JPS6297914A - Easily dyeable polyester fiber and its production - Google Patents

Abstract

PURPOSE:Polyethylene terephthalate copolymerized with a metal sulfonate group- containing component, isophthalic acid and 1,2-bis(4-carbophenoxy)ethane is subjected to high-speed spinning to produce the titled fiber with high resistance to alkalic hydrolysis. CONSTITUTION:A polyester which is mainly composed of ethylene terephthalate units and contains (A) an ester-forming component with metal sulfonate group (e.g., 5-sodiosulfoisophthalic acid), (B) isophthalic acid component and (C) 1,2-bis(4-carbophenoxy)ethane where the molars amounts of individual components satisfy equations I-III is melt-extruded through the spinneret, the heating chimney, the finishing nozzle guide and wound up at a speed over 5,000/min to give the objective fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyester fiber that can be dyed in a deep color with a basic dye at normal pressure and at a temperature of 95° C. or higher, and a method for producing the same. For more information on my husband, see Alkali Resistance N0
The present invention relates to an easily dyeable modified polyester fiber which has significantly improved water decomposition properties and is suitable for alkali reduction processing, and a method for producing the same.

[Conventional technology and its problems]

Conventionally, it is well known that polyester fibers dyeable with basic dyes can be obtained by copolymerizing an ester-forming component containing a metal sulfonate group into a polyester component for the purpose of improving the dyeability and coloring properties of polyester fibers. There is.

In addition, recently, it has become possible to improve the dyeability of polyester fibers that can be dyed with basic dyes, and to obtain fibers that can be dyed in a boiling state under normal pressure with sufficient color miscoloring. It is widely used because it expands its uses by interweaving it with fibers, etc.

Various methods have been considered to improve the dyeability of polyester fibers that can be dyed with basic dyes and to obtain fully rutted fibers that can be dyed in sufficiently deep colors under normal pressure boiling conditions. It is a known method to further copolymerize a third component in addition to the metal sulfonate group-containing ester-forming component serving as the seat, and in particular, isophthalic acid is commonly used as the third component. (% Publication No. 57-32139) By copolymerizing inphthalic acid 1&:* with a metal sulfonate group-containing ester-forming component, the ratio of 1 to 1 of the metal sulfonate group-containing ester-forming component can be reduced, and it can be boiled at normal pressure. Although this method certainly made it possible to obtain fibers that could be dyed in a sufficiently deep color under the conditions, it was unavoidable that the resulting fibers would be extremely poor in alkali hydrolysis resistance. Utilizing the moderate alkaline hydrolyzability of homopolyester, we have created a full-like material with a soft texture and drapability.The so-called alkaline damping blade Loe treatment has a more luxurious feel and is more versatile. In order to meet the needs of increased consumption for sexual entertainment, it is now common and popular.

However, the current basic dye-dyeable polyester fibers, which are highly hydrolyzable with alkaline compared to homopolyester, are susceptible to a decrease in fineness (11) or uneven fineness when subjected to an alkali reduction process of 710 degrees.

(2) Strength tends to decrease.

(3) Slits f etc. will collapse? Right.

These problems make the management of the alkali reduction process complicated and difficult, or the alkali reduction process itself is often impossible.

[Means of problem solving]

The present invention has been achieved as a result of diligent efforts to solve the above-mentioned drawbacks. That is, the object of the present invention is to improve dyeability by copolymerizing a metal sulfonate group-containing ester-forming component and isophthalic acid into a polyester mainly composed of ethylene terephthalate, and to obtain a sufficiently deep color at a temperature of 95° C. or lower under normal pressure. In addition to obtaining dyeable polyester fibers, by adding a specific copolymer component, the low alkali IJ 7J0 water decomposition performance of conventional basic dye dyeable polyester fibers is improved,
Another object of the present invention is to provide easily dyeable modified polyester fibers that can be dyed with basic dyes and which can be treated with alkaline dyes like ordinary homopolyesters, and a method for producing the same.

The basic dye-dyeable polyester fiber constituting the present invention must have a metal sulfonate group-containing ester-forming component, an isophthalic component, and a 1,2-bis(4-carbophenoxy)ethane component as copolymerized components; And when the respective copolymerization mol% is (4), (Bl, (O), the following formula (
There is a necessary concubine that satisfies 1), (2), and (3).

0.8≦Prison≦6.5... Song (Il l, 0≦(B)≦1 Ll, 0-+212.0≦(C)
S 20.0...(3j1-, that is, a metal sulfonate group 81r4 ester-forming component, has a bridge site that binds to basic dyes, so it is an essential component for dyeing with basic dyes, Specifically, the components include 5-sodium sulfoisophthalic acid, potassium sulfoterephthalic acid, sodium sulfonaphthalenedicarbone modified,
Dicarboxylic acids and their alkyl esters such as sodium sulfophenylzocarboxylic acid, oxycarboxylic acids and their alkyl esters such as sodium sulfobenzoic acid, and dihydroxy compounds such as sodium dihydroethoxybenzene sulfonate. - Sozoum sulfoinphthalic acid is preferred.

Isophthalic acid is necessary as a third component for dyeing in a sufficiently deep color at a temperature of 95° C. or less under normal pressure and with a small content of the metal sulfonate group-containing ester-forming component.

In order to obtain fibers that can be dyed in a sufficiently deep color under normal pressure boiling conditions using only the metal sulfonate group-containing ester-forming component without using a third component such as isophthalic acid, it is necessary to use a variety of sulfonate group-containing ester-forming components. As a result, the melt viscosity increases at the time of spinning, resulting in a decrease in yield due to yarn breakage during spinning. It is not preferable because it becomes f.

Gota, 1-2-bis(4-carbophenoxyethane) is the main component b for achieving the purpose of the present invention, and is indispensable in order to improve the water decomposition properties of alkali IJ UD. It is. Normally, when the third component gold is conjugated, the structure tends to become loose and water decomposition of alkali IJ 71O progresses, but what should be noted is that 1,2-bis(4-carbophenooxy)ethane is This has the effect of suppressing alkaline D-water decomposition. Direction, 1, 2-
Even when bis(4-carbophenooxy)ethane is copolymerized alone with a metal sulfonate group-containing ester-forming component, it is less effective in improving the dyeing properties of basic dyes than isophthalic acid. Therefore, isophthalic acid is absolutely necessary to dye sufficiently deep colors at temperatures below 95°C under normal pressure, and the effect of 1,2-bis(4-carbophenooxy)ethane is effective on polyester fibers dyeable with basic dyes. If anything, it mainly contributes to improving the water decomposition properties of Alka IJ UD.

The copolymerization mol% (A), (B), and (C) are expressed by the following formulas (11, (2+).

Is it necessary to satisfy (3)?

L], 8≦prisoner≦6.5... (1) 1.0≦(B
)≦10.0...(2)2.0≦(C)≦20.0・
(3) That is, the copolymerization mol% cA of the metal sulfonate group-containing ester-forming component is [J, 8≦V≦6.
5 is required. <A) is less than Ll, 8 (B)
No matter how large the value of , it is not possible to dye a sufficiently deep color at temperatures below 95°C under normal pressure, and if it exceeds 6.5, the ester-forming component containing metal sulfonate groups is present. When this happens, the damage during spinning becomes noticeable.

In addition, the copolymerization mol% (B) of isophthalic acid is 2.0≦(B
)≦10.0 is required; if it is less than 2.0, the expected dyeing effect will not be obtained, and if it exceeds 10.0, the strength will increase.
Other mechanical and thermal properties such as elongation and melting point are significantly reduced.

Furthermore, 1,2-bis(4-carbophenoxyethane)
Copolymerization mol% of components (C1 is 2.0≦(C)≦20.0
It must be. If (C) is less than 2.0, no improvement in alkalizing water decomposition properties can be expected, and if it exceeds 20.0, other physical properties such as a decrease in melting point will be significantly reduced, making it impractical.

Incidentally, the uneven distribution ratio of these six components can be freely selected within their respective ranges, or the ratio can be selected according to the purpose by considering the balance of dyeability, alkalizing water decomposition property, and mechanical and thermal properties. It is desirable to polymerize.

A known method can be used for polymerizing the copolymer components constituting the present invention.

In other words, the dicarboxylic acid component may be directly reacted with terephthalsan, ethylene glycol, etc. as an acid, or it may be converted into an alkyl ester component such as dimethyl ester and subjected to an ester exchange reaction with ethylene glycol, followed by condensation. .

The glycol component can be used in the same way as ethylene glycol.

The oxycarboxylic acid component can also be combined with the dicarboxylic acid in a one-bean-one-one method.

The birch fibers that are the object of the present invention can be obtained by combining the polymers by these known methods and bath-melt spinning them into fibers by any known spinning method.

In general, the spinning method can be roughly divided into the following six methods, but (spinning at a winding speed of 111,000 to 1,500 m/min and heat treatment to stretch the undrawn yarn to 6 to 4 times the undrawn yarn) A so-called POY is spun at a winding speed of f21 4000 m/or less, and the POY is stretched and false-twisted at a rate of 1.05 to 1.5 times.

(3) Island speed spinning at a stripping speed of 5000 m/part.

Among these, the method (3) using high-speed spinning is a preferred method because it can improve productivity, reduce costs by omitting the stretching step, and can also be expected to improve dyeability.

However, in general, when polyester copolymerized with metal sulfonate group-containing ester-forming components is spun at a speed of 5,000 m/min or more, fuzzing and yarn breakage occur frequently, and winding is often done in a circular manner. This was an inappropriate method for producing fibers.

However, the polyester of the present invention should have a polyester of 500%
Even when the yarn is wound and spun at a speed of 0 m/min or more, it can be produced with significantly less fluff and yarn breakage, and it has become possible to produce it in the same way as homopolyester.

〔effect〕

The easily dyeable polyester fiber dyeable with basic dyes of the present invention has the characteristic that it can be dyed in a sufficiently deep color at a temperature of 95°C or less under normal pressure. It also has high alkali resistance and water decomposition performance, which was previously impossible to achieve with basic dye cross-linkable polyester fibers.
This has the effect of making it possible to perform IO processing.

Another effect is that when the fiber is manufactured by spinning at a winding speed of 5 UODm/min or more, it solves the problems of fluff and yarn breakage that frequently occurred in the conventional fiber manufacturing of this strain, improving productivity. There are many things that can be mentioned.

〔Example〕

The present invention will be explained in detail with reference to Examples below.

Incidentally, the 'f+ value method of the characteristic values of the valley glaze used in the examples of the present invention is as follows.

(Strength, elongation) Shimadzu Urasakusho, Autograph DSCi []Q type tensile testing machine, initial strength 203, tensile speed 2 D Cm/m
Measured in.

(Diving shrinkage rate) L], the length of the sample under a load of 1 g/d is L, the load l is removed, the length is treated in boiling water for 30 minutes, the length gffiL is measured under the same load, and the diving shrinkage is calculated from the following formula. Rate (B,
(abbreviated as W, S) are defined and obtained.

O (Basic dye exhaustion rate) Base injection dyeing #+Max11on Blue 5C) (C
hiba ()eigy) Adjustment d; Sodium acetate 0.5 &/L Anhydrous e pressure' nitrate 4.0,
? / L acidity...=4.5 Bath ratio: 50 Dye attitude: 5 owf Solvent level: 95°C After adding the above dye to the adjustment solution and dyeing under the above conditions,
The remaining solution was diluted with a conditioning solution, and measured using a Shimadzu spectrophotometer UV-200 using a 1 cfn correct cell at wavelength λ = 6.
Total absorbance was measured at 55 mμ (U) The basic dye exhaustion rate (simply abbreviated as exhaustion rate) was determined from the absorbance (Uo) of the dye stock solution diluted and measured in the same manner.

O (melting point) Par # 71 Differential manufactured by Leur Co.
Using Scanning Ca4orimet, er-2 type, sample 7rnQ, valve temperature ff 20℃/min, side addition while performing N2 substitution.The peak of the endothermic peak in the chart obtained? Melting point.

(Alkali weight loss rate) After the pre-treated sample (yarn) was knitted in a tube at Iso, it was dissolved in distilled water at a ratio of surfactant (Sfarol 250, Kao Atlas Co., Ltd.) 'e2&/L, at a bath ratio of 1:200. 3 at a temperature of 60-70℃
Use the tree scouring oil for 0 minutes.

After scouring, drain the water thoroughly and dry for 24 hours in a constant temperature room maintained at a temperature of 26 degrees and humidity of 65 degrees.

Approximately 59% accuracy = iW of the pre-measured sample VJo)N
The sample was subjected to alkaline water decomposition in a 5% aOH solution in a boiling state for 15 minutes, then thoroughly washed with water, dehydrated and dried under the above conditions, and the weight after weight loss was accurately weighed as shown in the following formula. Define and find the alkali weight loss rate.

Ouma h1 tari 1 5-sodium sulfoiphthalic acid filter, 36mtitTh
1.2-bis(4-carbophenooxy)ethane 7.7
8 Adobe, dimethyl terephthalate 87.8m Sumirebe, ethylene glycol 70.0:&i [Th, bW-r7ganlj, 0411 Adobe and 0.061 parts by weight of lithium acetate were added to a rectification column. After distilling off all of the purified methanol, it was heated to 180-240°C for 2 hours with stirring to distill off more than 97% of the theoretical reaction methanol. Leave to react for an additional 2 hours.

Thereafter, the reaction product was transferred to a depressurizing autoclave, and 0.04 weight part of antimony oxide and 0.03 mt part of tinous acid were added.
00, raise the temperature to 260°C and remove it.
Polymerization was carried out at 280°C for 2 hours under vacuum conditions below 0.5mm/H, melting point: 230°C, intrinsic viscosity: 0.
．． The av co-N polyester obtained from No. 56 basic dye dyeable copolymerized polyethylene terephthalate was ground into pellets and dried under reduced pressure at 130° C. for 20 hours to adjust the moisture content.

The copolymerized polyethylene terephthalate pellet was prepared using a spinneret diameter of 0.23 mm at a bath melting temperature of 29L1'C.
Through a spinneret equipped with a hole, the output amount is 37.49
Extrusion at 2LIO/min and 4Ucrn temperature 2LIO just below the spinneret.
70D after the refueling nozzle guide located at 130 cIn below was tightened and focused through the entire heating cylinder kept at ℃
The fibers were wound as 5U denier/24 filaments at a winding speed of Om/min.

The evaluation results of strength, elongation, flood shrinkage rate (B, W, S), exhaustion rate, alkali weight loss rate, and spinning stability are shown in the table.

As you can see from the table, the exhaustion rate is 99.7%, which is sufficient.
It can be seen that the color is dyed, and the alkali weight loss rate also increases.
It can be seen that this is greatly improved compared to the comparative example described below.

Moreover, even though the spinning speed is 7,000 m/min, the yarn! ;lJ Eh, it can be seen that there is less occurrence of fluff.

Example 2 The copolymerized polyethylene terephthalate of Example 1 was dried under the same drying conditions as in Example 1, passed through the same spinneret all the way through, extruded at 29L)°C and discharge m-A 6.0&, kept warm,
The undrawn fibers were removed and unrolled at a speed of 800 m/min, and the undrawn fibers were further stretched to a drawing ratio of 3.617 times to 7Ll'.
It was stretched under temperature conditions of C.

The physical properties of the obtained fibers are also shown in the batter. As you can see from the crowd, the blood of the exhaustion rate is large and dyed in a sufficiently dark color.
And the alkaline #key ratio f@ is also 1.2-bis(
This is significantly improved compared to basic dyeable polyester fibers that are not copolymerized with 4-carbophenoxy)ethane.

Actual Sleeve Example 6 A continuous yarn was spun in the same manner as in Example 1, except that the ratio of the copolymerized components was changed. Record the results in the table -f.

From the table, it can be seen that the alkali weight loss rate is improved even compared to Example 1 due to the sufficient color dyeing GH at normal pressure of 95° C. and the reduction in the amount of copolymerization.

Ratio $991J 1-4 Using the same method as in Example 1, changing the copolymerization ratio to 1.2-
? :'s(4-carbophenooxy)ethane and polyethylene terephthalate without combining gold? Making,
Fibers were made in the same manner as Sleeve Examples 1 and 2. The results are written on the cloth.1゜1.2-Bis(4-carbophenooxy7)ethane is not copolymerized, so it can be seen that the alkali #% is high.

5 In the same manner as in Example 1, copolymerized polyethylene terephthalate without copolymerizing inphthalic acid was made, and Example 1
, 2, the results are shown in the table.

From the results, it can be seen that although the Alka IJ weight loss rate is greatly improved compared to the comparative example, the exhaustion rate remains unsatisfactory.

Claims (1)

[Scope of Claims] (1) Copolymerization mol% of metal sulfonate group-containing ester forming component (A) and copolymerization mol% of isophthalic acid component (B
) and 1,2-bis(4-carbophenooxy)ethane component copolymerization mol% (C) copolymerization ratio is expressed by the following formula (1
), (2), and (3) Easily dyeable modified polyester fibers mainly composed of ethylene terephthalate units 0.8≦(A)≦3.5 (1 ) 1.0≦(B)≦10.0...(2) 2.0≦(C)≦20.0...(3) (2) Metal sulfonate group-containing ester forming component Copolymerization mol% (A) and copolymerization mol% of isophthalic acid component (B
) and 1,2-bis(4-carbophenooxy)ethane component copolymerization mol% (c) copolymerization ratio is expressed by the following formula (1
), (2) A polyester mainly composed of ethylene terephthalate units that satisfies formulas (3) is 0.8≦(A)≦6.5 (1) 1.0≦(B)≦10. 0...(2) 2.0≦(C)≦20.0...(3) Production of easily dyeable modified polyester fiber characterized by spinning at a winding speed of 5000 m/min or more Method.