JP2557995B2 - Abrasion resistance improvement treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention mainly relates to a treating agent used for improving abrasion resistance and flex fatigue resistance of textiles such as ropes, cords and fabrics. More specifically, the wear resistance and flex fatigue resistance of a fiber structure braided or woven into a belt-like structure, a cord-like structure, a woven structure and a rope-like structure, or a felt-like (non-woven) fiber structure are evaluated. The present invention relates to a treating agent used for improving.

<Prior Art> Usually, as materials used for fiber structures such as belts, cords, ropes, woven fabrics and felts, polyester,
Nylon, vinylon, wholly aromatic polyamide (aramid), wholly aromatic polyester, etc. are used, and glass fibers and carbon fibers are also used for special purposes. These fibers are usually used alone or without any treatment, but depending on the application, abrasion resistance and bending fatigue resistance are insufficient, so that the excellent properties originally possessed by the fiber material cannot be sufficiently expressed. There is a situation. Such problems are likely to occur especially in applications involving water.

Conventionally, fiber surface coating and impregnation with various treatment agents have been widely used as the abrasion resistance improving means. Polyurethane-based and silicon-based resins are widely used as such treatment agents, and processing with these agents is widely used. Fiber structures used in the market. For example, as a technique using a polyurethane resin as an abrasion resistance improver, "fiber rope treated with a mixture containing polyurethane, polyethylene oxide and an ethylene urea compound as a main component" (Japanese Patent Publication No. 62-60511) or "Method of improving abrasion resistance by applying a resin whose main component is a urethane prepolymer block product to fiber belts and subjecting it to heat treatment"
(Japanese Patent Laid-Open No. 60-173174), "Second treatment agent containing polyurethane, polyethylene oxide, and ethylene urea compound as main components after treatment with a first treatment agent containing a silane coupling agent as a main component. Method (Japanese Patent Publication No. 29909/1989) or “a fiber structure obtained by treating a fluorine-based resin under specific conditions” (Japanese Patent Application No. 01-30005).
No.) etc. (hereinafter referred to as prior art). Certainly, it is recognized that the fiber structure surface-coated or impregnated with the treatment agent shown in the above-mentioned prior art has improved wear resistance and flex fatigue resistance. However, with the recent expansion and diversification of applications in the market, the required performances for products tend to be further improved and expanded, and the above-mentioned conventional techniques are insufficient, and it is not possible to sufficiently cope with them depending on the applications. For example, since para-aramid fiber has a high strength of 20 g / denier or more, various fiber structures using this fiber have recently been developed and are being utilized in fields of application such as belts, cords and ropes. Due to friction between fibers / fibers / fibers / objects, fibrils are easily formed, which causes strength deterioration mainly, and has the drawback that the excellent high-strength characteristics of the fiber body cannot be fully expressed. .

In order to remedy this drawback, measures such as using nylon-based fibers, which have relatively good wear resistance, for the surface layer of belts, cords, ropes, etc., and using aramid fibers for the core to form a composite structure, have been made. It has been put to practical use. However, even products of these composite structures are still insufficient,
In particular, it has not been possible to completely prevent fibrillation of aramid fibers. In addition, since the elongation of the composite fibers is different, the stress that is applied during use will be received only by the core body. For example, with ropes and cords, the degree of product strength development with respect to the outer diameter size (thickness) will decrease. Not only does it have drawbacks, but during repeated bending and use of the product, the fibers partially fibrillize due to friction between core fibers, resulting in the inability to maintain sufficient product strength for a long time. . Furthermore, recently, various studies and developments have been carried out in order to utilize the high strength of this para-type amide fiber to develop into the field of marine products, especially when it is used under high tension. The strength is remarkably deteriorated by being promoted by the interposition of water, and the excellent high strength characteristics originally possessed by the fiber cannot be sufficiently expressed. Further, even when the para-aramid fiber treated by the above-mentioned prior art is used, the coating formed by the treatment agent absorbs water and swells due to the presence of water to deteriorate the strength of the coating, resulting in sufficient coating performance. Therefore, the originally intended wear resistance and flex fatigue resistance cannot be sufficiently improved, and the performance required in the field of marine products cannot be fully satisfied.

<Object of the Invention> The present invention has been devised as a result of intensive research to solve such problems in the prior art, and its object is to provide a fiber structure composed of an organic fiber or an inorganic fiber with a high degree of degree. It aims to develop wear-resistant and flex fatigue resistance, especially in the field of marine products.

As a result of various studies to achieve such an object, the inventors of the present invention used a specific polyurethane, and added polyethylene oxide, a fluororesin, and an ethyleneurea compound in an appropriate ratio, thereby The inventors of the present invention have found that it is possible to obtain an excellent treatment agent for improving wear resistance which solves the problems.

<Structure of the Invention> That is, the present invention has a polyurethane (A) composed of a polycarbonate polyol and a polyisocyanate, a polyethylene oxide (B), a fluororesin (C) and an ethylene urea compound (D) as main components, and each component The weight ratio is a) ~
It is a wear resistance improving treatment agent which simultaneously satisfies the expression d).

a) (A) / [(A) + (B) + (C) + (D)] = 0.34 to 0.70 b) (B) / [(A) + (B) + (C) + (D)] = 0.24 to 0.60 c) (C) / [(A) + (B) + (C) + (D)] = 0.03 to 0.20 d) (D) / [(A) + (B) + (C) + (D)] = 0.03 to 0.15 Polyurethane here is a high molecular polymer obtained by the reaction of a polyol and a polyisocyanate,
In the polyurethane (A) of the present invention, the polyol is preferably a polycarbonate polyol from the viewpoint of water resistance, heat resistance and the like. On the other hand, examples of the polyisocyanate include hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthylene diisocyanate, and other aliphatic or aromatic polyisocyanates. Aliphatic polyisocyanates are preferred from the viewpoint of properties.

Oxidized polyethylene is a low molecular weight product obtained by oxidizing polyethylene, preferably having a hydroxyl group and / or a carboxyl end group, and more preferably a high density polyethylene oxide having a molecular weight of 1,000 to 7,000. .

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

[Wherein R is an aromatic or aliphatic hydrocarbon residue, n is 0.
1 or 2. When n = 0, the terminal of R is a hydrogen group. ] A typical compound is octadecyl isocyanate,
Reaction products of aromatic or aliphatic isocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, triphenylmethane triisocyanate, and ethyleneimine are usually dispersed in water. Used in liquid form.

Fluorine-based resin means tetrafluoroethylene polymer, trifluorochloroethylene polymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, 4 fluorine Examples thereof include ethylene oxide / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride polymer, vinylidene fluoride polymer, ethylene / tetrafluoroethylene copolymer.

The fluororesin is usually used in the form of a dispersion prepared by dispersing a fine particle fluororesin in a dispersion medium using a dispersant, or a water emulsion obtained by emulsifying the fine particle fluororesin in an aqueous medium using an emulsifier. To be done.

As a treatment method using the treatment agent of the present invention, a spray method,
Although any conventionally known method such as a coating method may be used, a liquid obtained by mixing an aqueous dispersion of polyurethane (A), polyethylene oxide (B), fluororesin (C) and ethylene urea compound (D). Yarn fiber,
Alternatively, the simplest is a treatment method in which a fibrous structure having a cord shape, a rope shape, a belt shape, a woven cloth shape, and a felt shape structure is dipped and impregnated, and then dried and heat treated. Of course, it may be formed into a fiber structure suitable for market use after applying the treating agent in the form of a filamentous fiber by the above method,
The treatment agent may be applied by the above-mentioned method after forming the fiber structure suitable for the market use.

The weight ratio of each active ingredient in the treatment agent is a) (A) / [(A) + (B) + (C) + (D)] = 0.34 to 0.70 b) (B) / [(A) + (B) + (C) + (D)] = 0.24 to 0.60 c) (C) / [(A) + (B) + (C) + (D)] = 0.03 to 0.20 d) (D) / [ (A) + (B) + (C) + (D)] = 0.03 to 0.15. When the weight ratio of a) is less than 0.34, the strength of the treatment agent coating formed on the surface of the treated fiber or fiber structure is not sufficient, and the interfacial adhesion between the coating formed by the treatment agent and the fiber is insufficient. Is also insufficient, which is not preferable. On the other hand, if it exceeds 0.70, the surface friction resistance of the coating becomes large and the smoothness becomes insufficient.

When the weight ratio of b) is less than 0.24, the surface friction resistance of the treatment agent coating formed on the surface of the treated fiber or fiber structure is not sufficiently reduced, and the desired smoothness cannot be obtained. Further, if it exceeds 0.60, not only the strength of the coating film formed by the treatment agent becomes insufficient, but also the interfacial adhesion between the coating film formed by the treatment agent and the fiber is deteriorated, which is not preferable.

When the weight ratio of c) is less than 0.03, not only is the reduction of the surface friction resistance of the treatment agent coating formed on the surface of the treated fiber or fiber structure insufficient, but also water absorption of the coating by water, Swelling cannot be prevented, and wear resistance and bending fatigue resistance in the presence of water cannot be sufficiently expressed. Also,
When it exceeds 0.20, the strength of the coating film formed by the treatment agent becomes insufficient, and the interfacial adhesive force between the coating film and the fiber decreases, which is not preferable.

Further, if the weight ratio of d) is less than 0.03, the strength of the coating film formed by the treating agent becomes insufficient, and if it exceeds 0.15, the flexibility of the coating film formed by the treating agent becomes insufficient and the fibers or fibers after the treatment are treated. Flexural fatigue resistance of the structure is reduced, and the intended purpose cannot be achieved.

Therefore, it is preferable to mix the treating agent within the ranges shown in the above a), b), c) and d) to control the weight ratio of each active ingredient. Fibers or fiber structures treated in such a weight ratio range generally not only greatly improve wear resistance and bending fatigue resistance, but also deteriorate wear resistance and bending fatigue resistance in the presence of water. Very few and very good.

The solid concentration of the treating agent is appropriately 1 to 25% by weight, preferably 5 to 20% by weight. Drying temperature is 100-1
50 ℃, drying time is preferably 0.5-20 minutes, drying temperature is 1
If the temperature is less than 00 ° C, the film formation by the treating agent will be insufficient,
On the other hand, when the temperature exceeds 150 ° C., the water content in the treatment agent evaporates rapidly, and a good film cannot be formed.

The heat treatment temperature is preferably 160 to 240 ° C, and the heat treatment time is preferably 0.2 to 10 minutes. If the heat treatment temperature is less than 160 ° C, crosslinking of the formed film is insufficient and good film strength cannot be exhibited, and it exceeds 250 ° C. If so, the coating deteriorates and the strength decreases.

It should be noted that the amount of the treatment agent coating adhered to the treated fiber or fiber structure (weight of the solid content of the treatment agent) is 1 to 15% by weight.
Is suitable, and preferably 3 to 10% by weight. If it is less than 1% by weight, the wear resistance and bending fatigue resistance are insufficiently improved and no practical effect is exhibited, and if it exceeds 15% by weight, the treated fiber or fiber structure becomes remarkably coarse and hard. Flexing fatigue resistance decreases.

The reason why the treatment agent of the present invention is excellent in wear resistance and flex fatigue resistance is that polyurethane having both weather resistance and water resistance and good adhesion to fibers is used in combination with low friction coefficient polyethylene oxide and fluororesin. By doing so, a coating having flexibility, smoothness, low water absorption and water resistance can be formed on the fiber surface, and by using an ethylene urea compound in combination, a crosslinking reaction is caused to improve the cohesive force of the coating. This is because Therefore, the fiber or the fiber structure treated with this treating agent has a small coefficient of friction and has an effect of reducing the friction between the single fibers and the friction between the fibers / objects, so that the fibrillation of the single fiber is prevented. Wear resistance and bending fatigue resistance are improved.

<Effects of the Invention> The present invention has the following effects.

(1) The abrasion resistance of the fiber or fiber structure treated with the treatment agent of the present invention in the atmosphere and in the presence of water is extremely excellent.

(2) The flexural fatigue resistance of the fiber or fiber structure treated with the treatment agent of the present invention in the atmosphere and in the presence of water is extremely excellent.

<Example> A cord-like fiber structure made of para-aramid fiber that is easily fibrillated by friction will be described below, and the effects of the treatment agent of the present invention will be specifically described with reference to Examples.
The abrasion resistance and flex fatigue resistance were evaluated according to the following methods.

1) Abrasion resistance evaluation method A An evaluation device is shown in FIG. In Fig. 1, 1 is 0.8m
mφ is a strained piano wire, 2 is a load, and 3 is a chord-shaped evaluation sample.

In the figure, after attaching a load of 0.2 g / de to one end of the cord-shaped sample 3, the other end of the sample is reciprocated,
The chord sample is compared and judged by the number of reciprocations until it is cut by friction with the piano wire 1.

2) Abrasion resistance evaluation method B An evaluation device is shown in FIG. In Fig. 2, 1 is a freely rotating roll having an outer diameter of 20 mmφ, 2 is a similarly freely rotating roll having an outer diameter of 10 mmφ, 3 is a cord-shaped evaluation sample, 4
The pad 5 for interposing water in the cord-shaped evaluation sample 3 is water.

In the comparative evaluation, the cord-shaped sample 3 was twisted 1.5 times, and a part of the cord-shaped sample 3 was immersed in water 5 as shown in FIG. 1. Then, a load of 0.2 g / de was attached to one end of the cord-shaped sample 3. The other end of the sample is reciprocated, and the cord-shaped samples are compared with each other by the number of reciprocations until they are worn and cut at the twisted place.

3) Bending fatigue resistance evaluation method It is carried out by the S bending method using two pairs of freely rotating rolls with an outer diameter of 30 mmφ. After the cord-shaped evaluation sample was applied to this roll in an S-shape, the tensile force was set to 2.5 g / denier, and the cord-shaped sample was reciprocated to cause bending fatigue until the cord-shaped sample was cut. Compare and judge by the number of round trips.

Example 1 An aqueous dispersion of polyurethane (A) consisting of polycarbonate polyol and an aliphatic polyisocyanate (35% by weight of active ingredient) and an aqueous dispersion of polyethylene oxide (B) having a molecular weight of 4500 (25% by weight of active ingredient) and 4 Aqueous dispersion of fluorinated ethylene polymer (C) (60% by weight of active ingredient) and aqueous dispersion of diphenylmethanediethyleneurea (D) (active ingredient)
25% by weight) was added to each of the aqueous dispersions so that the solid content ratio (% by weight) shown in Table 1 was obtained to prepare a treatment liquid.
The solid content concentration of the treatment liquid was 10% by weight.

Para-aramid fiber (Technora, Teijin Limited) consisting of 1500 denier / 1000 filaments and having substantially no oil agent added during spinning was immersed in the treatment solution for impregnation, and then dried at 120 ° C for 2 minutes. And then 1 at 180 ℃
It was heat treated for a minute to cause a crosslinking reaction of the treatment agent coating formed on the fiber surface. At this time, the solid content of the treating agent is 5.0.
% By weight. After arranging three obtained treated aramid filaments and twisting them in the Z direction with a twist number of 20 times / 10 cm, further combining two twisted yarn products, 20 times / 10 cm in the S direction.
Were twisted together to obtain a 9000 denier cord-shaped fiber structure. The results of evaluating the abrasion resistances A and B and the bending fatigue resistance of this cord-like fiber structure are as shown in Table 1.

Examples 2 to 10 Examples 2 to 10 were the same as those used in Example 1 (A), (B),
Each of the aqueous dispersions of (C) and (D) was subjected to the solid content ratio (weight% of active ingredient) of the corresponding Example shown in Table 1.
The same procedure as in Example 1 was carried out except that the treating agent was prepared by mixing so as to obtain the desired cord-like fiber structures, and the abrasion resistances A and B and bending fatigue resistance of the cord-like fiber structures were obtained. Comparative evaluation was performed. The results are as shown in Table 1.

Comparative Example 1 For comparison, the same aramid fiber as used in Example 1 was twisted in the same manner as in Example 1 without impregnating it with a treating agent to obtain a 9000 denier cord-like fiber structure, About this, the result evaluated in the same manner as in Example 1 is shown in Table 1 as Comparative Example 1.

Comparative Examples 2 to 13 Comparative Examples 2 to 13 were examined to clarify the optimum range of the solid content ratio of the compounding treatment agent in comparison with the Example, and were used in Example 1 (A) and (B). ), (C) and (D) were mixed in such a manner that the solid content ratio (% by weight of the active ingredient) shown in Table 1 was used to prepare the treatment agent. The cord-like fiber structure obtained by the above is evaluated.

[Brief description of drawings]

FIG. 1 is a side sectional view showing a wear resistance evaluation apparatus A. In the figure, 1 is a piano wire with a circular cross section of 0.8 mmφ, 2 is a load,
3 is an evaluation sample. FIG. 2 is a side sectional view showing a wear resistance evaluation apparatus B. In the figure, 1 is a freely rotating roll having an outer diameter of 20 mmφ, 2 is a freely rotating roll having an outer diameter of 10 mmφ, 3 is an evaluation sample, 4 is a pad, and 5 is water.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // (C10M 111/04 D06M 13/48 107: 44 107: 18 107: 38 105: 70) C10N 30:06 40:00

Claims (1)

(57) [Claims] 1. A polyurethane (A) comprising a polycarbonate polyol and a polyisocyanate, a polyethylene oxide (B), a fluororesin (C) and an ethylene urea compound (D) as main components, and the weight ratio of each component is as follows: )
~ D) A wear resistance improving treatment agent which simultaneously satisfies the expressions. a) (A) / [(A) + (B) + (C) + (D)] = 0.34 to 0.70 b) (B) / [(A) + (B) + (C) + (D)] = 0.24 to 0.60 c) (C) / [(A) + (B) + (C) + (D)] = 0.03 to 0.20 d) (D) / [(A) + (B) + (C) + (D)] = 0.03 to 0.15