JPS6018330B2 - Method for producing antistatic acrylic fiber with improved fiber performance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a dominating acrylic fiber with improved fiber performance, and more specifically, the present invention relates to a method for producing a dominating acrylic fiber with improved fiber performance. In producing acrylic fibers from the copolymer (D),
The present invention relates to a method for producing a dominating acrylic fiber with markedly improved fiber performance, the gist of which is the presence of a predetermined amount of a specific compound in the paper yarn stock solution of the above-mentioned mixed polymer.

It is well known that acrylic fibers have long exhibited excellent characteristics in terms of heat retention, shrinkability, shape stability, weather resistance, texture, dyeability, etc., and are increasing their demand for use in clothing and interior design. Are known.

However, such acrylic fibers are not without practical limitations, and there are some problems that require urgent measures to be taken.

For example, when clothing made of the acrylic fibers is worn or used as carpets, static electricity accumulates, causing inconveniences such as causing extreme discomfort to the human body, and significantly reducing their commercial value. was a drawback. Generally, as a method to remove such static fin air disturbance, a compound capable of imparting antistatic properties is applied to the fiber surface,
There is also known a method of obtaining antistatic fibers by introducing the above-mentioned compounds into the fiber structure during spinning.

However, in the above-mentioned method, since the antistatic compound used is a low molecular weight surfactant, the surfactant easily falls off from the fiber surface or fiber structure during fiber processing or fiber manufacturing. This resulted in a flaw in that there was a significant drop in dominating performance. Alternatively, as described in U.S. Pat. No. 3,507,935, a copolymer obtained by copolymerizing acrylonitrile with polyalkylene glycol acrylate (or methacrylate), etc. is used for the purpose of imparting dominating properties to the final fiber. A technique has been proposed in which a polymer and a well-known acrylonitrile polymer are mixed and then spun.

However, although such an antistatic imparting means certainly improves the drawbacks of using the low molecular weight surfactant, on the other hand, the incompatibility of the two types of polymers (the polyalkylene glycol acrylate-containing copolymer) In the case of polymers, their hydrophilicity becomes unnecessarily large. It was recognized. Incidentally, the degree of generation of such pores differs depending on the solvent used for the bran stock solution, and in particular, when a concentrated aqueous solution of inorganic salts such as sodium thiocyanate is used as the solvent for the spinning stock solution, the above-mentioned non-phase of the rain polymer may occur. It has been confirmed that the twilliness becomes noticeable and a large number of pores are generated. If a large number of pores appear in the fiber structure in this way, a fatal defect will occur in that the final acrylic fiber will not have practically satisfactory transparency (color development) and gloss. Not only this, but also in operational aspects, weavability and drawability are reduced, a large number of abnormal fibers such as undrawn yarn and fiber powder are generated, and the acrylic fibers are fibrillated, resulting in a decrease in bending strength and frictional strength. (More generally speaking, the physical performance of the final fiber of antistatic acrylic fibers has been significantly reduced (leading to problems such as stiffness and thread breakage in the spinning process). In manufacturing, if an attempt is made to improve antistatic properties, the above-mentioned fiber performance will conversely deteriorate, while if an attempt is made to improve fiber performance, antistatic properties will be hindered).

Taking the above circumstances into consideration, it is no exaggeration to say that an industrial technology that can impart practically satisfactory antistatic properties to acrylic fibers while at the same time improving fiber performance, which is contradictory to this, has not yet been established. do not have.

In this case, the present inventor has solved all of the various limitations associated with the conventional technology as described above, and has developed a fiber that is significantly improved in the final fiber without any deterioration in the antistatic performance of the acrylic fiber. As a result of intensive research to find and develop industrial means to impart performance, the object of the present invention was advantageously achieved by selecting and using an acrylonitrile-based mixed polymer paper yarn stock solution having a predetermined composition. Look at the possible facts
The present invention was achieved through this research.

The main object of the present invention is to propose a method for producing acrylic fibers that have permanent antistatic properties and have fiber performance that poses no problem in practical use.

Another main object of the present invention is to discover and provide a technical means for producing antistatic acrylic fibers that is highly industrially useful.

Further different objects will become apparent from the description below.

Therefore, the object of the present invention is to obtain polyacrylonite IJ.
An acrylic polymer (1) consisting of at least 7% by weight of acrylonitrile or acrylonitrile 7 and at least one other polymerizable unsaturated vinyl compound, and 30 to 7% by weight of acrylonitrile and a monomer represented by the following general formula (A) When producing an acrylic fiber from an acrylonitrile polymer spinning stock solution consisting of an antistatic copolymer (n) obtained by copolymerizing a monomer polymer having a proportion of 70 to 3% by weight, '1'
The monomer represented by general formula (A) is added to the spinning dope in an amount of 0.3 to 4. to be present in weight percent of '
2) Also, by integrally incorporating the compound represented by the following general formula (B) in the paper yarn stock solution in an amount of 0.05 to 1% by weight based on the mixed polymer, and forming the paper yarn. can be achieved.

C stop = CRCO0 (CH2CQO) mR' (A
) (In the formula, R is a hydrogen atom or a methyl group, R' is a hydrogen atom or an alkyl group having 8 or less carbon atoms, m is an integer from 5 to 100) R''(CH2CH20)nH
(B) (In the formula, R'' is an alkoxy group, an alkylphenoxy group, or a phenoxy group having 1 or less carbon atoms, and n is an integer of 1 to 15.) The acrylic fiber obtained according to the method of the present invention is , has appropriate antistatic properties, and since there are no cavities in the fiber, it has excellent transparency and gloss, and does not cause any decrease in the vividness of the hue of dyed products or decrease in color development. , which has extremely high commercial value.

What is particularly important in producing acrylic fibers with such unique fiber properties is to have a predetermined amount of an antistatic compound (compound A) present in the acrylonitrile polymer paper yarn stock solution, and at the same time to add a specific compound (compound B). A predetermined amount of a compound (a low molecular weight surfactant represented by the above general formula) is present.

In order to more clearly understand the significance of the technical configuration of the present invention, firstly, the correlation between the antistatic properties and fiber performance of conventional acrylic fibers when only compound A is used is shown in Figures 1 and 2. This will be explained using figures. First of all
The figure illustrates the relationship between the content of the above-mentioned antistatic compound and the degree of deterioration of color development due to drying of the dyed product of the final fiber (K/S ratio: this will be described later). From Figure 1, it can be seen that as the antistatic compound present in the acrylic fiber increases, the above K/S ratio decreases linearly, and the change in color development due to heat etc. of the final fiber becomes significantly worse. . In addition, Figure 2 illustrates the relationship between the content of the antistatic compound and the antistatic performance (evaluated by half-life). The fact that the antistatic effect increases as the is increased is clearly understood. In addition, in the present invention, the above K/
S ratio is 65% or more (the content of the antistatic compound inherent in the acrylic fiber is 4% by weight or less based on the weight of the total mixed polymer)
If so, it has been confirmed that there will be no disadvantages such as a decrease in the color development and sharpness of the hue of the dyed product of the final fiber. Furthermore, it has been confirmed that if the half-life is 6 seconds or less (the content of the antistatic compound is 4% or more), the antistatic performance of the final fiber can be improved. The above explanation shows that in the production of conventional antistatic acrylic fibers, if a large amount of antistatic compound is introduced as a component of the fiber in order to improve anti-crab properties, the fiber This clarifies the contradictory fact that the performance deteriorates, and that attempts to improve the chick performance actually impede the antistatic properties.

Next, when only Compound B is used, the resulting acrylic fiber has a smaller degree of decrease in fiber performance than when only Compound A is used, but shedding phenomenon occurs during the spinning process. The antistatic performance and the washing durability of the antistatic property deteriorated significantly, and a product of good quality could not be obtained.

The inventor himself has not yet obtained a clear theoretical basis as to why the desired effect can be achieved by introducing compound (B) into the fiber structure at the same time as compound (A). The disadvantages related to the incompatibility of the seed polymers are probably due to the effects due to interactions such as good compatibility between compound (A) and compound (B), i.e.
This is presumed to be because it was compensated for by the effect of increasing the residual efficiency of B), thereby improving the conquering performance and washing durability performance, and further suppressing the formation of cavities.

The antistatic properties (half-life) of the acrylic fibers and the degree of deterioration of the color development of dyed products (K/S ratio) were calculated by the following measurements.

[1] Antistatic properties The final knitted fabric made of acrylic fibers was soaked in a solution containing Monogeny (manufactured by Procter & Gamble Sunhome) (concentration 2#/zo, bath ratio 1/30).
), then add the liquid to 60 to 100 qo, 3
The temperature was raised for 1 and 2 minutes, followed by treatment for 10, 0, and 60 minutes to produce test fibers.

Next, the test fiber wire fabric was heated at a temperature of 20 oo and a relative humidity of 40
% conditions for two days and nights. The resulting knitted fabric was taken out and its half-life was measured using a static honest meter (manufactured by Shishido Shokai) under the following conditions. How to use static honest meter Applied voltage: 10,000 volts Application time: 3 minutes Sample rotation speed: 100 volts. P. m The above half-life indicates that the shorter the half-life, the better the antistatic property of the treated fiber.

In addition, the durability of the antistatic property against washing was determined by placing the finally obtained sample for measurement in a household electric washing machine (Mo/Gyuni concentration 2 hours/So, Yu ratio 1/50 to 1/loo 4 Bi○). After washing for 10 minutes, washing with water for 20 minutes, and drying (this operation was repeated to evaluate durability), the half-life was determined and evaluated using the method described above.

'2' Add 0.5% o. of Eisenkatilone Plue K-Momme LH (a thione dye made by Hodogaya Chemical Co., Ltd.) to the fiber for K/S ratio measurement. w. f(o.
w. f is the weight ratio of adsorbed dye to the dry weight of the fiber)
After complete exhaustion, it was dried for 60 minutes.

Next, the reflection density (K./S, value) of the dyed product after drying was measured using a Hunter type reflection light meter; Color Machine CM-20 model (manufactured by Color Machine KK), and the K/S value was determined by the following formula. The ratio was calculated. K/S ratio = Fukumaki Ayumu ×・〇. (%)In addition,
In the above formula, the denominator value 2/S2) indicates the reflection density of the dyed product obtained according to the above recipe for ordinary acrylic fibers, and the larger the K/S ratio, the lower the degree of color development of the final fiber. means that is small.

The acrylic polymer (1) composed of polyacrylonitrile or at least 7% by weight of acrylonitrile 7 and at least one other polymerizable unsaturated vinyl compound used in the present invention can be produced by well-known polymerization methods such as suspension polymerization, emulsification, etc. Polymerizable unsaturated vinyl compounds that can be produced by polymerization methods, solution polymerization methods, etc., and are copolymerizable components of acrylonitrile include acrylic acid, methacrylic acid, and esters thereof such as methyl ester and ethyl ester: acrylamide and methacrylamide. or N-alkyl substituted products thereof; vinyl esters such as vinyl acetate and pinyl propionate; vinyl halides or vinylidenes such as vinyl chloride, vinyl bromide, and vinylidene chloride; vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, Examples include unsaturated sulfonic acids such as p-styrenesulfonic acid or salts thereof; well-known unsaturated compounds copolymerizable with acrylonitrile such as styrene and methacrylonitrile.

Further, the copolymer (0), which is a mixing partner of the acrylic polymer (1), contains 30 to 7% by weight of acrylonitrile.
and general formula C=CRCO0(CH2CKO)mR'
70 to 3% by weight of the antistatic monomer shown in is copolymerized.

That is, if the acrylonitrile content is less than 3% by weight based on the weight of the copolymer, it is undesirable because it will cause problems in antistatic durability.On the other hand, if the content exceeds 7% by weight, , sufficient antistatic effect is not provided. Further, the above-mentioned copolymer (0) is obtained by employing the same polymerization method (suspension polymerization method, emulsion polymerization method, solution polymerization method, etc.) for producing the above-mentioned acrylic polymer (1). The polymerization catalyst used for the polymerization is also known (benzoyl peroxide, azobisisobutyronitrile, persulfate, hydrogen peroxide, redox initiators such as persulfate and acidic sodium sulfite, and radical polymerization initiation such as ultraviolet rays). It can be manufactured by arbitrarily selecting from the following. The two types of polymers thus obtained (1 and 0
) needs to be mixed so that the monomer represented by the general formula (A) is maintained at 0.3 to 4.0% by weight based on the weight of the entire mixed polymer.

In other words, the antistatic monomer is 0.0% based on the weight of the total mixed polymer. If it is less than 4% by weight of milk, it will be difficult to impart sufficient antistatic properties to the final fiber;
．． If the weight percentage exceeds , the dyeability of the final fiber (
This is undesirable because it impairs color development, sharpness of hue, etc.). In addition, as for means for adjusting the content of the dominating monomer as described above so as to satisfy a predetermined range, by appropriately determining the mixing ratio of the acrylic polymer (1) and the copolymer (0). It can be done. Further, regarding the mixing method of the above two types of polymers 0, there is no particular restriction on this method either, and any ordinary mixing means can be selected. For example 'a
}Method of mixing the acrylic polymer (1) and the antistatic copolymer (0) and then dissolving it in any solvent to make a stock solution of paper yarn, 'b' method of acrylic polymer (1) A method of mixing a yarn stock solution and a bush thread stock solution of copolymer (0), {dissolving copolymer (0) in a paper thread stock solution of c-acrylic polymer (1),
40 methods are used, including a method of preparing a stock solution for thread removal, or a method of dissolving the acrylic polymer (1) in a spinning stock solution of {d' copolymer (b) to obtain a stock solution of threads. Incidentally, as the solvent used for preparing the spinning dope of the above-mentioned copolymer (0) and acrylic polymer (1), organic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene carbonate, y-butyrolactone, etc. Alternatively, inorganic solvents such as concentrated aqueous solutions of sodium thiocyanate, zinc chloride, nitric acid, and the like can be used. Able to achieve objectives effectively. Furthermore, what is important in carrying out the present invention is that a compound represented by the following general formula (B) is added to the mixed polymer paper yarn stock solution prepared by the presence of a predetermined amount of the nine-electrode monomer as described above. 0 for the amount of mixed polymer used
．． 05 to 1% by weight. R''(C
H2CH20)nH (In the formula, R is an alkoxy group having 18 or less carbon atoms, an alkylphenoxy group, a phenoxy group, n represents an integer of 1 to 15) That is, when n exceeds 15 in the above single-pronged formula, The solubility of the compound (B) in water increases, and the compound (B) falls out of the acrylic fiber structure in the solvent removal step during the threading process, ultimately imparting satisfactory antistatic properties. It is undesirable to do so.

Furthermore, if the content of the compound (B) is less than 0.05% by weight, sufficient antistatic effect will not be achieved in the final fiber, while if the content exceeds 1% by weight, Not only will the physical properties such as bending strength and frictional strength of the final fiber deteriorate, but there will also be problems with the color development and clarity of the hue of the dyed product, and troubles will also arise in the workability of the twill yarn. Undesirable. The compound (B) is preferably selected from those with a molecular weight of 700 or less, and when using a compound with a molecular weight of 700 or less, the compatibility between the acrylic copolymer (1) and the anti-military copolymer (0) Problems may arise in this regard, and the antistatic performance may deteriorate. Therefore, it is preferable for the purpose and effect of the present invention to consider the molecular weight when using compound (B).

Furthermore, although the compound (B) used is such a low molecular weight surfactant, it does not fall off during the manufacturing process and maintains a good balance between fiber performance and dominating performance. This is presumed to be due to the good compatibility (easiness of compatibility) with compound (A) as described above. Furthermore, as a preferred embodiment of the present invention,
In addition to the above-mentioned compound (B), a compound represented by the following general formula (C) and, if necessary, a compound represented by the following general formula (D) can also be introduced into the acrylic fiber structure.

(C) (In the formula, X is a hydrogen atom or fCH2C ratio 0) IH, 1 is an integer from 1 to 30, Y is a hydrogen atom or a methyl group, q is 1
(D) (In the formula, R... represents an alkyl group having 1 carbon number) The amount of the above-mentioned compounds introduced is determined in relation to the amount of the compound (A) introduced. (A): Compound (C) = 1:0
．． 01-1.5 Compound (A): Compound (C): Compound (
0)=1:0.01 to 1.6:0.01 to 1.5, the antistatic performance can be further improved.

Further, the means for introducing these compounds may be arbitrarily selected, such as a method of mixing them into the mixed polymer yarn stock solution or a method of mixing them during polymerization.

The mixed polymer paper yarn stock solution prepared as described above is then made into paper yarn to form a fiber yarn body, and the yarn body is then subjected to solvent removal, water washing, hot stretching, drying and densification, and relaxation heat treatment. , winding treatment, etc. are performed to produce the final fiber.

The spinning means according to the present invention is not particularly limited, but a wet paper yarn method is preferably employed in order to advantageously achieve the features of the present invention. In producing acrylic fibers from a mixed polymer bushing solution of an acrylic polymer and an antistatic copolymer as described above, a predetermined amount of an antistatic monomer (11) is contained in the iron thread stock solution. By combining the '21 specific compound with the presence of a predetermined amount, the content ratio of the antistatic monomer, which plays the role of antistatic effect in the base pot, in the mixed polymer can be reduced. In addition, a specific compound newly added to the spinning stock solution plays a role in suppressing the degree of decrease in antistatic property (the rate of decrease in antistatic property commensurate with the amount of decrease in the antistatic monomer mentioned above), and it is surprising that In particular, this proposal was made based on the fact that there was no reduction in fiber performance that would result from suppressing the degree of deterioration in antistatic property.

Examples of the present invention will be described below, but the scope of the present invention is not limited in any way by these Examples.
Note that unless otherwise specified, all parts and percentages are expressed on a weight basis. Example 1 A superior copolymer was prepared by copolymerizing 5 parts of acrylonitrile and 5 parts of methoxypolyoxyethylene (30 moles) methacrylate.

On the other hand, 91 parts of acrylonitrile, 87 parts of methyl acrylate
1 part and 0.3 part of sodium methallylsulfonate were copolymerized to obtain an acrylic polymer. *Next, the two kinds of polymers thus prepared were mixed in a ratio of dominant copolymer: acrylic polymer: 1:24 (the amount of methoxypolyoxyethylene methacrylate relative to the weight of the total mixed polymer). (2.0%), and then dissolved in a 44% aqueous sodium rhodanate solution to prepare a spinning stock solution.

In the hem thread stock solution or the weaving thread stock solution prepared as above, the first
The grade yarn stock solution obtained by adding the compound (B) as described in the table can be prepared by adding wet paper yarn, shedding agent, washing with water, etc. under normal conditions.
After being hot stretched, it was subjected to dry densification and relaxation heat treatment of 100 oo to produce an acrylic fiber with a single fiber density of 3 deniers.

Table 1 shows the results of measuring the antistatic properties and fiber performance of the acrylic fibers thus obtained.

Table 1 (Note) (1) As compound B, C9-day 0 (CH2CH20) 4 days were used.

(2) The residual rate of compound B in the fiber was determined by dividing the residual amount determined by ultraviolet absorption measurement of the fiber by the amount added and converting the result into a percentage.

From the results in Table 1, it is clear that the acrylic fibers obtained according to the method of the present invention (integral combination of the above-mentioned constituent elements of the invention) have practically satisfactory antistatic properties, and have good fiber performance (in particular, color development). You will be able to understand that it is something that makes you possess the characteristics (sexuality). When the acrylic fibers produced by the method of the present invention were observed under a microscope, almost no pores were observed in the fibers. Example
2 The same acrylic polymer and antistatic copolymer as in Example 1 were prepared, and as shown in Table 2, Compound A was added to 1% of the whole polymer.
．． After mixing so as to account for 5%, it was dissolved in a 44% sodium rhodanate aqueous solution to prepare a 0-liquid grade yarn material.

- Next, compound [B}, compound 'C}, and compound plate as listed in Table 2 were added to the spinning dope, and a single acrylic fiber with a total denier of 3 deniers was produced in the same manner as in Example 1. did.

Table 2 (Note) (1) As compound B, use C9 days, 9 ○ (CH2CH20) 8 days. (2) As compound C, use (3) As compound D, use. From the results in Table 2, Compound B in the paper yarn stock solution according to the present invention
It is understood that the antistatic performance of acrylic fibers prepared by further introducing Compound C or, if necessary, Compound D in addition to Compound C, can be further improved.

Example 3 A spinning stock solution was prepared using the same acrylic polymer and tortoise control copolymer as in Example 1, and a compound represented by the following formula was added to it at a concentration of 2% based on the mixed polymer. Add,
A single acrylic fiber with a total denier of 3 deniers was obtained in the same manner as in Example 1.

C, 250 kg for 2 days CH2 CH20) The fiber obtained in 5 days has half-life: 2.2 seconds after 10 washes, K/S ratio of 0 dyed product: total %, and has practically satisfactory fly resistance. In addition, it had good fiber performance.

These results were obtained despite the fact that the acrylic polymer (1) and the crab-controlling copolymer (0) were used, which had poor compatibility with the original pot. This is understood to be due to the fact that it exhibited a good antistatic property imparting behavior.

[Brief explanation of the drawing]

Figure 1 shows the relationship between the content of anti-tormogenous monomers present in acrylic fibers produced by the lacquering method and the degree of deterioration of coloring properties (K/S ratio) due to drying of zero-dyed products of the fibers. FIG. 2 illustrates the relationship between the content of the above-mentioned dominating monomer and the antistatic property of the fiber. Figure 1 Figure 2

Claims (1)

[Claims] 1. Polyacrylonitrile or acrylonitrile 70
From an acrylic polymer (I) consisting of at least % by weight and at least one other polymerizable unsaturated vinyl compound, and from 30 to 70% by weight of acrylonitrile and 70 to 30% by weight of a monomer represented by the following general formula (A) When producing an acrylic fiber from an acrylonitrile polymer spinning solution consisting of an antistatic copolymer (II) obtained by copolymerizing a monomer mixture of (1) general formula (A) in the spinning solution, (2) In addition, a compound represented by the following general formula (B) is added to the mixed polymer in the spinning dope. Against 0.
1. A method for producing an antistatic acrylic fiber with improved fiber performance, characterized by integrally spinning the fiber in an amount of 0.05 to 10% by weight. CH_2=CRCOO(CH_2CH_2O)_mR'
(A) (wherein R is a hydrogen atom or a methyl group, R' is a hydrogen atom or an alkyl group having 8 or less carbon atoms, m is 5 to 10
(represents an integer of 0)R″(CH_2CH_2O)_nH
(B) (In the formula, R'' is an alkoxy group, an alkylphenoxy group, or a phenoxy group having 18 or less carbon atoms, and n is an integer of 1 to 15.)