JPS5818466B2 - Method for modifying hydrophobic fibers or their fiber structures - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for imparting antistatic properties, water absorbing properties, and soil release properties to hydrophobic fibers and their fiber structures through post-treatment, and more specifically, the present invention relates to a method for imparting antistatic properties, water absorbing properties, and soil release properties to hydrophobic fibers and their fiber structures, and more specifically, to hydrophobic fibers having a polymerizable vinyl group. The present invention relates to a novel modification treatment method for imparting permanent antistatic properties, water absorption properties, and soil release properties to these treated objects using hydrophobic modifiers.

1 Conventionally, hydrophobic fibers and their fiber structures are treated with a treatment solution containing a vinyl-based hydrophilic modifier such as acrylic acid, acrylamide, polyalkylene glycol cyacrylate, or a derivative thereof. It is known that these vinyl modifiers can be polymerized to impart antistatic properties, water absorption properties, and soil IJ properties to fibers.

In these conventional treatment methods, a polymerization initiator, such as a peroxide such as ammonium persulfate or potassium persulfate, is used to convert the modifier into 1. The method of imparting polymerization initiating ability by reacting on the fiber or by irradiating it with ionizing radiation is usually used, such as the pad dry method, pad steam method, or dipping method. The padding method does not allow firm adhesion to the fibers, and the dipping method adds a radicalizing agent to the water solution, so the modifier is absorbed into the water before it coagulates and deposits on the fiber surface. These methods tend to produce a large amount of homopolymer in the liquid, which significantly reduces the adhesion rate to the fiber surface. It is difficult to obtain soil properties and soil properties.

In addition, the method of irradiating with ionizing radiation and treating it has drawbacks such as being unsuitable for practical use in terms of process and operation.

On the other hand, recently, a polyalkylene glycol diacrylate has been proposed in which a bisphenol aromatic group is introduced into the skeleton to improve its affinity for hydrophobic weaving (Japanese Unexamined Patent Application Publication No. 1989-1992). -150392 Publication), by using such a modifier, it has become possible to eliminate the above-mentioned knocking rate to some extent, but in this case, depending on the type of fiber to be treated, the treatment effect may be sufficiently durable. Furthermore, the modifier may become colored during the treatment process or during washing, resulting in white discoloration of the treated material, loss of color clarity, and poor product quality. It has not been put into practical use because of the unexpected drawback of significantly lowering the performance.The inventors of the present invention have focused on these drawbacks and have conducted extensive and systematic research in an effort to improve them, and have developed the present invention. The purpose is to create hydrophobic fibers and structures,
Or, a novel modification treatment method that can impart durability and initial performance to textile products containing them, such as antistatic properties, water absorption properties, soil IJ IJ- properties, and even a soft texture. It is about providing.

The second object of the present invention is to provide the above-mentioned modified product which can be heat-treated without the addition of a catalyst during processing to impart washability and durability, and which is excellent in light resistance, durability and heat resistance, and has good hue stability. lies in providing quality processing methods.

A third object is to provide the above-mentioned modification method that is effective and can be applied to a wide range of hydrophobic fibers.

That is, the present invention provides general formula (i) [wherein R1, R2=H or CI (2 momme, k=o~25, l=5~50, k+1=5~5
It is 0.

] and the general formula (If) or +CH2CH2O month FCH2CHO rare - where m
=0~25. , n=5-50, m+n=5-50.

This is a method for modifying hydrophobic fibers or fiber structures thereof, which comprises applying a treatment solution containing the compound represented by the following formula or a salt thereof and subjecting the fiber to a heat treatment.

The compound represented by the above general formula (I) or (1) (hereinafter the former is referred to as compound (I) and the latter as compound (1)) is a hydrophilic monomer having two polymerizable vinyl groups. Moreover, because it contains a specific aromatic hydrophobic group in its skeleton, it has excellent affinity for hydrophobic fibers, and when this is applied to hydrophobic fibers, these compounds are It coagulates and deposits on the surface of fibers, giving them durable water absorbency, antistatic properties, and antifouling properties.

Furthermore, compounds (I) and (1) both have good thermal stability, which is probably due to the characteristics of their aromatic group moieties, which is similar to that seen in conventional bisphenol-based aromatic group-containing compounds. There is no coloring during the processing process,
Provides processed products with excellent white discoloration or hue clarity.

Therefore, although these compounds (I) and (1) are effective even when used alone, according to what the present inventors were able to clarify, when they are used together, the above-mentioned effects An additional advantage is that it allows treatment to be applied to a wider range of hydrophobic fibers than when used alone, yet with improved durability and initial performance. The present invention has been completed based on this knowledge.

Furthermore, since compounds (I) and (1) can be easily polymerized even in the absence of a polymerization initiator, and as mentioned above, film formation on the fiber surface takes precedence, according to the method of the present invention,
Because polymer formation in the treatment bath or in the interstices of the fibers is minimized, and because the effective adhesion of the treatment agent to the fibers is high, treatment agent losses are significantly reduced and the resulting coating is The treated product has many advantages over conventional methods, such as superior flexibility and texture.

Embodiments of the present invention will be described in detail below.

Hydrophobic fibers to which the method of the present invention can be applied include synthetic fibers such as polyamide fibers, polyester fibers, polyacrylonitrile fibers, and polyolefin fibers, and semi-synthetic fibers such as triacetate fibers. Examples include yarns, woven fabrics, knitted fabrics, nonwoven fabrics, felts, carpets, etc. that are made of fibers or contain them.

Although the method of the present invention is effective for a wide range of objects to be treated, particularly remarkable effects can be obtained when applied to polyamide fibers, polyester fibers, and fiber structures thereof.

Among the compounds (■) used in the present invention, some aromatic groups are derived from phthalic acid, inphthalic acid, and terephthalic acid, but residues of isophthalic acid or terephthalic acid are generally preferred.

Further, in both compounds (I) and (1), the molecular weight of the polyalkylene glyconyl moiety is preferably in the range of 300 to 3,000 (and preferably in the range of 400 to 2,000).

If the molecular weight is less than 300, the solubility of the compound in water will be insufficient, and the antistatic and water absorbing effects will also decrease.
On the other hand, if it is 3,000 or more, the hydrophilicity becomes excessively high, resulting in a decrease in affinity for hydrophobic fibers, resulting in a decrease in modifier adhesion rate and washing durability, both of which are unfavorable.

Furthermore, in the polyalkylene glycol chain, it is desirable that the number of moles of ethylene glycol residues (1, n) is smaller than the number of moles of propylene glycol residues (k, m), respectively, from the viewpoint of processing effects, and from the viewpoint of manufacturing. Considering the difficulty of
・.

In this case, it is desired that the number of moles (l, n) of ethylene glycol residues is 10 to 40.

Acrylate and methacrylate are not much different in their processing effects, and any one can be used as appropriate.

Specific examples of compounds (I) and (1) used in the present invention are listed above, but these are merely illustrative and do not limit the present invention in any way.

Compound (I): Regarding compound (1), potassium chloride can also be suitably used as in the case of the above-mentioned sodium salt.

The modification treatment method of the present invention comprises compound (I) and compound (1).
and generally 5:95 to 95:5, preferably 10:90
．． This is carried out by applying a treatment liquid containing a weight ratio of ~90:10 to the object to be treated and heat-treating it.

If the weight ratio of compound (I) is less than 5, the durability of the treatment effect tends to decrease, and if the weight ratio of compound (1) is less than 5, the initial performance In particular, there is a tendency for initial antistatic properties to be insufficient, and both are unfavorable.

The weight ratio of both compounds within the above range depends on the type of fiber to be treated, the purpose of processing, etc., and it cannot be said exactly, but from a cost standpoint, it is best to quantify compound (I) as much as possible. Considering that it is advantageous to use a compound (
It is appropriate to use compound (I) in excess of compound (1), usually in a weight ratio of 70:30 or more, and for polyamide fibers, compound (I) is used in excess of compound (1). It is preferable that the amount is equal to or in excess of [).

The amount of compound (I) and compound (1) (hereinafter collectively referred to as modifiers) to be applied (the amount of adhesion to the fibers) is preferably 0.5% or more in terms of solid content based on the weight of the fibers. is 1.0% or more, and if it is less than 0.5%, it is difficult for the modifier to form a uniform and strong thin film on the fiber surface, resulting in a decrease in washing durability and the expected result. This is not preferable as it is difficult to obtain the desired effect.

Methods of applying a treatment liquid containing the above-mentioned modifier to hydrophobic fibers or their fiber structures and heat-treating include a method of immersing the treated object in the treatment liquid and heat-treating it, or a method of applying the treatment liquid to a package. A method of spraying, spraying and then heating treatment can be used.

However, in this case, in order to make the properties of the modifier of the present invention more effective, that is, coagulation deposition on the fiber surface and preferential polymer film formation at that site, it is generally necessary to perform heat treatment in a wet state. This is important, and dry heat treatment tends to make it difficult to form a uniform film on the fiber surface, reducing the durability of the treatment.

From this point of view, the immersion heating method is the most preferable method, but when using the spraying method or the padding method, if tearing occurs, the object to be treated usually remains moist after spraying or padding without pre-drying. While doing that,
The steaming treatment may be performed in a steamer or a high-pressure steamer.

When using the immersion heating method, the object to be treated is placed in a treatment solution with a modifier concentration of 0.7 to 5% owf at a bath ratio of 1:5 to 1:1.
0.0, preferably 1:5 to 1:80, usually at 90 to 160°C, preferably 100 to 150° without a catalyst.
It is appropriate to heat treat for 1 to 60 minutes, preferably for 5 to 45 minutes, within the range of Thereafter, it is preferable to raise the temperature to the above-mentioned treatment temperature, thereby further increasing the adhesion rate of the modifier to the object to be treated.

When applying the spray method or padding method, a treatment liquid with a modifier concentration of 1 to 10 wt% is usually used, and this is applied to the object to be treated until the solid content of the modifier is 0.15 wt%.
% or more, preferably 1.0% or more, and then heat-treated under the same temperature and time conditions as in the immersion heating method described above.

In addition, in any of the above treatments, such as immersion heating method, spraying method, putting method, etc., from the viewpoint of further increasing the adhesion of the modifier, the treatment solution is adjusted in advance to pH 7 to 1, preferably 6.
It is desirable that it be adjusted within the range of ~3.

Of course, the pH is not limited to this range, and an appropriate pH can be selected depending on the type, shape, presence or absence of dyeing, etc. of the fiber to be treated.

Examples of acids used to adjust the pH include organic acids such as acetic acid, formic acid, and citric acid; inorganic acids such as sulfuric acid and phosphoric acid; and derivatives thereof.

In addition, in the method of the present invention, it is not necessary to use a polymerization initiator, and from the viewpoint of stabilizing the treatment process and making the treatment uniform, it is generally not used. And it is a preferable method.

According to the above method of the present invention, compound (I) and compound (1)
Through the synergistic action of these, it provides a wide range of hydrophobic fibers such as polyester fibers and polyamide 1 fibers with improved antistatic properties, water absorption properties, and antifouling properties in both washing durability and initial performance. Furthermore, unlike conventional methods, there is almost no discoloration of the treated material or the formation of homopolymers, resulting in high-quality products with excellent appearance and texture. You can get the product.

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

The evaluation methods for durability, antistatic properties, water absorption properties, and soil IJIJ-z properties as well as the washing method for evaluating durability shown in the Examples are as follows.

O charging voltage (V) Using a Kyoto University Kaken type rotary star tickster (manufactured by Koa Shokai), using pure gold medium No. 3 as a friction cloth, 20 ± 2 ° C, 40
Measured at ±2%RH.

O half-life (see) Measured using a static honest meter (manufactured by Sagetsu Shokai) under the conditions of applied voltage of 10 KV, 20±2° C., and 40±2% RH.

O water absorption (CIn/l 011tn) Measured by JIS L-1079B method (bisic method).

○Washing fastness: It was carried out according to JIS L-0844 method.

0 whiteness: Using a photoelectric spectrophotometer model EPR-2 manufactured by Hitachi, Ltd., and using magnesium oxide as a standard, the specific reflectance (%) at a wavelength of 450 mμ was determined.

O Washing method: Neutral detergent (product name Pinky, Lion Yushi Co., Ltd.) 01
% in a 40° C. washing solution using a home washing machine (fully automatic washing machine model EP-578, Hitachi, Ltd.).

One cycle consisted of washing at 40° C. for 10 minutes, rinsing at room temperature for 3 minutes in two directions, and dehydration, and this was repeated five times.

Example l A polyester fabric (75d/36f, taffeta) was immersed in a treatment bath with the following composition containing the following modifier (a:b) at the blending ratio (solid content weight ratio, hereinafter the same) shown in Table 1. Then, the temperature was raised from room temperature in about 30 minutes, and heat treatment was performed at 120° C. for 1θ minutes.

After finishing the treatment, it was washed with warm water at 40'C for 1 minute, further washed with water, and then dried in a hot air dryer at 40'C.

Table 1 shows the results of evaluating the antistatic properties and water absorption properties of the treated fabrics obtained above.

In this treatment, almost no homopolymer formation was observed in the treatment solution, and it was confirmed that most of the modifier was polymerized and fixed on the fiber surface.

Treated fabrics were obtained in exactly the same manner as in Example 1, except that they were used (examples of the present invention), and their antistatic properties and water absorption properties were evaluated, and the results shown in Table 2 were obtained.

For comparison, Table 2 also lists the physical property values of treated fabrics (comparative examples) obtained by treating in the same manner using the following compound alone instead of the above modifier.

As shown in Table 2, according to the method of the present invention, antistatic and water absorbing effects with excellent initial performance and durability can be obtained, and there is almost no deterioration in whitening of the treated fabric. In the conventional method using a modifier having a bisphenol aromatic ring,
In addition to being inferior to the method of the present invention in antistatic properties and water absorption, the whitening of the treated fabric was significantly reduced, particularly during treatment or washing, and the superiority of the method of the present invention is clear.

Example 3 The same polyester fabric as in Example 1 was treated with the following modifier e.
, f at a blending ratio of 90:10 and at a concentration shown in Table 3, immersed in a pH 5 treatment solution at a bath ratio of 1:20, as described in Example 1 below.
In the same manner as above, treated fabrics with different amounts of modifier deposited were obtained by dipping, washing, and drying.

The physical property values of these treated fabrics are shown in Table 3, and the results show that when the amount of modifier attached to the fibers is less than 0.5%, the washing durability of the treatment effect decreases. It is clear that there is a trend.

Example 4 Nylon fabric (70d/18f taffeta) as the object to be treated
The same procedure as in Example 2 (inventive example) was carried out except that the treated fabrics were obtained (inventive agent), and the results were reported in the fourth example.
Shown in the table.

In addition, Table 4 shows the results of the above-mentioned method using a treatment solution containing Modifier C or D alone (Comparative Examples ■, 1) and a treatment solution containing the following modifier (Comparative Example ■). The results when treated under the same conditions as the invention examples are also shown.

As is clear from the table above, the method of the present invention is also effective when applied to nylon fabrics.

Example 5 The same nylon fabric as in Example 4 was treated with the following modifier substance g.
, h at the blending ratio shown in Table 5 at a modifier concentration of 10 wt%, p
Immerse in H5 processing solution and apply the pass solution with a mangle to reduce the squeezing rate to 50.
%, immediately placed in a high-pressure methymer and steamed at 130° C. for io minutes, washed and dried in the same manner as in Example 1 to obtain a treated cloth.

Table 5 shows the physical properties of these treated fabrics. Example 6 A nylon fabric (70d/18f, tuck) dyed navy blue using an acid dye in a conventional manner was treated with the same modifiers e and f as in Example 3 at the blending ratio shown in Table 6. immersion treatment under the same conditions as in Example 1,
A treated cloth was obtained by washing and drying.

The results are shown in Table 6. Example 7 A polyester fabric ( 75d/36
f, taffeta) was immersed and heated to obtain treated fabrics.

Table 7 shows the antistatic properties and water absorption properties of the treated fabrics obtained in the above steps.

Example 8 A polyester fabric (75d/36f taffeta) was treated with the following modifiers m and n (where x and y are the average number of moles shown in Table 8).

) at a blending ratio of 50:50.
immersed in water, raised the temperature from room temperature in about 30 minutes, and heated to 1 in 120 minutes.
Heat treatment was performed for 0 minutes.

After the treatment was completed, it was washed with warm water at 40° C. for 1 minute.

Thereafter, it was dried in a hot air dryer at 40°C.

Table 8 shows the results of evaluating the antistatic properties and water absorption properties of the treated fabrics obtained using rice.

Claims (1)

[Scope of Claims] 1 A hydrophobic fiber or a fiber structure thereof, a compound represented by the general formula () % formula % and a compound represented by the general formula (1) or +CH2CH2O+n (CH2CHO+, where m = 0 to 25, n =5~50, m+n-5
~50. A method for modifying a hydrophobic fiber or a fiber structure thereof, which comprises applying a treatment solution containing a compound represented by the above or a salt thereof and subjecting the same to heat treatment. 2 The compound represented by general formula (I) and the compound represented by general formula (II) or a salt thereof are mixed in a ratio of 5:95 to 95:5.
The modification treatment method according to claim 1, using a treatment liquid containing a weight ratio of . 3. The modification treatment method according to claim 2, wherein a treatment liquid containing a weight ratio of 10:90 to 90:10 is used. 4 Claims 1 to 4, in which the compound represented by general formula (I) and the compound represented by general formula (1) or a salt thereof are applied in a total solid content of 0.5% or more based on the weight of the fiber. The modification treatment method described in Section 3. The modification treatment method according to claim 4, wherein the modification treatment method is applied by 510% or more. 6 The compound represented by the general formula (i) and the compound represented by the general formula (1) or its salt are polyalkylene gels, in which the repeating unit (l or n) of the ethylene glycol residue in the recall chain is glopylene. 6. The modification treatment method according to claim 1, wherein a repeating unit (k or m) of a glycol residue is used. 7 Claim 6 in which the polyalkylene glycol chain is entirely composed of ethylene glycol residues
Modification treatment method described in section. 8 Ethylene glycol remainder - ○ repeating unit (l or n)
8. The modification treatment method according to claim 7, wherein is 10 to 40. 9 Claims 1 to 8 in which the phthalic acid moiety consists of an inphthalic acid residue or a terephthalic acid residue are used as the compound represented by the general formula (I).
Modification treatment method described in section. 10. The modification treatment method according to claims 1 to 8, wherein a sodium salt or a potassium salt is used as the salt of the famous compound represented by the general formula (1). 11. The modification treatment method according to claim 1, in which heat treatment is performed in a wet state. 12. The modification treatment method according to claim 11, wherein the heat treatment in a wet state is an immersion heat treatment. 13 Claim 1 or 2, in which the heat treatment in a wet state is a steam treatment (the modification and treatment method described) The modification treatment method according to claim 11. 15. The modification treatment method according to claim 1, which uses a treatment liquid whose pH is adjusted in advance to 7 to 1.