JPS5916026B2 - Hydrophilic treatment method for synthetic fibers - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for making synthetic fibers hydrophilic.

Although synthetic fibers have various excellent chemical and physical properties, they have many drawbacks in terms of antistatic properties, water absorption properties, SR properties, etc. due to their hydrophobic nature, and their uses are currently limited. It is.

In order to improve these drawbacks, many methods have been studied so far, but they are still not sufficient.

In other words, methods are known in which a hydrophilic substance is blended at the spinning stage and a method in which a hydrophilic substance is attached to the fiber surface at the finishing stage, but the former results in a decrease in spinning properties, a decrease in yarn physical properties, and a decrease in dyeability. There are problems such as decline.

Also, in the latter case, problems such as insufficient washing durability and decreased color fastness remain unsolved.

In order to solve these problems in the modification of synthetic fibers, the inventors of the present application have conducted research and found a hydrophilic agent that has a strong affinity for synthetic fibers, and have already proposed it in Japanese Patent Application No. 51-66430. ing.

However, this hydrophilic agent also had a problem with its adhesion efficiency to fibers during dipping treatment.

That is, when the number of moles of ethylene oxide is high, the adhesion efficiency is greatly reduced and it is impossible to impart sufficient hydrophilicity for practical use.

The inventors of the present application have conducted intensive research to solve this problem, and as a result, have arrived at the present invention.

The gist of the present invention is as follows.

That is, a treatment solution containing at least one inorganic salt selected from the group consisting of alkali metal salts and ammonium salts of sulfuric acid, nitric acid, hydrochloric acid, formic acid, acetic acid, and oxalic acid, and a compound represented by the following general formula, is synthesized. A method for making synthetic fibers hydrophilic, which comprises soaking the fibers and heat-treating them in a bath.

(CH2CHO)y(CH2CHO)xC-C2CH2
(In the formula, R1 to R5 are H or an alkyl group having 1 to 2 carbon atoms.

X1y1 z is O or an integer from 1 to 30; −z or more.

Moreover, each of X1y1 z may be the same or different.

A indicates one type of H3 group selected from 10-1-NH-1-CH2-1H3, 18O2-1←C1, and 10-, or it does not exist (benzene nuclei are directly bonded to each other).

The present invention will be explained in detail below.

The hydrophilizing agent used in the present invention is a compound having a structure consisting of a part having fiber affinity and a part having hydrophilicity, and further having a vinyl group that can be made into a polymer.

The hydrophilic part, that is, the alkylene ether part, is polyoxyethylene (EO), polyoxypropylene (po
) and/or polyoxybutylene (BO), but there is a suitable range for their degree of polymerization; if the degree of polymerization is too low, the affinity with the fibers will be strong, and the adsorption effect will be produced, but the hydrophilic performance will be poor. There will be a shortage.

On the other hand, if the degree of polymerization is too high, it will not be adsorbed to the fibers.

Furthermore, as the number of carbon atoms in polyalkylene oxide increases, its affinity for fibers increases, but its hydrophilicity decreases.

Therefore, from the viewpoint of compatibility with fibers and performance, EOIP
The degree of polymerization of O and BO is preferably about 10 to 20 moles,
In addition, the degree of polymerization of PO and/or BO is 1/2 that of EO.
The following are preferred.

In this case, as the degree of polymerization of EO increases, it is expected that the performance of antistatic properties and water absorption properties will improve, but on the other hand, it becomes difficult to be adsorbed to fibers.

In the range of the number of moles of EO that actually has very good performance, even if synthetic fibers are immersed with this hydrophilic agent alone, the adhesion efficiency will be considerably reduced, which is problematic in practice.

However, in the immersion treatment method in the coexistence of a specific salt of the present invention,
The improvement in adhesion efficiency is remarkable, and a high level of performance that could not be achieved by single treatment can be obtained.

As the hydrophilic agent represented by the above general formula, for example, the molecular weight of the polyoxyethylene segment is 440 and 660.
Examples include 2,2'-bis(4-methacryloxypolyethoxydiphenyl)propane.

Salts added to improve the adhesion of these hydrophilic agents include Na2SO4, NaC1゜NaNo3
,(NH4)2SO4,CH3CO0NH,,HCO
ONH4, NH4Cl, (NH4), C2O4, CH
There are alkali metal salts and ammonium salts of sulfuric acid, nitric acid, hydrochloric acid, formic acid, acetic acid and oxalic acid such as 3COONa.

As additives for improving the adhesion of the hydrophilizing agent according to the present invention, the above-mentioned salts are essential, and acid, alkali and other salts have no effect at all.

Some even inhibit adhesion.

The synthetic fibers to be treated include long fibers, short fibers, spun yarns, knitted fabrics, nonwoven fabrics, etc. made of polyamide, polyester, polyacrylonitrile, polyolefin, and modified polymers thereof, and the manufacturing method and composition thereof It is not limited by components, arrangement, etc.

The effect is most remarkable when polyester fibers are targeted in terms of the durability of the imparted hydrophilic properties.

The polyester fiber may be one that has been subjected to a commonly used alkali treatment.

The processing method of the present invention will be described in further detail.

The treatment method of the present invention relates to a dipping treatment, in which the adhesion of a hydrophilic agent to an aqueous solution or an aqueous dispersion containing a hydrating agent with a weight factor of 0.5 to 20, preferably 1 to 10, by weight relative to fibers. The concentration of salt in the aqueous solution is 0.1 to improve the
Synthetic fibers are immersed in a treatment liquid that has been added and adjusted to have a ratio of 0.3 to 2, preferably 0.3 to 2, and then heat treated at 30 to 150°C.

At this time, a commonly used polymerization initiator may be added to speed up the polymerization reaction of the hydrophilic agent.

In particular, if a redox initiator is used, low-temperature, short-time processing becomes possible.

This dipping treatment can be performed either before or after dyeing. well,
It is also possible to carry out staining at the same time.

In this case, if a fiber swelling agent commonly used in carrier dyeing is used in combination, the penetration of the dye into the fibers will be aided and the adhesion of the hydrophilic agent will also be improved.

In the present invention, an aqueous dispersion of a hydrophilic agent refers to a state in which fine particles of a hydrophilic agent are dispersed in water, and if necessary, a general organic solvent such as toluene, xylene, benzyl alcohol, or chlorobenzene may be used. Common surfactants used as emulsifiers and dispersants may also be used.

Polymerization initiators used in the present invention include peroxides used as vinyl polymerization initiators such as ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoyl peroxide, and these peroxides, iron (II) ions, and sulfite. A redox initiator consisting of a combination of a salt, a reducing agent such as hydroxylamine, and hydrazine is used, and by selecting the type of polymerization initiator, it is possible to appropriately perform the treatment under desired treatment conditions.

One of the features of the present invention is that highly hydrophilic monomers have poor adhesion to fibers even when immersed in the presence of a hydrophilic agent alone or in the coexistence of dyes, but by adding a specific salt, it becomes extremely adhesive. is to become better.

Another feature of the present invention is that it can be subjected to hydrophilic treatment at the same time as dyeing, and has extremely high resistance.

It is possible to impart water absorbency with washing properties, antistatic properties, and SR properties.

The mechanism of adhesion of the hydrophilic agent to synthetic fibers is thought to be such that formation of a film on the fiber surface and adhesion within the fiber bundle occur simultaneously.

Next, examples of the present invention will be shown.

Example 1 2,2'bis(4-meccryloxypolyethoxydiphenyl)propane with a molecular weight of 660 and 59/I! of 3.0% by weight of polyoxyethylene segments based on the fibers.
A scouring-treated Tetron textured yarn fabric (basis weight 150 g/ynj) was immersed in an aqueous solution of anhydrous sodium sulfate (bath ratio 1:30) at 130° C. for 30 minutes.

As a comparative example, a sample without the addition of anhydrous sodium sulfate was also treated in the same manner.

After washing and drying, a portion of the treated fabric was washed in a 2 g/l aqueous solution of neutral detergent (ZABU, manufactured by Kao Soap) at 40°C for 5 minutes, and then washed and dried.

This washing, water washing, and drying operation was repeated five times.

The adhesion rate, water absorption, and frictional charging voltage of the treated fabric before and after washing were measured, and the measurement results are shown in Table 1.

It is clear that according to the treatment method of the present invention, the adhesion efficiency of the hydrophilic agent is high, and there is no drop-off or deterioration of performance due to washing.

The performance evaluation method is as follows.

Adhesion rate: Determined from the weight change before and after treatment.

Water absorption: A water droplet of approximately 0.03 ml was dropped on the test fabric, and the time required for it to be completely absorbed was measured.

Frictional charging voltage: Measured using a Kyoto University Kaken type rotary static tester in an atmosphere of 20°C and 140% RH using cotton cloth as the subject cloth.

Example 2 2,2'bis(4-meccryloxypolyethoxydiphenyl)propane with a molecular weight of 660 and 2.0% by weight of polyoxyethylene segment based on the fiber and 5 g/l
A treatment solution was prepared consisting of anhydrous sodium sulfate and 0.5% Resolin Red FB (manufactured by Bayer AG) based on the fiber.

A smelted polyester long fiber processed yarn fabric (basis weight 150.9/m') was immersed in this solution (bath ratio 1:30), 13
It was treated at 0°C for 1 hour.

Furthermore, as a comparative example, a sample to which anhydrous sodium sulfate was not added was also treated in the same manner.

A portion of the fabric was washed in the same manner as in Example 1.

The adhesion rate, water absorption, and frictional charging voltage of the treated fabric before and after washing were measured, and the measurement results are shown in the table.

It is clear that the treatment method of the present invention provides good adhesion and performance of the hydrophilic agent.

There were no problems with dyeability and color fastness.

Example 3 In an aqueous solution consisting of 2,2'bis(4-meccryloxypolyethoxydiphenyl)propane in which 3% by weight of polyoxyethylene segment with respect to the fiber has a molecular weight of 660 and 10 g/l of anhydrous sodium sulfate, 0.19/II
A treatment solution was prepared by adding ammonium persulfate (0.39/13) and Superlye (0.39/13) C (reducing agent, manufactured by Mitsubishi Gas Chemical).

Tetron processed yarn fabric dyed with this treatment solution (fabric weight 150
The samples were treated at 70°C for 30 minutes at a bath ratio of 1:30).

After thoroughly washing with water, it was dried and a part of the treated fabric was washed in the same manner as in Example 1.

Adhesion rate, water absorption, and frictional charging voltage were measured for the treated fabric before and after washing.

Furthermore, as a comparative example, a sample without the addition of anhydrous sodium sulfate was also treated in the same manner.

These results are shown in the table.

According to the treatment method of the present invention, good adhesion and performance of the hydrophilic agent can be obtained.

Furthermore, there were no problems with processing discoloration or color fastness.

Example 4 A scouring-treated Tetron processed yarn fabric (basis weight 15 og/m) was immersed in the same treatment solution as in Example 3 (bath ratio 1:30).
, and treated at 70°C for 30 minutes.

After thoroughly washing with water, the fibers were dyed at 130° C. for 1 hour using 2 weight width Sumikalon Blue 5BG (Sumitomo Chemical).

After washing with water, in an aqueous solution consisting of 47° Be' caustic soda, amylazine D (nonionic surfactant, Daiichi Kogyo) and hydrosulfide (1 g/l each) at 80°C for 30 minutes.
Reduction cleaning was performed.

After washing with water and drying, a part of the treated fabric was washed in the same manner as in Example 1.

The adhesion rate, water absorption, and frictional charging voltage of the treated fabric before and after washing were measured, and the good results shown in the table were obtained.

There were no problems with dyeability or color fastness.

Example 5 2,2'bis(4-methacryloxypolyethoxydiphenyl) polyoxyethylene segment having a molecular weight of 660 and 10 g/l of polyoxyethylene segments of 5 weight width relative to the fiber
0.1 g/l in an aqueous solution consisting of 11 um of anhydrous sodium sulfate
of ammonium persulfate and 0.39/l of Superlite C were added to prepare a treatment solution.

Polyamide long fiber fabric dyed with this treatment solution (fabric weight 10
0 g/m") at a bath ratio of 1:30) at 70°C.
After being heat treated for a minute, it was thoroughly washed with water and dried.

Further, as a comparative test, a similar treatment was performed on a sample to which anhydrous sodium sulfate was not added.

A portion of each treated fabric was washed in the same manner as in Example 1.

Adhesion rate, water absorption, and frictional charging voltage were measured for the treated fabric before and after washing, and the results are shown in the table.

The treatment method of the present invention provided good adhesion and performance of the hydrophilic agent, and there were no problems with processing discoloration or color fastness.

Example 6 0.1f! is added to an aqueous solution consisting of bisphenol A diPEG methacrylate and anhydrous sodium sulfate of iog7i, in which the molecular weight of polyoxyethylene segments of 5 weight width relative to the fiber is 660. /l ammonium persulfate and 0.39
A processing solution was prepared by adding Superlite C of /11.

A scouring-treated polyacrylic spun knitted fabric (basis weight 120 g β) was immersed in this treatment solution (bath ratio 1:30) at 70°C for 30 minutes.
Processed for minutes.

After thoroughly washing with water, the fibers were immersed in a dyeing solution consisting of 2 weights of Kayacryl Blue GR (Nippon Kayaku) and 0.5 g/l of acetic acid, and dyed at 100° C. for 1 hour.

Further, as a comparative example, a sample to which anhydrous sodium sulfate was not added was also subjected to the same treatment.

A portion of each treated fabric was washed in the same manner as in Example 1.

The adhesion rate, water absorption, and frictional charging voltage of the treated fabrics before and after washing were measured. As shown in the table, the treatment method of the present invention provides good adhesion and performance of the hydrophilic agent.

Moreover, there were no problems in dyeability and color fastness.

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Claims (1)

[Claims] 1. Contains at least one inorganic salt selected from the group consisting of alkali metal salts and ammonium salts of sulfuric acid, nitric acid, hydrochloric acid, formic acid, acetic acid, and oxalic acid, and a compound represented by the following general formula. A method for making synthetic fibers hydrophilic, which comprises immersing the synthetic fibers in a treatment solution and heat-treating them in the bath. R1 to R5 are H or an alkyl group having 1 to 2 carbon atoms, x
, y, z are 0 or integers from 1 to 30, and x +y -1-
z is 5 to 30, one of the alkylene ether moieties must be ethylene oxide, and the number of moles thereof is (x+y+z)/2 or more. Moreover, each of X1y1 z may be the same or different. A is a type of group selected from 10-1-NH-1-CH2-1-SO2-1R)-1 and CH310-, or CH3 does not exist (benzene nuclei are directly bonded to each other) Show that. ]