In order to suppress side reactions accompanying the addition of a phosphorus compound, a divalent metal compound is added in an amount such that the atomic ratio of phosphorus/metal is from 0.5 to 5 at the same time as or before or after the addition of the phosphorus compound. It is preferable. Such divalent metal compounds include magnesium, calcium, zinc,
Examples include organic acid salts such as manganese and cobalt, and halides.

The amount of phosphorus compound added is 150 to 11 phosphorus atoms.
000 ppm, preferably 200 to 600 ppm.

If it is less than 150 ppm, the effect of suppressing strength loss due to the alkaline weight loss treatment is small, and if it is more than 00 ppm, the resulting polyester will have decreased heat resistance and coloration, and problems such as filter clogging during melt spinning may occur. arise.

The polyethylene terephthalate group polyester used in the present invention is a polyester containing terephthalic acid as the main acid component and ethylene glycol, tetramethylene glycol, cyclohexane-1,4-dimethanol 1-ol, etc. as the main glycol component. A small amount, usually 16 mol % or less, of the gJ3 component may be copolymerized. Examples of the copolymerizable jI8 component include dicarboxylic acids such as isophthalic acid, sodium 8,5-di(carbomethoxy)benzenesulfonate, adipic acid, sebacic acid, and cyclohexane-1,4-dicarboxylic acid.

The polyoxyalkylene glycol or its derivative (POG) referred to in the present invention refers to thermoplastic synthesis 1jli! For example, Japanese Patent Publication No. 89 Sho.
As seen in Japanese Patent Publication No. 5214, Japanese Patent Publication No. 57-4724, etc., this term refers to all commonly known substances, and specific examples thereof include polyethylene glycol, polypropylene glycol, and random combinations of ethylene oxide and propylene oxide. Alternatively, block copolymers, polytetramethylene glycol, block copolymers obtained by adding polytetramethylene glycol polyethylene oxide, neopentyl glycol, and compounds in which ethylene oxide is added to bisphenol glycol have hydroxyl groups at both ends. polyoxyalkylene compounds, monophenoxypolyethylene glycol, nonylphenoxypolyethylene glycol, sodium sulfophenoxypolyethylene glycol, diphenoxypolyethylene glycol, and pieces such as compounds in which 2 moles of monophenoxy polyethylene glycol are combined with 1 mole of tolylene diisocyanate. Polyoxyalkylene compounds whose terminal or both terminals are blocked via an ether bond, polyethylene glycol laurate, polyethylene glycol phosphate, or a partial alkali salt thereof, polyethylene glycol phosphonate, or one terminal thereof such as a partial alkali salt thereof. Or a polyether compound esterified at both ends, a block copolymer of polyethylene glycol and polyethylene terephthalate, a block copolymer of polytetramethylene glycol and polyethylene terephthalate or polybutylene terephthalate, a block of polyethylene glycol and polypropyramid. Copolymer, polyethylene glycol with one or both ends cyanoethylated or polyethylene glycol with this cyano group as an amino group, compound obtained by adding ethylene oxide to a primary or secondary alkylamine, represented by the following formula Examples include amphoteric compounds.

It goes without saying that the POG referred to in the present invention is not limited to the above specific examples, and may be one of these compounds or a mixture of two or more thereof.

Moreover, in the above POG, both ends are -OH.

In the case of a group having active hydrogen such as -COOH, NHZ, etc., the weight average molecular weight (hereinafter abbreviated as molecular weight) of the POG is preferably 6,000 or more. Also, one end is
When a group has an active hydrogen and the other end is blocked by a group that does not have an active hydrogen, the molecular weight of POG is 40.
It is preferable that it is 00 or more. In addition, when both ends are blocked with groups that do not have active hydrogen, POG
The molecular weight of is preferably 1000 or more.

The POG to be used in the present invention is the above-mentioned POG.
It is fine as long as it is OG. Furthermore, this additional P should be contained.
Antioxidants, ultraviolet absorbers, pigments, organic or inorganic ionic compounds, and other additives may be mixed in advance with OG.

The amount of POG to be added in the present invention is from 0.1 to 5% by weight, preferably from 0JI to 5% by weight, based on the total composition. If it is less than 0.1% by weight, the antistatic effect will be small, and if it exceeds 5% by weight, the excellent properties originally possessed by polyester fibers will be impaired, and in particular, light resistance will be deteriorated, which is not preferable.

The method for obtaining the composition in the present invention is not particularly limited, but may be appropriately selected in consideration of productivity, operability, brand of modified polyester fiber to be produced, etc.
＼) The composition obtained as described above is usually processed using a spinneret having a single hole of a commonly used size (for example, a round hole with a diameter of 0.2 to 0.8 mm). When spinning, polyester fibers with practical levels of antistatic properties and water absorption can only be obtained when a large amount of POG is added. However, surprisingly, the same composition, which is a requirement of the present invention, has a single pore opening area of 0.2- or more, e.g.
If spinning is performed using a spinneret with a single hole with a diameter of
Even from a composition in which the amount of POG is 0.5% by weight, polyester fibers having practical antistatic properties and water absorption properties can be obtained.

The spinneret used in the present invention has a single hole opening area of 0.
．． As long as it has two or more single holes, the shape of the single holes is not particularly limited, and may be round, oval, Y-shaped, triangular, square, hexagonal, or any other shape. Preferably, a shape for forming a solid cross-section thread is better than a shape for forming a hollow cross-section thread.

Among the plurality of single holes of the spinneret having such single holes with an opening area of 0.2- or more, all of the single holes may have an opening area of 0.2- or more, and some of the single holes may have an opening area of 0.2- or more. is 0.2-
It may be a single hole as described above. Preferably, the opening area of the single hole is 0.4- or more, particularly preferably 0.4-
~1.6-.

In addition, the discharge amount (Ql/min) of the melt of the composition of the present invention per each single hole in the present invention is determined by calculating the opening area of the single hole by 5 (Ql/min).
−), an amount satisfying the formula S2O,0202-0.2 is preferable, and more preferably S2O,I Q”+
This is an amount that satisfies 0.4.

The melt spinning method for the composition of the present invention is not particularly limited, and any conventional method can be employed. That is, a method in which the yarn melt-spun through the spinneret is cooled in a conventional manner with a cooling air stream, wound as an undrawn yarn, and then stretched;
A method of drawing the yarn continuously during the spinning process and winding it as a drawn yarn.
Any method using high speed to ultra high speed spinning of 2000 to 10,000 m/min can be adopted. Furthermore, a highly oriented undrawn yarn obtained by high-speed spinning may be drawn (simultaneously) false-twisted to produce a false-twisted yarn.

According to the method of the present invention, a fiber product obtained by blending POG with a polyester to which a phosphorus compound or a phosphorus compound and a divalent metal compound has been added has a lower amount of POG than a polyester that does not contain a phosphorus compound. Not only does it provide excellent antistatic properties, but it also exhibits little fibrillation when subjected to alkali weight reduction treatment, with very little loss of strength.

Conventionally, in order to improve the antistatic properties of polyester fibers containing POG, an ionic compound including the phosphorus compound of the present invention has been added to POG and blended with polyester. The strength of the resulting fibers is significantly lowered due to alkali weight loss, and the strength is more likely to be lowered due to alkali weight loss than polyester fibers containing unmodified POG.

Therefore, [effect of the invention] In the method of the present invention, adding a phosphorus compound to polyester improves the above-mentioned alkali weight loss resistance and PO
It is effective in reducing the amount of G added, and using a specific spinneret is extremely effective in reducing the amount of POG added. By combining the two methods, it is possible to obtain for the first time highly practical, high-quality polyester fibers with antistatic and stain absorbing properties.

According to the present invention, the antistatic property and water absorption level and durability thereof (i.e., durable antistatic property and durable water absorption property) are extremely excellent with a small POG content, and furthermore,
Even by alkali weight loss treatment, polyester fibers with little loss of strength can be obtained, and the field of use of polyester fibers can be greatly expanded by removing the fibers.

〔Example〕

Examples of the present invention will be shown below. In the examples, unless otherwise specified, percentages (%) represent weight percentages (%).

In addition, in the examples, charge leakage half-life (hereinafter referred to as half-life) representing antistatic property, wicking representing water absorption property,
The washing process followed the method below.

b) Half-life: After knitting and weaving the obtained filaments or fibers, the half-life side
Measured by standard method). The sample fabric was kept at a controlled temperature and humidity of 20° C. and 40% R, H for 24 hours or more, and then measured under the same conditions.

(b) Wicking: After knitting and weaving the obtained filaments or fibers, it was measured by method 6-26-1-(1)A (dropping method) specified in JIS-1096-1979.

e-+ Light resistance: After knitting the obtained filaments, the knitted material was dyed with a dyeing solution of 1.0% owf of Resolin Blue FBL (dispersible dye manufactured by Bayer AG) at a bath ratio of 1:50.
After dyeing in a conventional manner at 80° C. for 160 minutes, washing with reduction and air drying, the fastness to sunlight was measured according to JIS-L-0842.

4. Weight loss treatment and strength retention: The knitted filament was hydroxylated at 109/l) under boiling conditions at a bath ratio of 1:100 with an IJium aqueous solution, so that the weight loss rate was 20% relative to the initial weight. I made it. Using the disassembled yarn of the knitted material before and after the weight loss treatment, the monofilament yarn strength (,9/d) was measured using Tensilon, and the ratio of the yarn strength after the weight loss treatment to the yarn strength before the weight loss treatment was calculated. It was calculated as a retention rate (%).

Laundry treatment The two knitted fabrics were washed with a neutral detergent 0.511/11 aqueous solution for 40° Cl2O minutes in a home washing machine, dehydrated, rinsed under running water at room temperature for 20 minutes, and dehydrated again. Dehydration was performed by rinsing with warm water at 40° C. for 5 minutes. After repeating the above operation 20 times, it was air-dried.

Examples 1 to 8, Comparative Examples 1 to 5 1000 parts of terephthalic acid, 790 parts of ethylene glycol, 0.44 parts of antimony trioxide and 1.82 parts of triethylamine were mixed at 245°C under a nitrogen pressure of 2.5 kg/Cd.
The mixture was reacted for 20 minutes to perform an esterification reaction. Next, zinc acetate (dihydrate) corresponding to 0.098 mol% of terephthalic acid and trimethyl phosphate corresponding to 0.186 mol% were added to the reaction system, and after stirring for 10 minutes, the temperature of the thread was increased from 245°C. While raising the temperature to 275°C over a period of 60 minutes, vacuum was gradually applied to reduce the thread pressure from normal pressure to 0. It was lowered to lffHg. Then increase the temperature to 275°C
Then, a polycondensation reaction was carried out for 90 minutes while maintaining the pressure at 0.1jffHg, and the intrinsic viscosity was 0.684, which was measured at 80°C using a mixed solvent of phenol/tetrachloroethane (6/4).
Polyethylene terephthalate (PET) containing phosphorus
) was obtained. Phosphorus content measured with Fluorescence XM is 260pp
It was m. For comparison, PET with an intrinsic viscosity of 0.681 without the addition of zinc acetate and trimethyl phosphate was also obtained under the same conditions as above. When melt-spinning the above PET by extrusion spinning using a screw at a spinning temperature of 290°C, the antioxidant 1,8.5-trimethyl-2,4,6-tris(8,5-ditertiary-butyl) Polyethylene glycol (PEG) having an average molecular weight of 20,000 and containing 1% of -4-hydroxybenzyl)benzene was fed in a fixed amount to the metering zone of a screw extruder in a predetermined amount per fiber obtained as PEG. As a spinneret, one has 86 circular spinning holes with a single hole opening area of 0.785-, which is within the scope of the present invention, and for comparison, one has 3 circular spinning holes with a single-hole opening area of 0.042-
Melt-spinning was carried out under the condition that the discharge amount per single hole was 0.5 fl/min, and the spun yarn was 90
It was wound at 0 m/min.

This was drawn by a conventional method to obtain a fiber of 75 denier/86 filaments. These filaments have a fabric weight of 15
It was knitted into a 0.9/- interlock, and its antistatic properties (half-life), stain absorption properties (wicking properties), light resistance, and strength retention after alkali weight loss (20%) treatment were evaluated. .

Note that the light resistance and strong retention rate were evaluated for unwashed samples. The results are shown in Table 1.

As is clear from Table 1, the method of the present invention exhibits excellent antistatic properties even with a small amount of P'EG, and is also superior in strong retention, dirt absorption, and light resistance after alkali reduction treatment. I understand.

! 1 Table 1

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R_1, R_2 and R_3 are the same or different groups, H, OH, OX (X is an alkali metal or alkaline earth (metals), oxyalkyl groups, oxyaryl groups, alkyl groups, and aryl groups having 1 to 20 carbon atoms with or without substituents.However, at least one of R_1, R_2, and R_3 is OH, oxyalkyl or oxyaryl group), the pentavalent phosphorus compound represented by
A composition containing 0.1 to 5% by weight of polyoxyalkylene glycol or a derivative thereof based on the total composition of polyalkylene terephthalate polyester obtained by adding 00ppm was prepared with a single pore opening area of 0.2mm^2. A method for producing a modified polyester fiber, which comprises performing melt spinning using a spinneret having a single hole as described above. (2) The polyalkylene terephthalate polyester is added with a pentavalent phosphorus compound represented by the general formula (I) and a divalent metal compound in an amount such that the atomic ratio of phosphorus/metal is 0.5 to 5. A method for producing a modified polyester fiber according to claim (1), which is polyester.