JPS63203874A - Treatment agent for aromatic polyamide fiber - 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] [Industrial Application Field] The present invention relates to a treatment agent for textiles, and in detail,
This invention relates to a processing agent for aromatic polyamide fibers that has excellent yarn conjugation properties and abrasion resistance.

[Conventional technology]

It is known that aromatic polyamides can be obtained from aromatic diamines and aromatic dicarboxylic acids, or aromatic aminocarboxylic acid derivatives, and it is also already known that lJ1 fibers can be obtained by wet spinning these aromatic polyamides. That's true. As expected from its molecular structure, such aromatic polyamide fibers have excellent mechanical properties, heat resistance, chemical resistance, etc., and are extremely useful fibers as industrial materials.

In general, not only aromatic polyamide fibers, #Jl! In the fiber manufacturing process, a treatment agent is applied to the fiber surface for the purpose of preventing static electricity, imparting smoothness, and the like.

In particular, when processing fibers into twisted yarn, knitting, R-type products, etc., processing agents with high resistance to friction between fibers, contact friction with processing machine parts, etc., that is, excellent abrasion resistance, or In order to prevent single yarns from becoming loose due to such abrasion, it is necessary to apply a treatment agent with high convergence and binding properties.

On the other hand, from the viewpoint of improving wear resistance, paraffin wax with a small coefficient of friction was used as a treatment agent component.
Alternatively, methods using high polymers of ethylene oxide and propylene oxide, so-called organosilane added to conventional textile treatment agents, or methods using such organosilane derivatives as a main component as treatment agents have been adopted. It's here.

On the other hand, a method has also been proposed in which a so-called sizing agent, such as polyvinyl alcohol, polyacrylamide, etc., is added to the fiber treatment agent for the purpose of increasing the conjugation property.

[Problem that the invention seeks to solve]

However, it has been found that the above-mentioned prior art cannot be sufficiently effective when applied to aromatic polyamide fibers.

That is, aromatic polyamide fibers have higher crystallinity and orientation than, for example, general-purpose polyethylene terephthalate fibers, nylon fibers such as polyhexamethylene adipamide, polycaprolactam, etc., and among them, para-oriented aromatic polyamide fibers As expected from the fact that the fiber surface tends to peel off in the form of fibrils due to abrasion and generate a large amount of fuzz, and from the molecular structure of the aromatic polyamide itself,
As a result of the high ratio of amide bonds and high hydrophilicity, e.g.
This is due to the fact that highly hydrophobic treatment agents such as paraffin wax or high molecular weight ethylene oxide or propylene oxide have weak adhesion to the fiber surface, making it impossible to obtain high oil film strength against wear.

Therefore, in the above-mentioned conventional technology, fuzz is generated due to contact friction with a machine during the process of winding the yarn, fuzz occurs during the yarn twisting process, fuzz occurs frequently due to single yarn breakage, or fuzz is caused by rubbing due to healds etc. during weaving process. However, problems such as the occurrence of pilling could not be solved.

On the other hand, even in the above-mentioned conventional technology for increasing the conjugation property as a yarn, aromatic polyamide has inherently rigid properties, and by applying a sizing agent etc., it becomes even more rigid as a yarn, making it easier to process. It has problems such as being inferior to the standard. Furthermore, in applications that take advantage of heat resistance, which is one of the excellent properties of aromatic polyamide fibers, such adhesives may reduce the heat resistance properties or significantly reduce the quality due to discoloration, decomposition, etc. In order to avoid this problem, once processing such as twisting and weaving,
This results in disadvantages such as the need to remove glue and the like.

The present invention solves the conventional problems as described above.
In post-processing processes such as spinning, winding, twisting, knitting, and weaving of aromatic polyamide fibers, it is stable and efficient without causing fuzz, single yarn breakage, or deterioration of processability and product quality due to loose yarns. Aromatic polyamide 11 with excellent wear resistance and conjugation properties that can be processed and manufactured into products.
The present invention provides a maintenance treatment agent.

[Means for solving problems]

However, as a result of intensive research from the above viewpoint, the present inventor found that a water-dispersible silica sol with a specific particle size has a high affinity for aromatic polyamide, and that a specific ethylene oxide/propylene oxide It has been discovered that a combination of a copolymer and the water-dispersible silica sol described above can achieve strong oil film strength with excellent wear resistance, and that the water-dispersible silica sol has a high binding strength due to its thickening effect, and has developed the present invention. This is the completed version.

That is, the object of the present invention is to remove the solvent or dispersion medium and to add (B) 0.1 to 10% by weight of water-dispersible silica sol having an average diameter of (A> -order particles of 50 mμ or less) into the practical active ingredient. Formula [1
] 30% by weight or more CI of an alkyl EO/PO copolymer having a weight average molecular weight of 10.000 or more.

This is achieved by a treatment agent for aromatic polyamide fibers characterized by containing R-0 day 11° CH20)-7(-CII 2CHO piece)-H(Ill).

The water-dispersible silica sol (A) is fine particulate anhydrous silica having silanol groups (→5i-Oil) on the surface, and the average diameter of the primary particles is required to be 50 mμ or less. If it is 50 mμ or more, it is difficult to increase the affinity for the aromatic polyamide fiber surface, and a high oil film strength with excellent abrasion resistance cannot be exhibited. Furthermore, the binding power of component (B), which will be described later, is not sufficiently expressed, which is not preferable.

Such water-dispersible silica sol can be used as it is in the form of particles, or as a commercially available water dispersion or alcohol dispersion. Specific examples of commercially available products include Cataloid SN (manufactured by Catalyst Kasei Co., Ltd.), Snowtex 20,
Snowtex C (all manufactured by 8san Kagakusha), ^ERO
Examples include SIL200 or 300 (manufactured by Nippon Aerosil Co., Ltd.), but are not limited to these.

In the treatment agent of the present invention, the water-dispersible silica sol described above is 0.1% by weight in the substantial active ingredients excluding the solvent or dispersion medium.
It is important that the content be 10% by weight. If it is less than 0.1% by weight, it is insufficient to enhance the affinity with the aromatic polyamide fiber surface, and effective abrasion resistance cannot be obtained. On the other hand, if it is more than 10% by weight, the hardness of the oil film becomes high, and as a result, the treatment agent often peels off and falls off during processing processes such as knitting and weaving, which may lead to a decrease in processability and the resultant product. do not have.

Alkyl EO/PO represented by formula [I] in (B) above
The copolymer needs to have a weight average molecular weight of 10,000 or more. If the weight average molecular weight is io or oooo and the groove is not formed, sufficient abrasion resistance cannot be exhibited and the conjugation property is also poor. Weight average molecular weight is 10,00
If it is 0 or more, even if the copolymer is a random copolymer, it will not cause any particular problem in the present invention, but block copolymers are superior in terms of wear resistance.
Particularly preferred. In such a copolymer, the polymerization ratio of ethylene oxide (E○) and propylene oxide (PO) is EO/
PO=90-40/10-60.

In the treatment agent of the present invention, the alkyl EO/PO copolymer must be present in an amount of 30% by weight or more in the actual active ingredients. If it is less than 30% by weight, sufficient wear resistance cannot be obtained.

In the treatment agent of the present invention, components other than the above-mentioned (A) and (B) are not particularly limited to the present invention. It may contain an electric agent, a surfactant for dispersion and emulsification, and the like. Specific examples of such components include esters of higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, alkyl EO/
In the present invention, it is also possible to add PO adducts, alkyl sulfates, alkyl sulfonates, alkyl phosphate-I type antistatic agents, or in the case of small additions, sizing agents such as polyvinyl alcohol and polyacrylamide. , if the above-mentioned (A) and (B) are in the above-mentioned composition ratio among the active ingredients, the abrasion resistance which is the object of the present invention,
It forms a processing agent with excellent conjugation properties.

The treatment agent of the present invention can be easily adjusted according to the usual method for preparing treatment agents. However, when dispersing the water-dispersible silica sol (A), it is important to ensure uniform and sufficient dispersion. Stirring is important, and dispersion using a high-speed stirring mixer, disperser, or ultrasonic waves is preferred. The method of use, that is, the method of application to the fibers, may be air lubrication, in which aerosol is applied by spraying, showering, etc., or straight lubrication, in which it is directly applied in high concentration by contact with a nozzle or roll surface, etc. The active ingredient may be attached to the fiber in an amount of 0.2 to 3.0% by weight.

The aromatic polyamide fiber referred to in the present invention has the following units, -
N11-^r+ Nil (II), CO-^r2
co-[■], and -CO-8r388 (■)
It refers to a fiber made of aromatic polyamide that is substantially composed of groups, specifically, ^rl+^"2 and ^" in the above formula.
For example, metaphenylene, paraphenylene, 4.4-
Biphenylene, 1,4-naphthylene, -CI+, -, -
S-), polymetaphenylene isophthalamide w! fibers, polyvara phenylene terephthalamide fibers, copolyvara phenylene/3.4' (oxydiphenylene) terephthalamide fibers, and the like. Among these aromatic polyamide fibers, the above unit formula [■
]～[■]In the case of ^r+, ^r2, and ^r, the chains are coaxially or linearly connected in opposite directions of the divalent aromatic groups, and the individually oriented aromatic polyamide fiber has high strength. is an extremely useful fiber that provides a high modulus of elasticity, and because of its high orientation, the fiber surface tends to be fibrillated and generates a lot of fluff. It exhibits particularly favorable effects on aromatic polyamide fibers.

〔Example〕

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples.

・　゛　ゞ's day Each characteristic value was measured as follows.

◎Reed abrasion test A stainless steel reed blade was set horizontally against the yarn, and the reed abrasion was photographed using a microscope after being rubbed for 24 hours at a rotation speed of 2000 rpm+, a yarn speed of 30 cm/win, and a running tension of 28 g. I evaluated it. The results were displayed in 5 stages from 1 to 5 (the higher the value, the greater the wear).

).

◎The number of frictions was 1000 times, the tension was 0°3 g/d, and the stroke was 30 I using a conjugated textile type yarn friction conjugation force tester (manufactured by Toyo Seiki).
After testing at a test speed of 200 strokes/win and an intersection angle of 45°, the friction points were photographed using a microscope.
Fluffiness and single yarn breakage were evaluated on a scale of 1 to 5 (
(The larger the number, the better the conjugation).

Prior to explaining the tr embodiment of Metalwork □, an example of the manufacturing process of aromatic polyamide fiber to which the embodiment of the present invention is applied will be explained.

Polybara phenylene terephthalamide was obtained by a low temperature solution polymerization method as follows, and subjected to wet spinning.

In the polymerization apparatus shown in Japanese Patent Publication No. 53-43988, 70 parts of anhydrous calcium chloride was dissolved in 1000 parts of N-methylpyrrolidone, and then 48.
After cooling to 8° C. without dissolving 6 parts, 91.4 parts of terephthalic acid dichloride were added at once in powder form. After a few minutes, the polymerization reaction product solidified into a cheese-like shape, so the
The polymerization reaction product was discharged from the polymerization apparatus according to the method described in Japanese Patent Application No. 3988, and immediately transferred to a two-screw closed Niegoo, and the polymerization reaction product was finely pulverized in the Niigoo. Next, the finely pulverized material was transferred to a Henschel mixer, and an equal amount of water was added thereto for further pulverization, followed by r-filtration, washing several times in warm water, and 110%
Dry in hot air at ℃.

The polyvalent phenylene terephthalamide thus obtained was dissolved in 99.8% sulfuric acid at 70° C. for 2 hours so that the polymer concentration was 19% by weight. The dissolution was carried out under vacuum, and after the dissolution, the mixture was allowed to stand for 2 hours to defoam, and then spun. This dope was anisotropic. This dope,
It was extruded from a spinneret with 1000 pores of 0.06 ma+φ, and after traveling through a 10 mm space, it was coagulated in 25% dilute sulfuric acid at 5° C. and drawn out at a speed of 300 m/min. The threads are then washed using the device shown in FIG. 1, which is an example of a known aromatic polyamide fiber manufacturing device, and then the oil composition of the present invention is applied to the yarn using the oil supply device shown in 12(a) or 12(b) in the figure. was added to produce a 1500 denier fiber.

Note that the oil supply device 12(a) in FIG.
It is a shower tray with many mmφ holes,
An oil agent is applied to the yarn as an aqueous dispersion.

Further, 12(b) is a so-called roll oiling device, which applies an oil by forming a treatment liquid film on the surface of a rotating roll and drawing the yarn while it is in contact with the roll.

In Figure 1, 1 is a spinneret, 2 is a spinning bath device, 3 is a spinning solution, and 4
5 is a coagulated yarn, 5 is a direction change roll, 7 is a take-up roll, 8
9 is a shake-off roll, 9 is a reversing net device H110 is a conveyor net device, 11 is a shower tray for washing with water, 13 is a drying device, 14 is a yarn pressing force net device, 1
5 indicates a winding machine.

Mineral oil (viscosity 500 seconds, 30°C), dioctyl sebacate, glycerin oleate, and water-dispersible silica sol with an average diameter of 7 mμ (manufactured by Nippon Aerosilnee, ^EROS IL300) ) and polyoxyethylene polypropylene glycol (manufactured by Kao Netami Co., Ltd.) having a weight average molecular weight of 20,000, a processing agent (an emulsion with an active ingredient concentration of 30%) whose active ingredient composition is shown in Table 1 was prepared.

These processing agents are indicated by 12 (b) in FIG.
It was put into a roll oiling device, and spinning and winding were performed. At this time, Table 1 also shows the results of evaluating the fuzz count of the spun and collected yarn, and the reed abrasion and conjugation properties of the wound GI fibers using each treatment agent.

From Table 1, it was confirmed that the treatment agent of the present invention was extremely excellent in 1llrt abrasion resistance and conjugation properties.

The following is a blank page.The active ingredients of the processing agent were as follows, and the treatment was carried out using the same equipment as in Example 1, except that the weight average molecular weight of polyoxyethylene polyoxypropylene was changed as shown in Table 2. A polyparaphenylene terephthalamide fiber was obtained. The abrasion properties and conjugation properties of the obtained fibers are as shown in Table 2.
The processing agent of the present invention was excellent in both properties.

Treatment agent composition Water-dispersible silica sol 2 parts Mineral oil (viscosity 500 seconds, 30°C) 28 parts Dioctyl sebacate 10 parts Glycerin oleate
10 parts [Effects of the Invention] As shown in the above examples, the aromatic polyamide fiber processing agent of the present invention has extremely excellent abrasion resistance and conjugation properties, and as a result, it is difficult to interact with equipment and equipment during spinning. It is possible to suppress the occurrence of fuzz on the fibers due to friction, and it is possible to efficiently produce high-grade aromatic polyamide fibers. Furthermore, when the fibers are processed into yarn, yarn, or knitted yarn, due to their high abrasion and conjugation properties, high-quality products can be obtained without generating fuzz, and processing speeds can also be increased. This is intended to improve efficiency.

[Brief explanation of the drawing]

FIG. 1 is a front view showing an example of a fiber manufacturing apparatus suitable for applying the oil composition according to the present invention. 1... Spinneret, 2... Spinning bath device, 4...
Coagulated thread, 12(a), 12(b)-processing agent application device, 13.
...Drying equipment.

Claims (1)

[Claims] 1. In the substantial active ingredients excluding the solvent or dispersion medium, (A)
0.1 to 10% by weight of water-dispersible silkasol whose primary particles have an average diameter of 50 mμ or less; (B) a weight average molecular weight represented by the following formula [I] of 10;
000 or more alkyl EO/PO copolymer 30% by weight or more ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] In the formula, R is the same or different alkyl group or alkenyl group having 4 to 22 carbon atoms, l, m , n represents an integer of 1 or more. A processing agent for aromatic polyamide fibers, comprising: 2. The processing agent for aromatic polyamide fibers according to claim 1, wherein the alkyl EO/PO copolymer represented by formula [I] is a block copolymer.