JP2891858B2 - Abrasion resistance improving agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a treatment agent mainly used for improving abrasion resistance of textile products, for example, ropes, cords, woven fabrics and the like. More specifically, a fiber structure braided or woven into a single yarn and a belt-like structure, a cord-like structure, a woven fabric structure, a net-like structure, a rope-like structure, or a felt-like (non-woven fabric) The present invention relates to a treatment agent used for improving abrasion resistance and bending fatigue resistance of a fiber structure.

[0002]

2. Description of the Related Art Conventionally, as a means for improving the abrasion resistance of textile products, surface coating or impregnation with a treating agent is often used.
Polyurethanes and fluororesins have been widely used as treating agents. As a technique using polyurethane as a treatment agent for improving abrasion resistance, a fiber rope treated with a mixture containing polyurethane, polyethylene oxide and an ethylene urea compound as main components is disclosed (Japanese Patent Publication No. Sho 62-60511).
Alternatively, a "method of improving abrasion resistance by applying a resin containing a urethane prepolymer block product as a main component to a fiber belt and subjecting the belt to a heat treatment" (Japanese Patent Laid-Open No. 60-1731)
No. 74) and further "a method of treating with a first treating agent containing a silane-based coupling agent as a main component, followed by treatment with a polyurethane, polyethylene oxide and an ethylene urea compound" (Japanese Patent Publication No. 1-29099). "A treating agent containing polyurethane, polyethylene oxide, fluororesin, and ethylene urea compound as main components" (JP-A-3-249280) and the like (hereinafter referred to as prior art). Indeed, it has been recognized that fibers and structures surface-coated or impregnated with the treatment agents described in the above prior art have improved wear resistance and flex fatigue resistance. However, when actually processing a large amount of yarn using the processing agent disclosed in the above prior art, a large amount of foam is generated in the processing agent and does not disappear for a long time, and the processing solution becomes jelly-like. The problem of not being able to control the viscosity and adhesion amount of the agent at the time of processing, and the problem that the smoothness of the treatment agent film, especially the smoothness under moisture intervening, is insufficient, and the fluff easily occurs at the time of processing and use. Have.

[0003] Further, with the recent expansion and diversification of applications in the market, the required performance of products tends to be more sophisticated and diversified. It is becoming impossible to respond. For example, para-aramid fiber has a high strength of 21 g / denier or more, and various fiber structures using this fiber have recently been developed and are being used in application fields such as belts, cords, and ropes. Since it is easy to fibrillate due to friction between fibers / fibers, fiber / object, etc., the fibrillation is the main cause during processing with a treating agent or during actual use in the above applications, and fluff is generated.
It has been pointed out that the strength is deteriorated, and the excellent high-strength characteristic inherent to the fiber cannot be sufficiently exhibited.

In order to remedy this drawback, nylon-based fibers having relatively good abrasion resistance are used for the surface layers of belts, cords, ropes and the like, and a composite structure is formed by using aramid fibers for the core. Has been put into practical use. However, even products with these composite structures are still insufficient, and in particular, have not yet completely prevented fibrillation of aramid fibers. Also, since the elongation of the composite fiber is different, the stress received during use is received only by the core body. For example, in ropes and cords, the degree of expression of product strength with respect to the outer diameter (thickness) is reduced. In addition to the drawbacks, the friction between the core fibers in the process of repeated bending of the product causes the fibers to be partially fibrillated, resulting in the inability to maintain sufficient product strength for a long period of time. ing.
More recently, various studies and developments have been carried out in order to exploit the high strength of this para-aramid fiber in the field of marine materials, but the fibrillation described above is particularly difficult when used under high tension. The strength is significantly deteriorated due to the intervention of water, and the excellent high-strength characteristics inherent to the fiber cannot be sufficiently exhibited. Further, as described above, due to the foaming of the treatment agent in the treatment step, not only the amount of adhesion to the yarn cannot be controlled, but also fluff is likely to occur during processing due to insufficient smoothness. In addition, the coating formed by the treating agent absorbs water and swells due to the interposition of water, and the coating performance cannot be sufficiently exhibited due to the deterioration of the strength of the coating. Therefore, the originally intended wear resistance and bending fatigue resistance are reduced. It cannot be sufficiently improved, and the required performance in the field of fishery materials cannot be satisfied.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent foaming of a treating agent, to reduce the frictional force of a treating agent film, and to provide a treated fiber structure with a high degree of smoothness, abrasion resistance, and bending fatigue resistance. An object of the present invention is to provide a treating agent capable of imparting properties and the like.

[0006]

More specifically, the present invention relates to a method of measuring the following method using "(Claim 1) polyurethane (A), polyethylene oxide (B), ethylene urea compound (C) and organopolysiloxane (D) as main components. 140% foaming rate
Less than 0.1 % . <Method of Evaluating Foaming Ratio by Stirring Compounding Treatment Liquid > The mixing treatment liquid was weighed and taken in an amount of 100 ml.
After placing in a 0 cm 250 ml graduated cylinder,
Measures the height from the bottom of the measuring cylinder to the liquid level of the processing agent
(H1). Next, two sheets with a maximum length of about 2.0 cm
Approximately 5 minutes at 2000 rpm with a stirrer having blades
Meanwhile, after stirring the treating agent, it is allowed to stand for about 30 minutes.
Measure the liquid level including the foaming part of the treatment agent (H2)
The foaming ratio was calculated by the following formula. Foaming rate (%) = (H2) / (H1) × 100 (Claim 2) The polyurethane (A) comprises a polyester polyol and an aliphatic polyisocyanate, and the polyethylene oxide (B) has a molecular weight of 1,000 to 7000; The urea compound (C) comprises a compound satisfying the following general formula;

[0007]

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The antiwear agent according to claim 1, wherein the organopolysiloxane (D) is at least one selected from the group consisting of dimethylpolysiloxane and modified polysiloxane represented by the following general formula.

[0009]

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(Claim 3) The weight ratio of each component of the treating agent is (A) / [(A) + (B)] = 0.5 to 0.9,
(C) / [(A) + (B)] = 0.05-0.3,
(D) / [(A) + (B) + (C)] = 0.0003-
The agent for improving abrasion resistance according to claim 1 or 2, which is 0.1. "
It is.

The polyurethane is a high molecular polymer obtained by reacting a polyester polyol with a polyisocyanate. Examples of the polyester polyol include a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1-4 butanediol, glycerin and sebacic acid. And polyester polyols obtained by the condensation reaction of polyaliphatic carboxylic acids such as adipic acid, oxalic acid, succinic acid and phthalic acid with aromatic carboxylic acids. Examples of the polyisocyanate include an aliphatic polyisocyanate or an aromatic polyisocyanate such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane diisocyanate, and naphthylene diisocyanate. Aliphatic polyisocyanates are preferred from the viewpoint of properties. The oxidized polyethylene is obtained by oxidizing polyethylene to have a low molecular weight, and preferably has a hydroxyl group and / or a carboxyl terminal group,
More preferably, it is an oxide of high-density polyethylene having a molecular weight of 1,000 to 7000.

The ethylene urea compound is represented by the following general formula.

[0013]

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Typical compounds include aliphatic or aromatic polyisocyanates such as octadecyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane diisocyanate and naphthylene diisocyanate, and ethyleneimine. And usually used in the form of an aqueous dispersion.

Further, as the organopolysiloxane,
In addition to dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, and the like, which are generally called silicone oils having a viscosity of 5 to 200,000 centipoise at 25 ° C., various modified polysiloxanes represented by the following general formulas are exemplified.

[0016]

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Among these organopolysiloxanes, those which are imparted with water dispersibility by modification can be used as they are when the other compounding agent is an aqueous composition. It is desirable to incorporate a mixture emulsified with an emulsifier or the like.

The fiber product is a product made of polyester fiber, nylon fiber, vinylon fiber, aramid fiber and the like, and includes, for example, rope, cord, woven fabric, felt and the like.

As the treatment method using the treatment agent of the present invention, any conventionally known method such as a spray method and a coating method may be used. Examples of the method include polyurethane (A), polyethylene oxide (B), ethylene urea compound (C) and organo urea. It is easiest to impregnate the fiber product with a mixture of the respective aqueous dispersions of the polyoxane (D) and then dry. Of course, the treatment agent may be applied in the form of a thread-like fiber by the above-described method.

The weight ratio of each component in the treating agent is as follows: weight ratio a (A) / [(A) + (B)] = 0.5 to 0.5.
9 Weight ratio b (C) / [(A) + (B)] = 0.05-
0.3 weight ratio c (D) / [(A) + (B) + (C)] = 0.
It is preferably from 0003 to 0.1. When the weight ratio a is less than 0.5, the strength of the treatment agent coating is not sufficient, and the interfacial adhesion between the coating and the fiber product is also insufficient. On the other hand, if it exceeds 0.9, the surface frictional resistance of the coating film becomes too large and the smoothness becomes insufficient. On the other hand, if the weight ratio b is less than 0.05, the coating strength becomes insufficient, and if it exceeds 0.3, the flexibility of the coating becomes insufficient and the bending properties of the treated fiber product deteriorate. Further, when the weight ratio c is less than 0.003, foaming of the treating agent during the treatment cannot be sufficiently prevented, and not only an effective defoaming effect cannot be exhibited, but also the smoothness of the treating agent film becomes insufficient. Thus, the effect of controlling the amount of the agent attached to the yarn, the effect of reducing the generation of fluff in the yarn guide portion and the like at the time of processing, the effect of water repelling the fibrous structure after the processing, and the like cannot be expected. On the other hand, if it exceeds 0.1, the coating strength on the surface of the fibrous structure formed by the treatment agent becomes insufficient, and the interfacial adhesive strength between the coating and the fiber is undesirably reduced. In our review, 0.001-0.0
When the compounding ratio is within the range of 9, the best improvement effect is exhibited with respect to various properties such as defoaming of the treating agent solution, generation of fluff during the treatment, surface friction resistance, abrasion resistance and bending fatigue resistance of the treated product.

Therefore, it is preferable that the treating agent liquid is blended so as to be in the range of the above-mentioned weight ratio a, weight ratio b and weight ratio c, and the weight ratio of each active ingredient is controlled. The treating agent liquid blended within such a weight ratio range not only reduces foaming and fluffing in the treating agent solution during treatment, but also increases the abrasion resistance of the treated fiber or fiber structure. In addition, the bending fatigue resistance is greatly improved, and in particular, there is little decrease in wear resistance and bending fatigue resistance when water is interposed, and it is very good.

The concentration of the solid content of the treating agent liquid is suitably from 1 to 25% by weight, preferably from 5 to 20% by weight.
The drying temperature is 100 to 150 ° C., and the drying time is 0.5.
-20 minutes is preferred. If the drying temperature is lower than 100 ° C., the coating strength of the treating agent is not sufficient, and if it exceeds 150 ° C., the coating strength is deteriorated. Heat treatment temperature is 160 ~ 240 ℃,
The heat treatment time is preferably from 0.2 to 10 minutes, and if the heat treatment temperature is lower than 160 ° C., the formed coating film is insufficiently cross-linked and cannot exhibit good coating strength. On the other hand, when the temperature exceeds 240 ° C., the coating is thermally deteriorated and the strength is reduced. The amount of the treatment agent attached to the textile product after the treatment is 1 to 10% by weight in solid content.
Is preferred. If the amount is less than 1% by weight, the abrasion resistance of the fiber product is insufficiently improved, and no practical effect is exhibited. If the amount exceeds 10% by weight, the fiber after treatment becomes extremely coarse and the bending fatigue property is reduced.

[0023]

The treatment agent of the present invention not only reduces the amount of foam in the treatment agent solution during treatment, and also reduces the generation of fluff in the treatment step, but also the fibers treated with the treatment agent.
Alternatively, the fiber structure also has excellent wear resistance and bending fatigue resistance. The reason why the fibers and fiber structures treated with the treating agent are excellent in abrasion resistance is that, by using polyethylene oxide and organopolysiloxane in combination with polyurethane having weather resistance, it has flexibility and high smoothness, Another object of the present invention is to form a coating film having low water absorption and excellent water resistance on the fiber surface, and further to cause a crosslinking reaction by using an ethylene urea compound in combination to improve the cohesive force of the coating film. Therefore, the fiber or the fiber structure treated with the treating agent has a small coefficient of friction, and reduces the friction between the single fibers and the friction between the fibers / objects. In addition, it has the effect of improving the resistance to bending fatigue and the characteristics under the presence of moisture.

That is, the present invention has the following effects. (1) In the case of treating with the treating agent liquid of the present invention, the foaming of the treating agent liquid is small, so that it is easy to control the viscosity and the amount of the treating agent attached to the fiber. (2) The treatment agent of the present invention not only does not easily generate fluff in the treatment step because the coating film is rich in smoothness, but also prevents fibrillation of fibers during use and improves durability. (3) The fibers or fibrous structures treated with the treating agent solution of the present invention have extremely excellent abrasion resistance in the air and under the presence of moisture. (4) The fiber or fiber structure treated with the treating agent solution of the present invention has extremely excellent bending fatigue resistance in air and under the presence of moisture.

A rope-like fiber structure made of para-aramid fiber which is liable to fibrillate by friction will now be described in detail with reference to examples. The abrasion resistance, flex fatigue resistance, foaming property of the treating agent solution, and evaluation of fluff generation in the treatment step were performed according to the following methods.

<Method of Evaluating Wear Resistance> FIG. 1 shows an evaluation apparatus. In FIG. 1, impregnated rope (evaluation sample) 1
On the other hand, an abrasion test was performed for 10 minutes while applying a load 3 of 0.2% of the tensile breaking strength of the rope while rotating a sand grinder 2 having a surface roughness of No. 120 at about 3450 rpm. Reference numeral 5 denotes a guide roll (a roll that freely rotates) of the impregnated rope. Also funnel 6
Is a water application device for dropping water as needed, and 7 is a cock that opens when water 8 is dropped. The method of evaluating without dropping water is classified as method A, and the method of evaluating with dropping water is classified as method B.

<Evaluation Method for Bending Fatigue Resistance> The bending fatigue resistance is evaluated by an S-bending method using two pairs of freely rotating rolls. The evaluation rope is applied to two freely rotating rolls in an S-shape, and a tensile force of 1/10 of the tensile breaking strength of the rope is applied to the rope. Was determined by comparison. However, at this time, the ratio of the roll diameter (D) to the freely rotating roll diameter (D) is 20.
The diameter of the roll is selected so that (D / d = 20).

<Evaluation method for foaming property of compounding treatment agent solution by stirring> The compounding treatment agent solution was weighed and taken in 100 ml, placed in a 250 ml measuring cylinder having an outer diameter of 4.0 cm, and then placed in the measuring cylinder. The height from the bottom surface to the liquid level of the processing agent is measured, and is defined as (H1). Next, the maximum length is about 2.0
2000 rpm with a stirrer having two blades
Then, after stirring the treatment agent for about 5 minutes, the mixture is allowed to stand for about 30 minutes, and then the liquid level including the foamed portion of the treatment agent is measured to obtain (H2). The foaming property was calculated by calculating the foaming rate (defoaming property) according to the following formula, and used as a scale for judging the foaming property. Foaming rate (%) = [Height of liquid surface including foamed portion after stirring (H2) / Height of liquid surface before stirring (H1)] × 100 Defoaming including difficulty of foaming Regarding the properties, referring to the above calculation results, 100 to less than 120%: 、,
120 to less than 140%: ○, 140 to less than 140%:
Δ, 160% or more: Classified as X and judged.

<Evaluation Method of Fuzz Generation in Processing Step> Para-type aramid long fiber yarn 1 substantially free of oil agent
500 denier / 1000 filament [Technola:
Using a test impregnating machine, 1kg winding x 30 strands = 30kg was processed using a test impregnating machine, and the fluff generated on the end face portion and surface portion of the processed yarn wound on a paper tube was measured. Observation was carried out and classified. No fuzz was generated = ◎, fuzz generation amount = 微量, fuzz generation amount = 少量, fuzz generation amount = ×.

[0030]

Example 1 Aqueous dispersion of polyurethane (A) obtained by reacting adipic acid, polyester diol composed of 1,4-butanediol and hexamethylene diisocyanate (active ingredient 25% by weight) and oxidation of molecular weight 4500 Aqueous dispersion of polyethylene (B) (active ingredient 25% by weight), ethylene urea compound (C) comprising reaction product of diphenylmethane diisocyanate and ethylene imine
The aqueous dispersion (active ingredient 25% by weight) and the aqueous dispersion containing dimethyl silicone (D) as the main component (active ingredient 40% by weight) were added to the active ingredient ratio (solid component ratio; weight%) shown in Table 1. Each of the aqueous dispersions was blended so as to obtain a treating agent liquid. The solid content concentration of this treating solution was 13% by weight. An outer diameter of 14 mm made of a para-aramid long fiber yarn of 1500 denier / 1000 filament [Technola: manufactured by Teijin Limited] having an oil content of 0.5% by weight or less.
Is immersed in the above-mentioned compounding treatment solution to impregnate it, and the amount of the treatment solution attached is controlled by passing through a compressed air nozzle, followed by drying at a temperature of 130 ° C. for 15 minutes. At 3 ° C. for 3 minutes to effect a cross-linking reaction of the treating agent coating formed on the surface of the fiber constituting the rope. At this time, the solid content of the treatment agent attached to the entire rope was 3.5% by weight. The obtained ropes were evaluated by the abrasion resistance evaluation methods A and B and the bending fatigue resistance test, and the results were as shown in the corresponding portions of Table 1. In addition, the classification of the foaming rate (defoaming property) measured for this compounding treatment agent liquid was a circle mark as shown in the corresponding portion of Table 1. Table 1 shows the results of the evaluation and determination of the state of the fluff occurring in the processing step, by observing the processed yarn wound on the paper tube after the processing.

[0031]

Examples 2 to 5 In Examples 2 to 5, the respective aqueous dispersions (A), (B), (C) and (D) used in Example 1 were subjected to the respective operations shown in Table 1. The procedure was performed in the same manner as in Example 1, except that the treating agent liquid was prepared and used so as to have a solid content ratio (% by weight) corresponding to the example. These were compared and evaluated by the wear resistance evaluation methods A and B and the bending fatigue resistance test. The results are shown in Table 1. In addition, Table 1 shows the measurement results of the foaming ratio (defoaming property) of the compounding treatment solution used in each example, and the results of observation and evaluation of the occurrence of fuzz on the treated yarn wound around the paper tube after the treatment. .

[0032]

Examples 6 and 7 Examples 6 and 7 are shown in Table 1 using an aqueous dispersion containing a self-emulsifying type silicone (D) as a main component instead of the dimethyl silicone used in Example 1. The procedure was performed in the same manner as in Example 1 except that the solid content ratio (% by weight) was added. The results of comparative evaluation of the wear resistance evaluation methods A and B and the flex fatigue resistance test were as shown in Table 1 at the corresponding locations. Example 1
Table 1 shows the foaming rate (defoaming property) of the treating agent liquid evaluated in the same manner as described above, and the results of the observation and determination of the fluff generation state regarding the yarns wound on the paper tube after the treatment.

[0033]

[Table 1]

[0034]

[Comparative Example 1] For comparison, the results of comparative evaluation and judgment of the rope used in Example 1 before the impregnation treatment with the treating agent liquid in the same manner as in Example 1 are shown in Table 2 as Comparative Example 1. Was.

[0035]

Comparative Examples 2 to 8, Comparative Example 10, and Comparative Example 11 Comparative Examples 2 to
8, Comparative Example 10 and Comparative Example 11 examined the optimal range of the solid content ratio (% by weight) of the compounding treatment solution and the defoaming effect of the compounding treatment solution in comparison with the examples. Except that the aqueous dispersions (A), (B), (C) and (D) used in Example 1 were blended so as to have a solid content ratio (% by weight) shown in Table 2, It carried out like Example 1. The results are shown in Table 2 as a comparative example. In addition, the defoaming property of the treating agent liquid and the state of generation of fluff on the treated yarn were determined in the same manner as in Example 1, and the results were compared and determined. The results are shown in Table 2.

[0036]

Comparative Example 9 For comparison, (A) used in Example 1 was used,
Using each of the aqueous dispersions (B) and (C) and the self-emulsifying silicone (D) used in Example 6, the solid content shown in Comparative Example 9 in Table 2 was used. The procedure was performed in the same manner as in Example 1 except that the blending was performed in the ratio (% by weight). Table 2 shows the results
It was shown to. Also, regarding the foaming rate (defoaming property) of the treating agent liquid and the generation of fluff of the treated yarn wound on the paper tube after the treatment,
Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.

[0037]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a side sectional view of a wear resistance evaluation device.

[Explanation of symbols]

 DESCRIPTION OF REFERENCE NUMERALS 1 Impregnated rope for evaluation (evaluation sample) 2 Sand grinder with surface roughness No. 120 3 Load 4 Fixing device for fixing evaluation sample 1 5 Guide roll that rotates freely 6 Roto 7 Opening and closing cock 8 Water

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI D06M 15/643 D06M 15/643 (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 15/00-15/72

Claims (3)

(57) [Claims] 1. Polyurethane (A), polyethylene oxide (B), ethylene urea compound (C) and organopolysiloxane (D) as main components, measured by the following method.
An abrasion resistance improving agent characterized by having a foaming rate of less than 140% . <Method of Evaluating Foaming Ratio by Stirring Compounding Treatment Liquid > The mixing treatment liquid was weighed and taken in an amount of 100 ml.
After placing in a 0 cm 250 ml graduated cylinder,
Measures the height from the bottom of the measuring cylinder to the liquid level of the processing agent
(H1). Next, two sheets with a maximum length of about 2.0 cm
Approximately 5 minutes at 2000 rpm with a stirrer having blades
Meanwhile, after stirring the treating agent, it is allowed to stand for about 30 minutes.
Measure the liquid level including the foaming part of the treatment agent (H2)
The foaming ratio was calculated by the following formula. Foaming rate (%) = (H2) / (H1) × 100 2. A polyurethane (A) comprising a polyester polyol and an aliphatic polyisocyanate, a polyethylene oxide (B) having a molecular weight of 1,000 to 7000, and an ethylene urea compound (C) comprising a compound satisfying the following general formula: , Embedded image 2. The agent according to claim 1, wherein the organopolysiloxane (D) comprises dimethylpolysiloxane or a modified polysiloxane represented by the following general formula. Embedded image 3. The weight ratio of each component of the treatment agent is (A) /
[(A) + (B)] = 0.5-0.9, (C) /
[(A) + (B)] = 0.05-0.3, (D) /
3. The treatment agent for improving abrasion resistance according to claim 1, wherein [(A) + (B) + (C)] = 0.003 to 0.1.