JPS63165516A - Water-soluble polyester fiber - Google Patents

Abstract

PURPOSE:To obtain the titled fiber, consisting of a polymer prepared by copolymerizing polyethylene terephthalate with respective specific amounts of sodium sulfoisophthalate, isophthalic acid and aliphatic dicarboxylic acid. CONSTITUTION:The aimed fiber, obtained by using a copolyester containing terephthalic acid and ethylene glycol as principal components, 5-sodium sulfoisophthalate in an amount of 8-16mol% based on the total acid component, isophthalic acid in an amount of 5-20mol% based on the total acid component and a 3-20C aliphatic dicarboxylic acid in an amount of 5-20mol% based on the total acid component as a single component constituting the fibers and having >=0.8g/d fiber strength. Furthermore, in order to increase the fiber strength to >=0.8g/d, a nonhydrous oiling agent is preferably used for oiling in spinning the fiber and heating at >=90 deg.C is preferably carried out in the fiber spinning step.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to water-soluble polyester fibers that can be manufactured by melt spinning and can be easily dissolved and removed with hot water. This fiber is extremely useful for improving quality and saving labor in processes such as manufacturing bases for chemical sillage, creating patterns for knitted and woven fabrics, and separating continuously knitted socks and sweaters. It is.

[Prior art] Polyvinyl alcohol (
Fibers made of PVA (hereinafter abbreviated as PVA) are widely used. However, since this PVΔ fiber is generally produced by a dry spinning method, there is a problem in that the productivity is lower and the manufacturing cost is higher than in the case of melt spinning.

In addition, as other water-soluble polymers, 12 copolymerized polynisdels and copolymerized polynomides have been proposed.

For example, 5-sulfoisophthalic acid butylhelium salt is
171 Publication No. 58-39926 ¥'
J: is proposed in the official gazette. However, when a large amount of 5-sulfoisophthalic acid sodium salt is added as described in this publication, it becomes difficult to obtain a sufficient degree of polymerization due to the foaming and thickening effects in 1.1 of the polycondensation reaction. Moreover, the spinning properties during melt spinning are also not satisfactory. Moreover, since this water-soluble polyester is eluted even with cold water, water cannot be used for cooling the molten polymer after the polymerization reaction and when it is made into a solid. is necessary. In the case of this discharge air cooling, a long cooling zone and a belt or 1]-
However, such a long cooling zone will reduce the oxidative decomposition of the polymer to Vl.

Furthermore, after being made into OIi fibers, they are subject to deformation due to moisture in the air, making them difficult to handle during processing, and they have not yet been put to practical use.

Furthermore, water-soluble polyester can be used as adhesives, sizing agents, etc.
Many proposals have been made for use as an aqueous solution such as 114 (for example, Japanese Patent Publication No. 47-40873, 57-2
No. 6309, No. 60-1334, etc.), but these proposals only consider use as an aqueous solution.

Furthermore, it is written in Japanese Patent Publication No. 55-1374, +,!
The water-soluble polyamide (31, heat pacifying and
However, there are many problems such as poor l'l, J: due to the oligomers and T threads contained, and the long time it takes to dissolve in hot water, so it has not been put to practical use. .

In this way, a large number of water-soluble polymers that can be melt-spun have been developed, but in actual production, there are many problems such as spinability and handling of post-addition IIL'+, and PVA At present, water-soluble ↑ [Navy blue, 17 water-soluble fibers] have not been studied.

[Problems to be Solved by the Invention] In addition, the present invention does not have the above-mentioned drawbacks, can be easily made into fibers by melt spinning, and can be easily made into fibers by melt spinning. It is easy to dissolve and remove by etc., and
The main objective is to provide a polyester fiber that is insoluble in cold water and soluble in hot water.

That is, the present invention is a water-soluble polyester that can be stably spun with high productivity even at high speeds, is easy to process, and is suitable for industrial production! 1lli navy blue is provided.

[Means for solving the problem] In order to achieve this object, the present invention uses terephthalic acid and ethylene glycol as main components, and contains 5-sodium sulfoisophthalate in an amount of 8 to 16 mol% based on the total acid components. acid, 5-20 mol% isophthalic acid, J5 J:bi5
A substantially single-component fiber composed of a copolymerized polyester containing ~20 mol% of aliphatic dicarboxylic acid having 3 to 20 carbon atoms, and having a fiber strength of at least 0
．． 89/d water-soluble polyester fiber.

Thus, the present invention provides polyethylene terephthalate 1 to
at least 5-sodium sulfoisophthalic acid, isophthalic acid, and an aliphatic dicarboxylic acid having 3 to 20 carbon atoms,
It is characterized in that it is a substantially single-component fiber manufactured from hot water-soluble bamboo copolyester copolymerized in specific proportions.

The copolymerization component 5-sodium sulfoisophthalic acid is 8 to 16 mol% of the total acid component, preferably 4J, "j
Q~・11% is good. 8T nitrogen% has not been reached ("1i is not dissolved and removed in hot water, etc.").On the other hand, 16
If the amount exceeds mol %, the polymer will be eluted even with cold water, making it difficult to handle the polymer during cooling, melt spinning or stretching, making it unsuitable for industrial production.

Furthermore, it is necessary to use the above-mentioned 5-sodium sulfoisophthalic acid and isophthalic acid and an aliphatic dicarboxylic acid having 3 to 20 carbon atoms (If, in this case,
The copolymerization ratio of isophthalic acid to the total acid component is 5 to 5.
The content of the aliphatic dicarboxylic acid having 3 to 20 carbon atoms is 5 to 20% by mole based on the total acid component.

When isophthalic acid and aliphatic dicarboxylic acid (71) are used, if the isophthalic acid content is less than 5 mol%, the solubility in hot water, etc. will be low (1 will be low, and luke-like insoluble matter will be formed when dissolving in hot water, etc.) On the other hand, if this isophthalic acid exceeds 20%, the undrawn yarn that is spun (1:I!) becomes brittle and fluff is often generated during high-speed drawing. Since it becomes difficult to reel yarn stably at high speed, production costs increase.

Further, if the C3-20 aliphatic dicarboxylic acid is less than 5 mol %, the effect of improving the flexibility of the undrawn yarn and improving high-speed drawability is insufficient. On the other hand, if this aliphatic dicarboxylic acid exceeds 20 mol%, the softening point of the polymer becomes too low, making it difficult to perform melt spinning because the drying time before melt spinning cannot be completed at 1°j every 11 minutes. Even if melt spinning is possible, it is difficult to produce fibers that are satisfactory in practical use because fusion occurs between single yarns or between yarns in the wound yarn during spinning or drawing.

In this copolymerized polyester, the main component (ie, about 50 mol % or more of the other components) is ethylene glycol phthalate. If the proportion of terephthalic acid is too small, the softening point of the polymer will be too low, resulting in roughness in the wound yarn during chip drying before melt spinning, spinning, and drawing.

In addition to the above-mentioned essential copolymerized components, this copolymerized polyester contains hydrophilic polyols, etc., which are insoluble in cold water and soluble in hot water and hot water, so that they do not inhibit the excellent properties of 1?1.i. If so, they may be copolymerized.

The hydrophilic polyol component to be copolymerized is preferably a WS conductor of polyfulkylene glycol having a number average molecular weight of 1A400 to 6000;
If the content is 15wt% or less based on the total polymer,
It is preferable to set it as 10 wt%.

In order to determine the solubility effect in dilute alkaline water, t: upper,
A copolymerization coverage of at least 3 wt% is desirable. on the other hand,
If it exceeds 15 wt%, the stability of the fibers against cold water will decrease.

Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol,
Examples include Polite 1 to Ramedylene Green 1. In addition, examples of derivatives include polyether compounds which can be converted into 17 by adding ethylene oxide, propylene oxylide, butylene oxylide, etc. to the noenolic hydroxyl group of a bisphenol compound such as bis-7''nol-8. can be mentioned.

yIi average molecule of this polyalkylene glycol [d
is preferably 400 to 6000, more preferably 600 to 4000. If it deviates from this number average numerator, it is 1! Since the fiber-forming property of the copolymerized polymer becomes insufficient, fiber production becomes difficult.

[Function] The fiber according to the present invention has a 1.
It is a substantially single-component fiber composed of a copolymerized polyester having a polyester of 21. This property of being insoluble in cold water and soluble in hot water etc. is very important and necessary in producing I-navy blue by melt spinning. In other words, if it is soluble in cold water, the cooling method of discharging it into a water bath, which is generally used when converting the molten polymer into a discharged glass after the completion of the condensation reaction, cannot be used, and the chip Since the fibers and fibers are deformed by moisture in the air, stable industrial production is difficult.

Copolymerization of a specific amount of 5-sulfoisophthalic acid is essential for making polyester water-soluble, but it makes it soluble in hot water and insoluble in cold water, making it easier to manufacture chips and fibers and their handling. In order to achieve this, it is necessary to copolymerize 15% isophthalic acid and C3-20 aliphatic dicarboxylic acid.

Furthermore, when a specific amount of the above-mentioned polyalkylene glycols is copolymerized as other copolymerization components, it becomes soluble in dilute alkaline water without impairing the 1Fi property of being soluble in hot water and insoluble in cold water. I can do it. As the dilute alkaline water, a concentration of 2 to 2N is used, and examples thereof include a mono-lithium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a soda carbonate aqueous solution, and the like. In addition, this very thin fa-maro dilute alkaline water is used during wastewater treatment.
Since there is no need to dilute it, it is suitable for industrial use.

The water-soluble fiber according to the present invention, which is formed by combining isophthalic acid J3 and C3-20 aliphatic dicarboxylic acid together with 5-sulfoisophthalic acid, can be dissolved in hot water or hot water to form a transparent liquid or a transparent liquid. can be made into a liquid in a finely dispersed state, and can be dissolved in hot water or the like without using any auxiliary agents and without leaving any foreign matter residues.

Furthermore, since the fiber according to the present invention has a fiber strength of 0.8 o/d or more, preferably 1.0 g/d or more,
Through normal textile manufacturing processes such as knitting and weaving, the fiber can be easily manufactured by itself or by mixing it with other fibers.

The fiber according to the present invention can be produced by a melt spinning method and conditions similar to the ordinary polyethylene terephthalate 1 to fiber spinning method, if the spinning oil and the heating conditions during spinning are appropriately selected as shown below. It can be easily manufactured. For example, there is a method in which the fiber is melt-spun, wound into a -11 package, and then stretched, a method in which spinning and stretching are performed continuously, and a so-called high-speed method in which the fiber is spun at high speed and wound as it is without mechanical stretching. The yarn may be spun using a yarn reeling method. Furthermore, the spinning temperature and the winding speed at the time of winding the undrawn yarn, etc., can basically be set by applying the fiber spinning thread f1 to the ordinary polyethylene terephthalate 1. However, in the case of the fiber according to the present invention, in order to obtain a fiber strength of 0.8 c + / d or more, it is necessary to use a non-hydrous oil for lubricating during spinning, and to apply heat of 90 polish or more in J3 during the spinning process. I need to do something.

The non-water-containing oil agent Ll1 is actually an oil agent that does not contain water. For example, 11 is added to an oil made by adding 11 of J dylene oxylide to A rail alcohol, adding a . A very small amount of water should be 1.1 volumes, or as large as 3% or less.

Further, the heating polishing in step d3 of the spinning process may be performed as long as the culm degree is lower than ')O'C and 3°C lower than the softening temperature of the polymer.

The crushed fibers can be used, for example, as a material to be temporarily mixed for convenience of the weaving process when producing textile products using a knitting/weaving basket. For example, by mixing with X(,4 fibers,
Chemical race river! ,t? The fibers according to the present invention are produced by knitting and weaving knitted fabrics and woven fabrics that are susceptible to ti and weaving diseases, and then treating the knitted fabrics that have been subjected to ti and weaving diseases by immersing them in hot water or the like. It is possible to efficiently produce knitted fabrics in which the watermark is removed by dissolving it from the product. It can also be used at dividing positions when continuously knitting socks, sweaters, etc., and the separation control operation can be performed by treatment with hot water or the like.

In the process of manufacturing these textile products, the fibers of the present invention undergo twisting and carding processes like ordinary water-insoluble fibers. It is possible to stably apply the material without causing any processing problems such as fluffing, tangles, etc.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the Examples, the part means the weight part, and the solubility of the fiber in cold water and hot water, the strong elongation, and the softening point of the polymer were evaluated by the following methods.

Dissolution in cold water ↑ 4: 1 g of thread was soaked in 100 J water at 30°C for 20 hours, taken out and vacuum dried, and the change in weight of the thread was examined.

Solubility in hot water: 1 q of yarn was immersed in 100 g of hot water at 95°C for 20 minutes, taken out and vacuum dried, observed changes in the surface and cross section of the yarn, and mirror photograph of the cross section C1i. We also investigated small changes.

Strong stretching: Toyo Baldwin Co., Ltd. Denji [1-R]
Using TM-100, try 20cm of rimple fishing 4 and 31
The fiber was pulled at a pulling speed of 20cm/min for 20″
Measured under an atmosphere of C165%II +-1.

Softening point: Heat treatment of polymer depth (70'CX3hr)
After L/L, it was measured with a penetrometer. Temperature rising speed If1
The softening point was defined as the temperature at which a 3 mm chip covered the o, immc type by one stroke at 0'C/min.

・Example 1 methyl ester of lenocric acid (-1 △), 99.7 parts of dimebthal terephthalate, isophthalic acid M (IP
Dimethyl isophthalate 16, the methyl ester of Δ)
．． 6 parts,) 27.2 parts of dimethyl adipate, which is the methyl ester of Nodipine II (AA>), 93.3 parts of ethylene glycol, and 0.135 parts of calcium acetate were charged into a reaction vessel, and the by-product methanol was distilled at 130 to 230°C. Nisdell exchange reaction was carried out while the solution was being removed.Next, dimethyl 5-sodium sulfoisophthalate 30, which is the methyl ester of 5-sodium sulfoisophthalate M (SI)
．． 7 parts, antiseptane trioxide 0.03 parts, phosphoric acid 0.00
Add 75 parts and 0.3 parts of lithium acetate to 230~
After reacting at 250'C for 1 hour, condensation polymerization was carried out at 250-275°C and under reduced pressure (1 mmHg or less) for 13 hours. After polymerization, the polymer was discharged into a water bath at room temperature and cooled.
It was made into guts and cut into chips. The IV (intrinsic viscosity in 10 phenol solution) of the crushed polymer was 0.70 and the softening point was 120°C.

After vacuum-drying the chips prepared at 90°C for 24 hours, using a spinneret with a diameter of 0.23 mm and a number of holes of 0,
Melt spinning was performed at 95°C. The spun yarn was air-cooled, oiled with a non-hydrous oil, and then heated at 2000 m/min at 90°C.
The film was passed around a heated first Nelson roller 11-) 6 times, then passed around a second JI+ heated Nelson roller 5 times at 3500 m/min and 105°C, and then stretched and wound. The yarn obtained was approximately 30 j'' niels, 10 filaments 1 to 1, and was 7r't?
did. J3, As a non-S water oil agent, an oil agent consisting of an A rail alkaline additive, an imidacillin antistatic agent, and mineral oil was used.

The yarn was spun by direct spinning and drawing at a high speed of 3,500 m/min, but thread breakage during spinning was hardly a problem, and the yarn could be reeled stably. In addition, J: sea urchin shown in Table 1 is insoluble in cold water and easily soluble in hot water, and has a yarn strength of 1.60 u/d, which is sufficient to withstand post-processing processes. Ta.

Next, the water-soluble fiber M (17) was knitted at the dividing position when continuously knitting the threads 1 to 1, and after that, it was immersed in clean water for 20 minutes and dried. It showed divisibility.

・Examples 2 to 3 Comparative Examples 1 to 6 TPA, IPA, ΔA, S in comonomerized polyester
Copolymerized polyesters having various compositions shown in Table 1 were polymerized in the same manner as in Example 1 by changing the copolymerization ratio of I.

Example 1 except that those copolymerized polyesters were used.
It was dried, melt-spun, stretched, and made into yarn in the same manner as described above. The results are shown in Table 1.

From the results in Table 1, it is clear that the water-soluble bamboo fiber obtained from the copolymerized polyester having the composition specified in the present invention is both easily soluble in hot water and insoluble in cold water, and has sufficient resistance to post-processing steps. The yarn strength was right.

On the other hand, the water-soluble + The fibers were easy to handle and were not easily soluble in hot water. Further, in Comparative Example 4, the polymer stuck together during the drying stage, and melt spinning could not be performed.

The water-soluble polyester fiber according to the present invention has the characteristics of being insoluble in cold water and soluble in hot water, etc.
r I+, 'l are easy to handle and can be easily dissolved and removed from textile products by treatment with hot water or the like.

However, this fiber can be produced by a melt spinning method similar to that used for ordinary non-hydrocarbon fibers, and can be produced stably at high speed and with high productivity.

In addition, since the polymer used has sufficient drawability, it is necessary to optimize the oil agent and heating strip for spinning yarn, which are necessary for post-processing such as knitting and weaving. strength strip (
't can be obtained.

Moreover, since the fibers according to the present invention can be dissolved and removed with warm water or hot water, they are advantageous for industrial applications from the viewpoint of wastewater treatment.

J: Uni, the fiber according to the present invention can be produced with high productivity by melt spinning and has excellent properties such as being easy to handle. It can be widely used for beef cutting. For example, temporary blended fibers are used in processes such as manufacturing base fabrics for chemical lace, creating patterns for knitting and woven fabrics, and separating socks and sweaters. It can be widely used as a fiber.

? '5th edition application applicant Co., Ltd.

Claims (1)

[Claims] The main constituents are terephthalic acid and ethylene glycol, and based on the total acid components, 8 to 16 mol% of 5-sodium sulfoisophthalic acid, 5 to 20 mol% of isophthalic acid, and 5 to 20 mol% of carbon number 3 A substantially monocomponent fiber composed of a copolyester containing ~20 aliphatic dicarboxylic acids, characterized in that it has a fiber strength of at least 0.8 g/d. Polyester fiber.