JPS61162528A - Copolymer composition suitable for production of highly hydrophilic synthetic fiber and its production and related fiber and product - 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 [Background of the Invention] It is known that the presence of a hydrophilic substance is necessary to make polyamide 6 used as a fiber material hydrophilic. Among the hydrophilic substances, polyethylene glycol (PEG)
) and I-lyethylene-oxide are the most commonly used, and the latter has the advantage of being widely used industrially and being inexpensive. All polyamide P including polyamide 6
There are two methods for adding EG:

(,) Simply P while melting or stirring the polyamide
This method is suitable for blending by adding EG. However, a drawback of this method is that the PEG is not chemically bonded to the polyamide. Alternatively, even if chemical bonds are formed as described in a certain literature, the bonds are inherently static and random and cannot be controlled. Therefore, it has poor copolymer properties, and furthermore, PEG will be extracted if it is in contact with water at high temperatures for a long time.
This results in a loss of the hydrophilic properties imparted by the polyamide.

When dyeing textiles using polyamide, the dyeing t
- All of the above apply when performing in water at temperature M.

(b)/IJ amide monomer or comonomer (-) acid-cyamine salt, lactams) is added prior to polymerization.

In the case of polyamide 6, caprolactam is added. In this example, PEG reacts during polymerization in the melt and attaches to the macromolecular chains of the polyamide.

In order to facilitate the reaction in which the polyamide binds to the PEG, both are made to be in a reactive state.

According to the knowledge obtained from known techniques, the following methods can be used to facilitate the reaction with the above techniques.

l) Increase the number of amino groups in the polyamide and react with carmexyl groups of PEG subjected to appropriate modification (modlfcation). However, this reaction has a force N
The disadvantage is that the goxyl groups are thermally unstable, so that the changes that occur in the reaction of polyamide with PEG are rather small.

2) Increase the number of φcarxyl groups in the polyamide and react these terminal groups with the terminal amino group of PEG (PEG containing a 7-mino group instead of the usual hydrosyl group is manufactured by Texaco Corporation) (There is a fact that it is more commercially available). Patents describing the known technology are: U.S. Patent No. 3,594,266
No., British Patent No. 108812, U.S. Patent No. 3
946089, U.S. Patent No. 3509106, U.S. Patent No. 3558419, U.S. Patent No. 363
No. 9502, US Patent No. g351449B, US Patent No. 3661510.

U.S. Patent No. 3,549,724.

3) Increase the number of polyamide or carxyl groups that react with the hydroxyl groups of PEG to form polyesters. Alternatively, a polyamide with carboxy end groups is prepared in advance and then reacted with regular PEG.

The polycondensation reaction takes place in the presence of a titanium, zirconium or nophnium catalyst under high vacuum (US Pat. No. 4,331,786, UK Pat. No. 2,093,469,
U.S. Patent No. 4,349,661.

U.S. Patent No. 4345052, U.S. Patent No. 43
No. 45064, U.S. Patent No. 4,252,920.

British Patent No. 1473972).

(a) is excluded because it lacks practicality; (a) forms a one-block copolymer.

This "dfcl" consists of a macromolecule/IJ amide and polyethylene glycol moieties with different molecular weights (the molecular weights are different for each individual).
f-lock" distribution is not regular. In fact, when modifying PEG with modified or unmodified end groups (examples b, 1. and 2), polyamide monomer (polyamide 6) Therefore, if we name the PEG block terminated with a hydroxyl group or other group as B, the distribution of A and B blocks is not predetermined. No, (b)
For example 3, the subsequent polymerization of A and B is either disordered or predetermined, with the sequence described below.

As described above, when homopolymerized polyamide or copolymerized polyamide K PEG coexists, hydrophilicity occurs to some extent depending on the amount of PEG.

Such properties are generally welcomed when polyamides are used as textiles. However, there are disadvantages to using homopolymerized or copolyamides modified with PEG for fibers, and these disadvantages include mechanical and woven properties,
For example, modulus of elasticity, shrinkage/extensibility, etc. are poorer for modified fibers than for unmodified polyamide or copolyamide fibers.

The more hydrophilic the modified fiber is, and consequently the greater the water absorption capacity, the more severe the property degradation.

The conclusion is that, no matter how much water is absorbed, it is not possible to produce fibers that are comparable in mechanical and textile properties to the PEG-modified polyamides or copolyamides themselves, no matter how much water they absorb. A filament made of PEG-modified nylon 6 with an elastic modulus comparable to that of conventional nylon 6 has already been described in U.S. Patent No. 3,593,266, but the disclosed filament has a one-bag-one-core type composition. The cross-section of the fibers has concentric rings and one of the block copolymer components is bonded to a predominant amount of conventional polyamide.

[Purpose of the invention and field of application]

The object of the invention is to provide polyethylene glycol-modified polyamide or copolyamide heavy metal articles suitable for the production of fibres, fibres, and textile products, with sufficient mechanical and textile properties (same properties of unmodified polyamides). >1 imparts in addition to the hydrophilicity present in all modified polyamides.

A further object of the present invention is to provide a method for producing polyamides in an orderly manner that gives them the desired structure and properties that can be controlled.

It is further object of the present invention to provide polymers of the above type which, in addition to hydrophilicity and a high degree of mechanical and textile properties, are suitable for producing fibre, filament and woven products having a high dyeability. An object of the present invention is to provide a polymer and a method for producing the same.

[Summary of the invention]

It has been unexpectedly discovered that a linear block copolymer of regular structure consisting of polyamide and 4-lyethylene glycol blocks, in which two polyamide blocks (A) are combined with an intermediate polyethylene glycol - It has been found that the above object can be achieved through a linear block copolymer characterized by having a structure (A-B-A) bonded by blocks (B).

According to the invention, the polyamide blocks have an average molecular weight of 5
,000~15,000. Desirably 7,000-12
．． 000. At the reed, on the other hand polyethylene block t-j
Average molecular weight 600-10,000. Preferably 1,00
0 to 5,000.

Block copolymers (B-B-B) have terminal amino groups attached in the form of salts, so that they can capture dye during the coloring process.

The block copolymers of the present invention have a molecular weight between 2.1 and 2.7, preferably 2.2. It has a relative viscosity between ~2.5.

As raw shell U, the polyethylene glycol 10 and 7 I nailed polyamide blocks are ester 1. That is, it is an ester bond resulting from a reaction between a hydroxyl group and a hydroxyl group, or an amide bond resulting from a reaction between a silyl group and an amino group.

According to the invention, the preferred polyamide is polycaprono-2 (also known as polyamide-6 or nylon-6).
) and is usually obtained by polymerizing caprolactam.

Fibers and filaments having high moisture absorption and dyeability as well as high mechanical properties can be obtained from the copolymers of the invention by known melt spinning processes. The advanced physical and mechanical properties of the fibers and fibers of the present invention are detailed below.

〔Effect of the invention〕

Moisture sorption onto the fibers is a function of the amount of PEG present in the (A-B-A) copolymer. When the amount of PEG is 6-9%, the moisture content (determined as saturated at 20°C and 95% relative humidity) is usually 13-17%, compared to 8-9% for nylon 6. Modulus of elasticity is similar to nylon 6 and higher than other conventionally made fibers (see Examples 1 and 2).

Furthermore, depending on the conditions during polymerization and the amount of molecular control agent added during polymerization, the dyeability is equal to or superior to conventional nylon.

The inventive process for the production of block copolymers is within the scope of the invention and essentially consists of the following steps: synthesis of a polyamide with a molecular weight value within the abovementioned limits; and polyethylene glycol with a molecular weight within the above limits and deliberately kept at a suitable stoichiometric ratio to achieve the (A-B-A) structure in the presence of the catalyst defined below. This is the stage of condensation carried out. The starting material 4-lyethylene glycol may have terminal hydroxyl or amino groups, the structure of which governs the final condensation conditions. In particular, when the polyethylene is terminated with hydroxyl groups, the polymerization operation must be carried out under high vacuum.

The synthesis of polyamide components consists of monomers, especially caprolactam,
The polymerization is carried out in the presence of at least one, preferably at least 2'm, molecular weight regulator. Such a regulator must first of all determine the molecular weight of the polyamide, which is one component of the f-lock copolymer of the present invention, and must maintain the molecular weight within the above-mentioned range; At least one of them is regular (A
-B-A) It must act so that the structure is obtained. For that purpose, the polyamide has only one reactive end group, and the polyethylene glycol with which it is condensed has ft2 reactive end groups, each of which is bonded to two polyamide ends. In this way, the polymerization reaction will not continue and the desired structure will be obtained. If the conditions are different), or if the above-mentioned requirements are ignored, the polymer formed will not be ordered and the polymerization reaction will continue to proceed in a disordered manner and will not exhibit the expected properties. It produces a wide variety of polymers. As a result, the problem to be solved by the present invention will not be effectively solved.

Considering these criteria, it is desirable that one of the molecular weight modifiers in 2m be selected from monocargenic acids p) having an acid dissociation constant (Ka) between 10 and 10. For example, acetic acid! Ropionic acid, caproic acid, benzoic acid, methylbenzoic acid are suitable for this purpose. The second monobasic acid component must have a first acid dissociation constant greater than 10°. Lead inorganic and organic acids belonging to this series include 7talenesulfonic acid, benzenesulfonic acid, phosphoric acid, hydrochloric acid, and phosphorous acid.

The combined amount of both e) and (g) is 106 capro2cutam.
The amount of I is preferably 50 to 200 moles, preferably 90 to 150 moles. Both reaction samples may be added separately or as a mixture. In particular, the amount of component (2) is 109 to 20 to 170 equivalents, and the desired polymerization reaction medium is caprolactam and water. .

The amount is, apart from (2) + (g), water is 1 to 10 qlI (by weight) of caprolactam, preferably 2 to 5%.
.

Good.

It is already a well-known technique to polymerize caprolactam in the presence of water (with stirring in a suitable vessel). The reaction mixture was heated to 240-260°C and subjected to a self-generated pressure of 1
The reaction is carried out under ~15 atmospheres, then the autoclave is opened and depressurized. When the autoclave returns to atmospheric pressure, add the polyethylene glycol component while stirring under a gentle nitrogen stream or under a slightly reduced pressure. The amount of preethylene glycol with a hydroxyl group at the end is PEG
There will be a similar amount of hydroxyl groups present in stoichiometric amounts with respect to carboxy polyamide groups. This criterion also holds true even if the PEG is terminated with an amino group; therefore, the number average molecular weight of the molten polyamide 6 must be such that it reacts with PEG (B) as follows.

(1) PA C0OH+HO-PEG-OH
+HOCOPA・・・・・・・・・・・・・・・・・・
PA COOPEG-OCOPA (block (B-B-A) structure) Generally, the obtained (polyamide 6 (B) molecular weight varies depending on the amount of (B) + (T) used, but is 5,000 to 1
5,000), preferably 7,000 to 12,00
It's 0. PEG average molecular weight is 600-10.00
The number is between 0 and preferably 1,000 to 5,000. Therefore, the average molecular weight of the copolymer (A-B-A) is at most 1
Reeds in the range of 1,000 to 40,000, of which 15
,000 to 29,000 is desirable, but the efficiency of converting -〇〇H groups and -OH groups to ester groups is 1o
Since it is not necessary to obtain os, the actual molecular weight value obtained will be lower than the above value. In other words, (A-
The amount of system B-A) should be at least 45% of the theoretical value. - The above-mentioned conversion to (A-B-A) is independent of the violet of PEG contained in the polymerization composition. PEG is generally 5-10
% (ratio to the total amount of the composition), but it is preferably between 6 and 9%.

Since the ester production reaction occurs under limited conditions, it is specified that the residual pressure is 2 ■Hg or less, and the reaction is carried out at a temperature above the melting point of polyamide 6 (230 to 260°C) in the presence of an appropriate catalyst. .

Under these conditions, ester formation is impossible unless the present 7-mino group is blocked by (F) to prevent the condensation of the amino group to the car-xyl end group of polyamide 6. (as explained earlier).

If the amino groups were not blocked (by salt formation), the resulting polyamide 6 would contain PEG that is not chemically bonded and therefore have an extremely large molecular weight. Therefore, based on the present invention, reaction (1) can be rewritten as: (2) R-NH3-PA-C0O
H+HO-PEG-OH・・・・・・・・・・・・R-
NH-PA-COOPEG-OCONH, +・R-+2
H20 here KR-.H+ represents strong #1 of the (F) series.

Furthermore, the ester production reaction can be easily carried out as follows.

Stir so that the PEG is dispersed in the nylon 6 formed at the tip.

In the present invention, i) To disturb the production equilibrium,
Adopting high vacuum to favor polyester production equilibrium,
Generally, the residual pressure should be 1 to 2 smHg or less.

The reaction conditions described in 1 and b are clear) and are also shown in the existing technology. Regarding catalysts, it is known in the prior art to use tetravalent thymene compounds (alkoxyl) (UK Patent No. 1473972, IRIS% Patent No. 1518060, British Patent No. 2011450,
America% Fraud No. 4331786, America → ff No. 4
a4sos2-+, US Patent No. 4252420)
, there are also some that use tetravalent zirconium compounds (
British Patent No. lfFg2093469, British Patent No.2011450).

Tetravalent haconium compounds (alkoxides) are also used, but they are expensive.

Organic and inorganic acid catalysts are also used (benzenesulfonic acid, hydrochloric acid and phosphoric acid), but are less efficient; zinc and antimony compounds are also used in the polyester forming reaction between the (B) blocks, but These catalysts have disadvantages in that they are easily reduced to produce free metals (gray color) and their catalytic activity is insufficient.

As has been experimentally confirmed by the applicant using known techniques,
Tetravalent titanium, norconium, and noconium compounds are active catalysts for ester formation, but they have two drawbacks, and the present invention (A-B- A) Limitations when using the composition;
Or it may not be usable.

The first drawback is the high viscosity of the reaction mixture upon melting even when the percentage of (A-B-person) structure is low. Harmful for a reason. Namely, 1) (A-B-m) High temperatures are required to spin the composition. High temperatures result in loss of color and mechanical textile properties of the resulting fibers.

2) At high temperatures, gluing particles are present during the spinning process, which is unrealistic and makes the known problems even more serious. When the polyesterification conversion exceeds 70, it is clear that glue is formed, which is due to the branched or cross-linked structure caused by the presence of the four active functional parts of the catalyst.

A second drawback is the coloration of the polymer (amide ester), which is particularly related to the presence of tetraalkoxytitanium.

This is obvious since it has been reported that if the polymer is colored from the beginning, it will turn yellow due to spinning.

We unexpectedly discovered that by limiting the active function of the catalyst to 2, we keep the rate of conversion to the (A-B-me) structure constant, and therefore the number average molecule fft of this material constant. and,
This material was found to have a low melt viscosity. In other words, this polymer is two-dimensional rather than three-dimensional.

As a result of this discovery, the spinning and subsequent elongation operations can be facilitated while providing woven fabric properties comparable to nylon 6-ply filaments.

Using such a catalyst, the ``KYjjjlL rate to (A-B-A) obtained by operating under the conditions described below is 45 to 75%.
The viscosity of the material is 100 to 5000 poise, and a desirable value is 1500 to 4000 poise. On the other hand, when a tetravalent catalyst was used, the viscosity was 6,000 to 14,000 boids when the conversion rate to It is a compound with the chemical formula 2.

Here, Me is Ti, Zr, or Hf, R is alkyl, aryl, acyl, aroyl, carboxy-acyloyl, and Cal is xy-aroyl (7-syl or the car-xyl group bonded to the aroyl group is an alkali group). salts of metals or alkaline earth metals).

The amount of catalyst used ranges from 0.05 to 0.5% of the total amount of reactants.

As mentioned above, an alternative reaction to the ester-forming reaction using PEG with a terminal hydroxyl group and catalytic reaction is P with an amino terminal.
Found in reaction with EG. In this case, the catalyst is necessary.

When the composition is spun, it will have the same composition and properties as when the nylon amine groups of the precursor are suitably converted to salts to achieve the (A-B-A) structure in the method of the present invention.

Next, the analytical methods used to determine various characteristic values will be described.

Relative viscosity: Dissolve the polymer in 97.5% sulfuric acid to make a 1% solution, and use the Uperhord viscometer to determine the relative viscosity (or specific viscosity) of the polymer as the ratio of the flow time of this solution to the flow time of the sulfuric acid itself. Measure using.

Free amino groups: Acid titration is performed on a polymer solution made into a phenol/methanol solution to quantify free 7-mino groups. Thymol blue or an electrical conductivity meter can be used to indicate the end point.

Total amino groups: Dissolve the polymer in phenol, reprecipitate by adding a water-a7tone mixture, dry the precipitate, and then titrate to quantify the total amino groups using the method described in the section for quantifying free amino groups. do.

Carmexyl group: Dissolved in polymerized gold pencil alcohol and determined by alkaline titration, using phenolphthalene as an indicator.

Polyethylene glycol content di-polymer is dissolved in phosphoric acid and sodium iodide while heating, and liberated iodine is titrated with thiosulfate to determine the polyethylene glycol content.

Poise viscosity: ASTM D 1238-S 7
2 using the M@lt index measuring device described in T.
Determine the poise viscosity at 60°C. Capillary radius 0.103
5 m, length 2 tm, velocity gradient (r) on the wall is I
Qsec-' or less O Saturated dye absorption amount: *The amount of dye absorbed onto the fiber was determined using a two-dominant solution of -4 orenzo r1 (Sandoz expansion).

Saturated moisture: A pre-dried fiber sample is sown in an environment controlled at a temperature of 20° C. and a relative humidity of 95% and kept until it reaches a constant weight. The saturated moisture is determined as the difference in weight between them.

Example 1 Synthesis of hydrophilic copolyamide polyamide with regular (A-B-A) groups according to the present invention, the properties of the synthetic yarn are similar to those of regular polyamide yarn, except that it has high moisture absorption. It is comparable to

113 parts of caprolactam, 3.39 parts of water, 0.44 parts of acetic acid
1.07 parts of benzene/sulfonic acid, 1.3.5-trimethyl-2,4,6-)lis-3,5-notart-
When 0.11 parts of butyl-4-hydroxypencylbenzene is heated to 240 DEG C. in a closed container with a stirrer, the naturally occurring pressure is at least 3 atmospheres. This condition is maintained for 2 hours, then the pressure is gradually reduced to a residual pressure of 250-Hg within 3 hours. Data on the produced polymers are as follows.

1.9: CalM xyl group = 110 equivalents/1
069: Mn (number average molecular weight) - 10,000° Polyethylene glycol 10.2 with an average molecular weight of 2,000
7 parts, potassium oxytitanium oxytoxate dihydrate 0023
Part, 1, 3.5-) Limeteru 2.4.6-Dorisu 3
．． 0.17 parts of dibenzylbenzene in 5-note t-rt-butylhydro is added to the reaction vessel.The pressure is then gradually reduced to 0.3-Hg and maintained at this value for 3 hours.

The granular polymer obtained by cooling was washed four times with water at 95°C and dried, and the following data were obtained.

Relative temperature 0.02 η1゜12.
30 total amino groups 35 equivalents/10 g acid
Base: 33 equivalents/10I Polyethylene glycol content: 7.0% Copolymerized polyamide was spun and drawn and compared with polyamide 6.

This fiber showed the following properties. Example 2 Synthesis of hydrophilic copolyamide by directly treating PEG with terminal amino groups with adipic acid and water, cyamine-based PEG
The polymer produced by the reaction of dicarboxylic acidic polyamide and dicarboxylic acidic polyamide has disordered block distribution within the polymer chain, and its fiber properties (elastic modulus and shrinkage coefficient) are similar to those of the equivalent polyamide fiber of Example 1. (A-B-A) Significantly lower than copolymerized polyamide fibers.

113 parts of caprolactam, 3.39 parts of water, 0 adipic acid
．． 91 parts, PEG with terminal amino group modification 10.27 parts,
1,3.5-)dimethyl-2,4,6-tris3,5
-Pt.rt-butyl-4-hydroxybenzylbenzene (0.28 parts) is placed in a closed container and heated to 240°C and stirred. The pressure should naturally be at least 3 atmospheres and this state should be maintained for 2 hours.

Then, gradually reduce the pressure inside the container to a final level of 250 smHg within 3 hours, and keep this state for 4 hours. Cool the polymer, wash the granules four times with 95°C water, and dry the polymer. Shows the following properties.

Relative humidity 0.02 ηre1 2.40 ηpals・4,300 amino groups
31 equivalents/10 ji acid groups
37 equivalents/10! i Polyethylene glycol content: 6.8% The gourd obtained by spinning and elongating this polymer and the obtained filament as in Example 1 have the following properties.

Example 3 Direct addition of 2,000 molecular weight 4-lyethylene glycol and an esterification catalyst along with caprolactam to create a disordered block copolymerized 4-lyamide. The mechanical and textile properties of the obtained filaments are as claimed in claim 1. It is inferior to the filaments obtained by.

Cabloctam 113 parts, water 3.39 parts, acetic acid 0.44 parts
parts, benzenesulfonic acid 1.07 parts, 1,3.5-trimethyl-2,4,6-)lis-3,5-di-t·rt-
0.28 parts of 4-hydroxybenzylbenzene,
Polyethylene glycol with an average molecular weight of 2,000 10.
27 parts of potassium oxytitanium oxalate and 0.23 parts of potassium oxytitanium oxalate were placed in a sealed stirring reaction vessel and heated to 240°C. The pressure will naturally rise to at least 3 atm and this state will be maintained for 2 hours. Then, the atmospheric pressure is gradually reduced to a residual pressure of 0.3-Hg within 5 hours, and this pressure is maintained for 3 hours.

The cooled granular polymer was washed four times with water at 95°C and dried, exhibiting the following properties.

Relative humidity 0.02 ηr@l 2.30 ηpois 4,500 Free amino groups 3 equivalents/10 g Total amino groups
35 equivalents 7xog cargoxyl group 34 equivalents/
1 oll PEG content 7.1% This polymer was spun and compared to polyamide 6, and the resulting fiber had the following properties.

Examples 4 and 5 Using tetravalent titanium or zirconium catalyst (A-B-
A) Synthesis of W block copolymer polyamide This polymer has high viscosity in a molten state and is not suitable for processing into fibers.

The procedure is as in Example 1, except that the catalyst includes 0.22 parts of titanium tetrabutoxide and 0.2 parts of tetravalent zorconium derivative.
Use 1 part.

The polymer exhibits the following characteristics.

This polymer was spun. At 260°C it is not possible to spin threads from this polymer (spinning test); at 280°C it is possible to extrude it into threads, but the threads cannot be picked up.

Example 6 Polyamide precursor KPE with terminal carboxyl groups
(A-B-A) type hydrophilicity by cocondensation polymerization of G! Rock copolymerization? The filaments produced by synthesizing lyamide cannot be dyed adequately due to a lack of amino groups.

As described in Example 2, the terminal zocal? Polyamide 6 having xyl groups is obtained, and 100 parts thereof are reacted with 10.27 parts of polyethylene glycol having a molecular weight of 2,000.

The reaction vessel was stirred at 250 DEG C., and the pressure was slowly lowered to a residual pressure of 0.3 ■Hg, which was maintained for t-13 hours.

After cooling, the granular polymer was washed four times with water at 95°C and dried, exhibiting the following properties.

ηr@1 2.32 NH22 equivalent/10'fi cooH451 amount/10'I PEG% 7.3% The conversion rate to the (A-B-A) structure is approximately 67% (PEG%
between quantification).

Example 7 Synthesis of a hydrophilic polymer according to the invention. However, only monocarboxylic acid (Ka between 10'' and 10'') is used.

? Conventional methods used for Lyamide fibers cannot dye the yarns produced here. This indicates that an acid having a Km of 1o-1 or more must be used in combination as a molecular weight regulator.

113 parts of caprolactam, 3.39 parts of water, 0.68 parts of acetic acid
part, 1,3.5-)limethyl-2,4,6-tris[
0.11 parts of 3,5-di-t@rt-butyl-4-hydroxypencyl]benzene are reacted according to the process of the invention as described in Example 1.

A granular polymer product washed four times with water at 95°C and dried in a vacuum has the following characteristics.

Relative humidity 1 0.03 ηr@l (Sulfuric acid (B) 2.30Wpoise
(260°C, r=11) 1,900 amino groups g equivalent/10.9 acid groups
37 equivalents/10, p polyethylene glycol content
Conversion rate to 7.4chi (A-B-A) structure: approx. 70
Although this polymer was spun and drawn in the same manner as in Example 1, the stockings produced could not be dyed.

Example 8 Copolymerization of PEG with terminal carboxyl groups and hydrophilic copolymerization with amino terminal groups/There is evidence that the reaction of IJ amide is hampered by the thermal instability of the former. This reaction does not occur.

113 parts of caprolactam, 3.39 parts of water, 1.03 parts of benzylamine, 1,3.5-trimethyl-2,4,6-
The operation of Example 1 was carried out using 0.11 parts of tris[3,5-di-t@rt-butyl-4-hydroxybenzyl]benzene, except that the same amount of /IJ ethylene glycol in Example 1 was used. 4-lyethylene glycol with a terminal carboxylic group is used.

The obtained polymer has the following properties.

Relative humidity 0.03% η. 1 2.07 ηpots・ 800 Amine group 99.8 equivalents/10g Carboxyl group 14.5 equivalents/10g PEG content
7.4% ()゛

Claims (1)

[Claims] 1. Two polyamide blocks (A) are linked to each other via a polyethylene glycol block (B) located between them according to the structural type (A-B-A). A linear block copolymer with a regular structure consisting of blocks of polyamide and polyethylene glycol. 2. The average molecular weight of the polyamide block is 5,000 and 1
Between 5,000 and preferably 7,000 and 12,000
and the molecular weight of the polyethylene glycol block is between 600 and 10,000, preferably 1,000.
and 5,000. 3. The linear copolymer according to claim 1, wherein the block (B) is bonded to each of the blocks (A) through an ester bond -CO-O-. 4. The linear copolymer according to claim 1, wherein the block (B) is bonded to each of the blocks (A) through an amide bond -CO-NH-. 5. The linear copolymer according to claim 1, wherein the polyamide is polycaproamide (nylon 6). 6. The linear polymer according to claim 1, wherein the amino group at the free end of the polyamide block (A) is blocked by a group that easily separates under dyeing conditions. 7. The linear copolymer according to claim 6, wherein the blocking group is a sulfone group. 8. Linear copolymer according to claim 1, characterized in that it has a viscosity between 1,000 and 5,000 poise. 9. Consists of blocks of polyamide and polyethylene glycol, in which two polyamide blocks (A) are linked to each other via a polyethylene glycol block (B) located between them according to the structural type (A-B-A) Woven fibers and fibers made from a linear block copolymer with a regular structure are characterized by having high moisture absorption, mechanical properties, and dyeability. Filament. Woven fibers and filaments according to claim 9, characterized in that they exhibit a saturated moisture uptake of between 13 and 17% at 10.20°C and 95% relative humidity. 11. Regular blocks of polyamide and polyethylene glycol in which two polyamide blocks (A) are linked to each other via a polyethylene glycol block (B) in the middle according to the structural type (A-B-A) It is characterized by being made from a linear block copolymer with a linear structure, and made from woven fibers and/or woven fabrics that have high moisture sorption properties, mechanical properties, and dyeability. Textile products. 12. I) Synthesis of polyamide (A); II) Synthesis of polyethylene glycol (B); III)
Polyamide (A) and polyethylene glycol (B) are A
- A method for producing a linear block copolymer having a regular structure consisting of blocks of polyamide and polyethylene glycol, the method comprising: a condensation reaction under conditions that yield a B-A structure. 13. Polyamide is polycaproamide (nylon 6)
The method according to claim 12, characterized in that: 14. The method according to claim 12, wherein the polyethylene glycol has a terminal OH group. 15. The method according to claim 12, characterized in that the polyethylene glycol has a terminal NH_2 group. 16. The method according to claim 12, characterized in that the synthesis reaction is carried out in the presence of a catalyst substance. 17. The catalyst substance contains at least one substance represented by the chemical formula (1), OMe(OR)_2(1), where Me is selected from Ti, Zr, and Hf, and R is alkyl, aryl, acyl, 17. Process according to claim 16, characterized in that it is selected from aroyl, carboxy-acyloyl and carboxy-aroyl. 18. The method according to claim 17, wherein the carboxyl group bonded to the acyl group or the aroyl group is converted into a salt of a metal selected from alkali metals and alkaline earth metals. 19. The method according to claim 17, wherein the substance of chemical formula (1) is potassium oxytitanium oxalate dihydrate. 20. The method according to claim 17, wherein the substance of chemical formula (1) is tetrabutoxytitanium and a tetravalent zirconium compound. 21. Catalyst material from 0.05% to 0.5% of the total amount of reactants
18. A method according to claim 17, characterized in that it is used in amounts ranging up to %. 22. For the synthesis of polyamide (A), a condensation polymerization reaction is carried out in the presence of at least one kind of molecular weight regulator, and the molecular weight of the polyamide is between 5,000 and 15,000, preferably 7,000. 13. A method according to claim 12, characterized in that between 12,000 and 12,000. 23. In the synthesis of polyethylene glycol (B),
The molecular weight of polyethylene glycol is 600 and 10,00.
between 0, preferably between 1,000 and 5,000,
13. The method according to claim 12, wherein the synthesis is carried out under conditions such that: 24. The synthesis of polyamide (A) is carried out in the presence of at least one kind of molecular weight regulator, and the molecular weight regulator blocks the terminal amino groups of (A) during the reaction, but under the conditions during the next dyeing. The method according to claim 12, characterized in that a substance that is easily released is used. 25. The method according to claim 22, wherein the molecular weight regulator is at least one of carboxylic acid and sulfonic acid. 26. The method according to claim 22, wherein the molecular weight modifier comprises at least one carboxylic acid and at least one sulfonic acid. 27. The method according to claim 26, wherein the carboxylic acid is a device and the sulfonic acid is benzenesulfonic acid.