JP2928571B2 - Fiber rope - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fiber rope excellent in wear resistance, bending fatigue resistance, flame retardancy and the like. More specifically, by using a fiber treated under a specific condition by a processing agent of a specific composition, particularly abrasion resistance, bending fatigue resistance, water resistance,
The present invention relates to a fiber rope having improved flame retardancy.

[Prior Art] Usually, materials used for a fiber rope include polyester, nylon, vinylon, wholly aromatic polyester, ultrahigh molecular weight polyethylene, wholly aromatic polyamide (aramid fiber) and the like. These fibers may be used alone or in an untreated state, but usually, in order to sufficiently exhibit the characteristics of the fibers used, the fibers are treated with a suitable treating agent and then braided or knitted into a rope. After being processed or braided into a rope shape or knitted and woven, it is treated with an appropriate treating agent and used in each application. In this case, the common important required characteristics in the market for the rope-shaped material include abrasion resistance, bending fatigue resistance, water absorption resistance, and flame retardancy.

In order to satisfy these required characteristics, fiber surface coating and impregnation with various treatment agents are currently used in many cases. As such treatment agents, polyurethane-based and silicone-based resins are widely used. Processed fiber ropes are used in the market. For example, as a technique using a polyurethane-based resin as an abrasion resistance improver, there is disclosed a "fiber rope treated with a mixture mainly composed of polyurethane, polyethylene oxide and an ethylene urea compound" (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 fiber belt to heat treatment" (Japanese Patent Application Laid-Open No. 60-173174), A method of treating with a first treating agent containing a ring agent as a main component, followed by treating with a second treating agent containing polyurethane, polyethylene oxide, and an ethylene urea compound as main components ”(Japanese Patent Publication No. 1-29099). Prior art).

Indeed, it has been found that fiber ropes surface-coated or impregnated with the treatment agents shown in the above prior art have improved abrasion resistance. However, with the recent fragmentation of applications and the advancement of technology in the market, the required performance of products tends to be further improved and expanded, and the above-mentioned prior art (conventional technology) has poor wear resistance and bending fatigue resistance. It is still insufficient, and cannot be adequately handled depending on the application. For example, para-aramid fiber has a high strength of 20 g / deny or more, and various fiber ropes using this fiber have recently been developed and are being used in application fields such as cords and ropes. It is easy to fibrillate due to friction between fibers / fibers and between fibers / metals, and this is the main cause of the deterioration of strength, which has the disadvantage that the excellent high strength characteristics inherent to fibers cannot be sufficiently exhibited.

In order to remedy this drawback, a relatively good wear-resistant nylon fiber etc. was used for the surface layer of the fiber rope-like material. Have been. However, even these fiber ropes having a composite structure are still insufficient, and in particular, they have not yet completely prevented fibrillation of aramid fibers. In other words, due to friction between core fibers in the process of repeated use of aramid fiber using products,
The fiber is partially fibrillated, resulting in a problem that sufficient product strength cannot be maintained for a long period of time.

Further, recently, especially in the field of electric construction, high waterproofness, flame retardancy, and electrical insulation have been required, but fibers coated with a surface coating are generally waterproof, electrically insulative, and difficult to use. Since the flammability is inferior to that of the untreated one, there is also a problem that the excellent electrical insulation and flame retardancy inherent in the aramid fiber cannot be sufficiently exhibited.

<Object of the Invention> The present invention has been devised as a result of intensive studies to prevent such problems in the prior art, in particular, fibrillation of fibers due to friction. The purpose is that the thermal decomposition temperature
It is intended to impart electrical insulation, high abrasion resistance, flex fatigue resistance, waterproofness, and flame retardancy to a fiber rope made of organic heat-resistant fibers of 230 ° C or higher. The present inventors have conducted various studies in order to achieve such an object, and as a result, by heat-treating a fluororesin under specific conditions to coat or impregnate and adhere to the fiber surface in a special form, the market has been developed. The present inventors have found that a fiber rope having excellent abrasion resistance, bending fatigue resistance, waterproofness, and flame retardancy that can sufficiently meet the requirements can be obtained, and the present invention has been accomplished.

<Constitution of the Invention> That is, the present invention relates to: 1) a fiber rope-like material comprising a fiber having a thermal decomposition temperature of 230 ° C. or higher and a fiber surface coated with a fluororesin; Is 80 ~ 130 ℃
After being dried at a temperature of, it is heat-treated in a temperature range of the melting point of the fluorine-based resin ± 60 ° C. and fixed to the fiber surface in the form of fine particles having a diameter of 0.1 to 1.0 μm. Is 35% or more, and the fiber has a twist coefficient of 0.4 to 10.0
A fiber rope-like material characterized by being twisted with:

2) A fiber rope having a pyrolysis temperature of 230 ° C. or higher and a fiber coated with a fluororesin on the fiber surface, wherein the fluororesin is 80 to 130 ° C.
After being dried at a temperature of, it is heat-treated in a temperature range of the melting point of the fluorine-based resin ± 60 ° C. and fixed to the fiber surface in the form of fine particles having a diameter of 0.1 to 1.0 μm. Is 35% or more, and the fibers are braided.

3) A fiber having a pyrolysis temperature of 230 ° C. or higher, and a core-sheath structure made of a fiber whose surface is coated with a fluororesin, wherein the fluororesin is 80 to
After drying at a temperature of 130 ° C, the melting point of the fluororesin ± 60
Heat treated in a temperature range of ℃ and the fiber surface has a diameter of 0.1 ~ 1.0μm
Is fixed in the form of fine particles, and the surface coverage of a single fiber with the fine particle fluororesin is 35% or more, and the core has a twist coefficient of 0.4.
A fiber rope-like material characterized in that the sheath is braided at 10.0 to 10.0.

4) Fibers having a thermal decomposition temperature of 230 ° C. or higher and a core-in-sheath rope made of fibers having a fiber surface coated with a fluororesin, wherein the fluororesin is 80 to
After drying at a temperature of 130 ° C, the melting point of the fluororesin ± 60
Heat treated in a temperature range of ℃ and the fiber surface has a diameter of 0.1 ~ 1.0μm
A fibrous rope-like material which is fixed in the form of fine particles having a surface coverage of a single fiber of 35% or more with the fine particle-like fluororesin, the core portion is aligned and the sheath portion is braided.

5) A rope having a core-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or higher and a fiber coated with a fluororesin on the fiber surface, wherein the fluororesin is:
After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C and the fiber surface has a diameter of 0.1-1.0.
μm is fixed in the form of fine particles, the surface coverage of the single fiber with the fine particle-like fluororesin is 35% or more, the core part is a plied yarn of the fluororesin-coated fiber, and the sheath part is polyester fiber or nylon fiber. A fiber rope-like material characterized by being braided.

6) In a rope having a core-in-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, the fluororesin is:
After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C and the fiber surface has a diameter of 0.1-1.0.
μm is fixed in the form of fine particles, the single-fiber surface coverage of the fine-particle fluororesin is 35% or more, the core is made of the fluororesin-coated fiber, and the sheath is made of polyester fiber or nylon fiber. A fiber rope-shaped material characterized by being braided.

7) In a rope having a double-coated core-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, the fluororesin is: After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluorine-based resin ± 60 ° C,
0.1 to 1.0 μm is fixed in the form of fine particles, the surface coverage of the single fiber with the fine particle-like fluororesin is 35% or more, and the core and the inner coating layer are composed of the fluorine-containing resin-coated fibers, A fibrous rope-shaped article characterized in that the fibers are aligned, the inner covering layer is braided, and the outer covering layer is braided of polyester fiber or nylon fiber.

8) In a rope having a double-coated core-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, the fluororesin is: After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluorine-based resin ± 60 ° C,
It is fixed to fine particles of 0.1 to 1.0 μm, the surface coverage of a single fiber by the fine particle-like fluororesin is 35% or more, and the core portion is made of the same fluororesin-coated fiber, and the inner coating layer and the outer coating The layer is a fiber rope-like material characterized by being braided with polyester fiber or nylon fiber.

9) In a rope having a core-in-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or higher and a fiber coated with a fluororesin on the fiber surface, the fluororesin is:
After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C and the fiber surface has a diameter of 0.1-1.0.
μm is fixed in the form of fine particles, and the surface coverage of the single fiber with the fine particle fluorine resin is 35% or more, and the core is a plied yarn in which the fluorine resin coated fiber is plied with a twist coefficient of 0.4 to 10.0. A fiber rope-shaped material, wherein the sheath is made of resin.

10) A fiber having a core-in-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, wherein the fluororesin is:
After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C and the fiber surface has a diameter of 0.1-1.0.
μm is fixed in the form of fine particles, the surface coverage of a single fiber with the fine particle fluorine resin is 35% or more, the core is braided with the fluorine resin coating fiber, and the sheath is resin. Fiber rope-like material.

11) In a rope having a core-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, the fluororesin is:
After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C and the fiber surface has a diameter of 0.1-1.0.
μm is fixed in the form of fine particles, the surface coverage of the single fiber with the fine particle fluorine resin is 35% or more, the fluorine resin coated fiber is aligned in the core, and the sheath is resin. Fiber rope-like material.

12) In a rope having a double-coated core-sheath structure including a fiber having a thermal decomposition temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, the fluororesin is: After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluorine-based resin ± 60 ° C,
0.1 to 1.0 μm is fixed in the form of fine particles, the surface coverage of the single fiber with the fine particle-like fluororesin is 35% or more, the core is made of the fluorine-containing resin-coated fiber, and the inner coating layer is the fluorine-containing resin. A fibrous rope-shaped article which is braided with a base resin-coated fiber and the outer coating layer is a resin.

13) A fiber having a core-in-sheath structure including a fiber having a pyrolysis temperature of 230 ° C. or more and a fiber coated with a fluororesin on the fiber surface, wherein the fluororesin is:
After drying at a temperature of 80-130 ° C, it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C and the fiber surface has a diameter of 0.1-1.0.
μm is fixed in the form of fine particles, the surface coverage of a single fiber with the fine particle-like fluorine-based resin is 35% or more, and the core portion is made up of resin-coated fibers obtained by coating the fluorine-based resin-coated fibers with a resin, A fiber rope-shaped material characterized in that the sheath is made of resin.

Here, the term "fiber rope-like material" includes, in addition to a normal fiber rope, a fiber cord used for the same purpose as the rope.

The fibers constituting the fiber rope and having a thermal decomposition temperature of 230 ° C. or higher include, for example, aramid fibers and wholly aromatic polyester fibers.

Fluorinated resins include tetrafluoroethylene polymer, trifluoroethylene chloride polymer, tetrafluoroethylene hexafluoropropylene copolymer, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, Ethylene / propylene hexafluoride / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride polymer, ethylene / tetrafluoroethylene copolymer and the like.

As the fluororesin, use is made of a dispersion obtained by dispersing a particulate fluororesin in a dispersion medium using a dispersant, or a water emulsion obtained by emulsifying the particulate fluororesin in an aqueous medium using an emulsifier. The amount of the fluorine resin adhered to the fiber rope is 0.5 to 80% by weight, preferably 4 to 70% by weight as a solid content. If the content is less than 0.5% by weight, sufficient wear resistance, bending fatigue resistance, water absorption resistance, electric insulation and flame retardancy cannot be obtained. If the content exceeds 80% by weight, not only does the workability of the fluororesin deteriorate, but also the cost is high for the properties obtained, and the film strength of the fluororesin also decreases. A conventional method may be used to apply the fluororesin to the fiber or the fiber rope. For example, impregnation method,
A spray method, a coating method, or the like may be used. After a predetermined amount of the particulate fluororesin is adhered to the fiber or the fiber rope by these methods, it is dried at a temperature of 80 ° C. or more by an ordinary dryer such as a non-touch drier or a tenter. After drying, the melting point of the fluororesin ± 60 to increase the adhesion of the particulate fluororesin to the fiber
Heat treatment at a temperature of ° C.

By performing the treatment in such a temperature range, a part of the particulate fluororesin remains and adheres to the surface of the fiber in an island shape (on the surface of Kazunoko). For example, when the fluororesin is an ethylene tetrafluoride polymer, at 270 to 380 ° C. for 0.3 to 15 minutes, in the case of an ethylene tetrafluoride / propylene hexafluoride copolymer, 21
By performing a heat treatment at about 0 to 310 ° C. for about 0.3 to 15 minutes, a part of the particulate fluorine-based resin remains and adheres to the surface of the fiber in the form of a kazunoko. The particle size of the fine particles of the fluorine-based resin fixed on the surface of the fiber in the form of a fir tree depends on the fiber diameter, but is preferably 0.1 to 1 μm. When the particle size is less than 0.1 μm, the adhesion between single fibers or between fibers and metal becomes high, and the fine particles are easily aggregated, so that the roller-like effect becomes insufficient. If the particle size exceeds 1 μm, the adhesion to the fiber becomes incomplete and the roller-like effect is not sufficiently exhibited.

The entire surface (100%) of the fiber surface may be covered with fine-particle fluorine-based resin on the surface of Kazunoko. Between the fibers / fibers or between the fibers / objects, the fixed fine particle-like fluororesin serves as a roller and reduces the friction between the fibers or between the fibers / objects, so-called roller effect (between the objects / objects). In this case, an effect of improving the slip between the objects by interposing the rollers is developed. By using the fiber whose surface is coated with the particulate fluorine-based resin for all or a part of the fiber rope, the following effects aimed at by the present invention can be achieved.

<Effects of the Invention> 1) The fiber rope-shaped material of the present invention is extremely excellent in abrasion resistance.

2) The fiber rope of the present invention is extremely excellent in bending fatigue resistance.

3) The fiber rope of the present invention has improved flame retardancy.

4) The fiber rope of the present invention has good water absorption resistance.

 Hereinafter, the present invention will be described specifically with reference to examples.

<Examples> In general, a para-aramid fiber, which is said to be most likely to cause fibrillation of a single fiber by friction,
An example in which the effects of the present invention were confirmed by trial production of a cord-shaped and rope-shaped fiber rope while applying the present invention to this will be described in detail. Evaluation and measurement of abrasion resistance, bending fatigue resistance, water absorption, flame retardancy, and surface coverage of a single fiber with a particulate fluorine resin were performed according to the following methods.

1) Evaluation method for abrasion resistance [Evaluation method mainly for cord type] An evaluation device is shown in FIG. In the figure, 1 is 2.0mmφ
The tensioned piano wire, 2 is the load, and 3 is the evaluation sample.
The evaluation was performed as follows. That is, after a load 2 of 0.2 g / de is attached to one end of the sample 3 in the form of a cord, the other end of the sample is reciprocated to withstand a reciprocating circuit until the sample 3 is cut by friction with the piano wire 1. The abrasion was compared and determined.

2) Flexural fatigue evaluation method [Evaluation method mainly for rope form] Comparative evaluation is performed by the S-bending method using two pairs of free rollers. The test conditions are selected so that the ratio (D / d) of the free roller diameter (D) to the fiber rope (evaluation sample) diameter (d) is 6 to 7, and the tensile force applied to the fiber rope is adjusted to After setting to 1/3 of the tensile breaking strength (safety factor = 3), the fiber rope is reciprocated to give S-bending bending fatigue, and the bending fatigue resistance is determined by the number of reciprocations until the fiber rope is cut. Were evaluated comparatively.

3) Water absorption rate evaluation method (evaluation of water absorption resistance) Approximately 3 g (filament) or approx.
Collect 10g (rope-like material) and dry in a dryer at a temperature of 70-90 ° C.
Pre-dry for 0 to 120 minutes. Next, this sample was heated to a temperature of 20 ±
It is placed in a desiccator adjusted to 2 ° C. and a relative humidity of 85 ± 3% RH, left for three days or more to allow sufficient water absorption, and then weighed (W). Thereafter, the sample was dried in a dryer at 105 ± 2 ° C. for 120 minutes (filament) or 240 minutes (rope), immediately weighed (W ₀ ), and the water absorption was calculated according to the following formula. did.

Water absorption (%) = (weight before drying W-weight after drying W ₀ / weight after drying W ₀ ) × 1
(Note) The higher the water absorption, the lower the durability.

4) Flame retardancy evaluation method It was carried out according to the JIS K7201-72 oxygen index method. However, in order to clarify a significant difference between samples, a circular knitted fabric having a relatively coarse density was experimentally produced and evaluated.

(Note) Knitted fabric for evaluation: circular knitting, knitting with 5G (needle, 5 needles / inch) 5) Calculation method of single fiber surface coverage by fine particle fluorine resin Scanning electron microscope (JEOL, JSM-840) 200 using
The surface of the single fiber is observed in the range of about 0 to 8000 times, and from the photographed image, the surface coverage of the single fiber with the particulate fluororesin is calculated according to the following criteria.

A: Definition of surface area of single fiber surface; whole area where single fiber is observed in flat form in electron micrograph (planar observation) (all side areas of fiber in the photograph) B: Fine-particle fluorine-based resin Definition of the surface coating area according to the following formula: In the electron microscope photograph (planar observation) of the above A, the area where the fluororesin is fixedly scattered in the form of fine particles, provided that the distance between the fine particles is within 20 times the particle diameter. In some cases, since a roller-like effect can be exerted, the area is regarded as an area covered with the fine-particle fluorine-based resin.

C:% surface coverage by fine-particle fluorine resin = (B / A)
× 100 <Example 1> The fiber is composed of 1500 denier 1000 filaments
Aramid long fiber yarn [Technora ; Teijin Limited]
This was mixed with an aqueous tetrafluoroethylene polymer dispersion (concentration 15
%) And then immersed at the specified temperature shown in Table 1
After drying for a period of time, heat-treat at a predetermined temperature for a predetermined time.
Was. Two of the obtained treated aramid filament fibers are aligned and Z
After twisting 25 times / 10cm (twisting coefficient: about 4.8) in the direction
Combine these three more and twist them 16 times / 10cm in the S direction (twist
Multiplied by a factor of about 5.3) 9000 denier cord-shaped row
(Twisted yarn) was obtained. This rope is wear resistant and resistant
Flexural fatigue, water absorption, surface made of particulate fluororesin
Table 1 shows the results of evaluating and measuring various properties such as coverage.
It was exactly what I did. In addition, this treated aramid filament yarn
The nitrogen-based resin adhesion rate is 7.9 to 8.4% by weight.
Approximately 7.5 turns of the treated yarn so that the twist coefficient is near 1 in the Z direction.
After twisting 10 cm, knit a circular knitted fabric and evaluate the flame retardancy
The results are also shown in Table 1.

<Example 2> 1500 denier 1000 obtained by carrying out in the same manner as in Example 1
Two treated aramid filament yarns consisting of filaments are aligned and twisted 8 times / 10 cm in the Z and S directions,
The same number of 0-denier ply-twisted yarn products were trial-produced, and two of them were aligned and braided (2 × 4) to obtain a braided fiber rope. The characteristics of the braided fiber rope were evaluated and measured, and the results are as shown in Table 1. Table 1 also shows the results of evaluating the flame retardancy of the treated aramid long fiber yarn used here in the same manner as in Example 1 for confirmation.

<Example 3> A cord obtained by carrying out in the same manner as in Example 1 was used as a core (core material of a fiber rope), and the outside thereof was braided (2 × 4) with the plied yarn obtained in Example 2. Thus, a core-sheath structured fiber rope was obtained in which the core material was a cord-shaped fiber structure and the sheath portion was braided.
The evaluation results of the obtained rope were as shown in Table 1.

<Example 4> In Example 3, a trial production was performed in the same manner as in Example 3, except that the treated aramid long fiber yarn (1500 denier 1000 filaments) of Example 1 was simply used for the core in a aligned state. The evaluation results of the obtained core-sheath structured fiber rope were as shown in Table 1.

<Example 5> In Example 3, the fiber constituting the sheath portion was 1000
Using a polyester filament consisting of 96 denier 96 filaments, three of them are aligned and twisted 10 times / 10 cm in the Z direction to produce a 3,000 denier Z-direction plied yarn, and a 3000 denier S-direction yarn. A twisted yarn was prepared in the same manner, a Z-direction twisted yarn and a Z-direction twisted yarn were aligned to form a knitting yarn, and this was braided (2 × 4) to form a sheath portion. The results of evaluation of the core-sheath structured fiber rope obtained as described above are shown in Table 1.

<Example 6> In Example 5, evaluation was performed in the same manner as in Example 5, except that the treated aramid filament yarn composed of untwisted 1500 denier 1000 filaments was used for the core in a state of being simply aligned. . The results were as shown in Table 1.

<Example 7> In the core-sheath structure fiber rope, in order to improve particularly abrasion resistance and weather resistance, the same polyester filament as used in Example 5 was further used for the outer layer of the fiber rope prototyped in Example 4. Then, the braid was braided in the same manner as in Example 5 to obtain a double-coated multilayer-structured fiber rope having an outermost sheath layer.

<Example 8> A double-coated multilayer structure fiber rope was obtained in the same manner as in Example 7, except that the inner sheath and the outer sheath were formed of the same polyester filament. The evaluation results of the obtained rope were as shown in Table 1.

<Example 9> After the cord of Example 1 was immersed in a polyether-based urethane solution (solution concentration 70%) dissolved in dimethylformamide, an extra polyether-based urethane solution was removed through a circular hole. After that, it is dried at 110 ° C for about 8 minutes and then heat-treated at 160 ° C for about 0.5 minutes to obtain a double-coated multi-layer fiber rope whose outermost layer is coated with a polyether urethane resin. Was. The results of the evaluation are as shown in Table 1. The adhesion rate of the polyether urethane resin was 45% by weight.

<Example 10> About the braided fiber rope obtained in Example 2, Example 9
In the same manner as described above, the outermost layer was surface-coated with a polyether-based urethane resin to obtain a braided double-coated fiber rope in which the core was made of a braided fiber and the sheath was made of a polyether-based urethane treatment. The evaluation results were as shown in Table 1. The adhesion rate of the polyether-based urethane resin was 55% by weight.

<Example 11> The treated aramid long fiber yarn of Example 1 was twisted about 4.7 times / 10 cm so that the twist coefficient was about 1, and then 20 pieces of this were aligned to form a core strand. And resin solution concentration 80
Example 9 using a polyether-based urethane solution having a weight percentage of 9%
Was carried out in the same manner as in Example 1 to obtain a resin-coated fiber rope having a core made of a twisted twisted strand. The evaluation results were as shown in Table 1. The adhesion rate of the polyether urethane resin was 68% by weight.

<Example 12> The outermost layer portion was formed by the same method as in Example 9 using the core-sheath structured fiber rope of Example 4 in which the core portion was formed of a non-twisted drawn strand and the sheath portion was a braided structure. The surface was coated with a polyether-based urethane resin to obtain a double-coated fiber rope. The evaluation results were as shown in Table 1. The resin adhesion rate was 52% by weight.

<Example 13> The treated aramid long fiber yarn of Example 1 (1500 denier 1000
After two filaments were aligned and immersed in the polyether-based urethane solution used in Example 9, excess resin was removed through small circular holes, and dried and heat-treated in the same manner as in Example 9. Thus, 3000 denier surface resin coated fiber strand was obtained. After further arranging 10 of these, they were immersed again in the polyether-based urethane resin solution used in Example 11, then the excess resin was removed through the circular holes, and dried and heat-treated in the same manner as above. A double coated fiber rope was obtained. Table 1 shows the evaluation results. The resin adhesion was 78% by weight.

<Example 14> As a fiber, an fiber consisting of 200 denier 133 filaments was used.
Lamid filament yarn (Technola ; Teijin Limited)
This is treated with a 20% concentration of fluorotetrafluoroethylene polymer.
After fully immersing in the base resin aqueous dispersion, lighten with a roll.
After drying at a predetermined temperature shown in Table 1 for a predetermined time
, 15 yarns are aligned and twisted 20 times in the Z direction with a twist of 10cm
Then, three twisted yarns are combined, and 20 times / 1 in the S direction
Twisted with 0cm twist to create 9000 denier cord
And heat it at a predetermined temperature shown in Table 1 for a predetermined time.
After processing, the desired rope was obtained. About this one
Surface coverage, abrasion resistance, bending resistance of fine particle fluororesin
Table 1 shows the results of evaluating bending fatigue, water absorption and flame retardancy.
Indicated. However, the production of circular knitted fabric for flame retardancy evaluation is 200 denier.
8 yarns and twisted 6 times / 10cm
Was organized and evaluated. Fluorine resin adhesion rate is 12.9
% By weight.

Furthermore, in order to clearly understand the relationship between the heat treatment temperature and the wear resistance, using the 9000 denier rope, the heat treatment time was fixed at 3.0 minutes, and the heat treatment temperature was variously changed within the range of 260 to 400 ° C. FIG. 2 shows the results of evaluating the abrasion resistance of the obtained rope.

From FIG. 2, it is apparent from FIG. 2 that the abrasion resistance is particularly good in the heat treatment temperature range of 280 to 370 ° C. in the case of this fluorine-based resin.

Therefore, in order to grasp the relationship between the state of fixation of the fluororesin in these ropes and the abrasion resistance, several single fibers were taken out from a portion relatively close to the inner layer of the rope created under the conditions of FIG. Scanning electron microscope (JEOL, JSM-84
Using 0), the state of fixation of the fluororesin fixed to the surface of the single fiber was observed at a magnification of 3000 times and photographed for comparative evaluation. FIG. 4 shows a drawing drawn with reference to the photograph. A in FIG. 4 is based on the condition shown in FIG. 2A, and the same applies hereinafter.

As is clear from FIG. 4, in the case of heat-treated at a relatively low temperature, most of the fluorine-based resin adheres to the surface of the single fiber in a state where the fine-particle form is retained and retained. It can be understood from FIG. 4 that a roller-like effect is exerted at the time of friction with another object or at the time of friction between the fiber and the fiber to improve the wear resistance.

On the other hand, when heat-treated at a relatively high temperature (400 ° C. or higher), the fine-particle fluororesin is melting to form a film-like film, and the ratio of the fluorine-based resin remaining and retained in the fine-particle form is low. It has been greatly reduced. As a result, the wear resistance tends to decrease as shown in FIG.

In the case of this fluororesin, the one treated at a heat treatment temperature of less than 280 ° C., particularly at a heat treatment temperature of less than 260 ° C., has remarkably reduced wear resistance. This is because although most of the fluorine resin adheres to the fiber surface in the form of fine particles,
Due to the low heat treatment temperature, the adhesive strength between the fiber and the fluororesin or fluororesin is insufficient, and the particulate fluororesin falls off during the evaluation of abrasion resistance, resulting in abrasion resistance and abrasion durability It is understood that the sex is reduced.

In order to further clarify the above relationship, FIG. 3 shows the results of examining the change in peel adhesion strength between the aramid fiber and the fluororesin when the heat treatment temperature was changed. The study method is as follows. First, this embodiment
Aramid filaments composed of 133 filaments of 200 denier used in 14 were used for the warp and the weft so that the warp density and the weft density were the same number of 34 yarns / 25 mm, respectively, and a flat-woven fabric was trial-woven. Next, the woven fabric is subjected to deoiling treatment and dried, and then sufficiently immersed in the same fluororesin aqueous dispersion (liquid concentration: 20%) used in this example, and further dried under the same conditions as in this example. did. Next, the woven fabric after drying is 15cm x 20cm
, And two sets of these were stacked to make several sets.

These are sandwiched between presses that can be heated and pressurized.
Heating and pressing were performed at 0 kg / cm ² , heat treatment time of 3.0 minutes, and heat treatment temperature of 260 to 400 ° C. The obtained two-ply woven fabric is cut into a width of 2 cm in the length direction to obtain a measurement sample, and has a T-type peeling strength (strength required for peeling when the woven fabric and the woven fabric are peeled off in a T-shape). Was measured comparatively. FIG. 3 shows a graph of the results.

From this figure, the adhesive force between the aramid fiber and the fluororesin gradually increases from around 280 ° C. to around 350 ° C., and becomes almost constant at a temperature higher than that. This phenomenon is that at a heat treatment temperature of less than 280 ° C., the adhesion (fixation) between the aramid fiber and the fluororesin is insufficient, and the fluororesin tends to fall off. This is considered to indicate that a sufficiently satisfactory wear resistance cannot be exhibited. In addition, the fact that the adhesive strength did not increase even though it was heat-treated at a temperature of 360 ° C or higher was because the fluorocarbon resin had already melted at a lower temperature than when heat-treated at this temperature, and had sufficiently adhered to the fibers. It is thought that it is. When the heat treatment is performed at a temperature higher than this, almost no particulate fluororesin is found on the fiber surface.
In this case, in the cord-shaped rope shown in FIG. 2, even in the heat-treated product under the same conditions, the presence of the particulate fluorine-based resin is still recognized. The reason is that the cord rope is 9000
It is considered that the denier is relatively thick and has a thickness several times as large as that of the two-ply fabric, so that the calorific value becomes substantially insufficient at the same heat treatment temperature as that of the woven fabric. Even in the case of this cord-shaped rope, when the heat treatment temperature is set to 400 ° C. or higher, as described above, the abundance ratio of the particulate fluorine-based resin is greatly reduced, and the wear resistance is also reduced.

From the above, in the case of this fluorine-based resin, although it depends on the structure of the rope-like material, the melting point of the fluorine-based resin is within a temperature range of ± 60 ° C., and the time within which the particulate fluorine-based resin can sufficiently remain. It can be understood that the heat treatment is favorable from the viewpoint of improving the wear resistance. Therefore, completely coating the fluororesin completely does not exhibit the roller-like effect, and is inferior in terms of wear resistance and bending fatigue resistance.

<Comparative Example 1> For comparison, a fiber rope was trial-produced in the same manner as in Example 1 using an aramid long fiber yarn untreated with a fluororesin in Example 1, and evaluated. The results were as shown in Table 2.

<Comparative Example 2> A braided fiber rope was trial-produced in the same manner as in Example 2 using aramid filament fibers not treated with a fluororesin, and evaluated. Table 2 shows the results.

<Comparative Examples 3 and 4> A core-sheath structured fiber rope was prototyped in the same manner as in Examples 3 and 4, except that an aramid long fiber yarn not treated with a fluororesin was used. The evaluation results are shown in Table 2.

<Comparative Examples 5 and 6> A core-sheath structured fiber rope was produced in the same manner as in Examples 5 and 6, respectively, except that a core portion was formed using aramid long fiber yarn not treated with a fluororesin. The prototype was evaluated. The results are shown in Table 2.

<Comparative Examples 7 and 8> Except that an aramid long fiber yarn not treated with a fluororesin was used, a fiber rope having a multilayer structure was trial-produced in the same manner as in Examples 7 and 8, and each was evaluated. The results are shown in Table 2.

<Comparative Examples 9 to 13> Resin-coated fiber ropes were trial-produced and evaluated in the same manner as in Examples 9 to 13 respectively, except that aramid long fiber yarns not treated with a fluororesin were used. Second
The results are shown in the table.

<Comparative Example 14> A cord-like rope was obtained in the same manner as in Example 14, except that an aramid long fiber yarn not treated with a fluororesin was used. The evaluation results are shown in Table 2.

<Comparative Examples 15 and 16> In Example 1, the heat treatment conditions were changed to the corresponding predetermined conditions shown in Table 2 to change the surface coverage of the single fiber with the particulate fluororesin after the heat treatment. Except for the above, the same procedure as in Example 1 was carried out to obtain a target cord-like rope, and the results of the evaluation are shown in Table 2.

[Brief description of the drawings]

FIG. 1 is a side sectional view showing a wear resistance evaluation device. 1 is a 2.0 mmφ circular piano wire, 2 is a load, and 3 is an evaluation sample. FIG. 2 shows the relationship between wear resistance and heat treatment temperature. Points A to E correspond to electron micrographs A to E, respectively. FIG. 3 shows the relationship between peel adhesion strength and heat treatment temperature. FIG. 4 is a drawing drawn with reference to an electron micrograph showing a state in which a fluororesin is attached or fixed to the fiber surface. FIGS. 2A to 2E are diagrams showing the state of adhesion or fixation of the fluororesin for the sample corresponding to each point (A to E) in FIG. In the drawing, 1 is a single fiber, 2 is fine particles of a fluororesin adhered to the surface of the single fiber, and 3 is a fluororesin forming a film-like film.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/256 (56) References JP-A-60-75675 (JP, A) JP-A-52-96233 (JP, A) JP-A-54 JP-A-42444 (JP, A) JP-A-53-31851 (JP, A) JP-A-2-46895 (JP, U)

Claims (13)

(57) [Claims] 1. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a fiber rope-like material made of fibers coated with a fluororesin on the fiber surface, the fluororesin is 80 to
After drying at a temperature of 130 ° C, the melting point of the fluororesin ± 60
Heat treated in a temperature range of ℃ and the fiber surface has a diameter of 0.1 ~ 1.0μm
Is fixed in the form of fine particles, and the surface coverage of the single fiber with the fine particle fluororesin is 35% or more, and the fiber has a twist coefficient of 0.4.
A fibrous rope-like material characterized by being twisted at 10.0. 2. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a fiber rope-like material made of fibers coated with a fluororesin on the fiber surface, the fluororesin is 80 to
After drying at a temperature of 130 ° C, the melting point of the fluororesin ± 60
Heat treated in a temperature range of ℃ and the fiber surface has a diameter of 0.1 ~ 1.0μm
A fiber rope-shaped material which is fixed in the form of fine particles, has a surface coverage of a single fiber of 35% or more by the fine-particle fluorine-based resin, and is formed by braiding fibers. 3. A fiber having a pyrolysis temperature of 230 ° C. or higher,
The fiber surface is a core-sheath rope formed of a fiber coated with a fluororesin, and the fluororesin is dried at a temperature of 80 to 130 ° C., and then the melting point of the fluororesin ± 60. Heat treated in a temperature range of ℃ C
It is fixed to fine particles of up to 1.0 μm, the surface coverage of a single fiber with the fine particle fluororesin is 35% or more, the core is twisted with a twist coefficient of 0.4 to 10.0, and the sheath is braided. Characteristic fiber rope. 4. A fiber having a pyrolysis temperature of 230 ° C. or higher,
The fiber surface is a core-sheath rope formed of a fiber coated with a fluororesin, and the fluororesin is dried at a temperature of 80 to 130 ° C., and then the melting point of the fluororesin ± 60. Heat treated in a temperature range of ℃ C
The fiber rope is fixed in the form of fine particles of about 1.0 μm, has a surface coverage of a single fiber of 35% or more by the fine-particle fluorine-based resin, and has a core portion aligned and a sheath portion braided. Stuff. 5. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a rope-shaped material having a core-sheath structure containing a fiber coated on a surface of a fluororesin, the fluororesin is dried at a temperature of 80 to 130 ° C., and then the melting point of the fluororesin ± Heat treated in a temperature range of 60 ° C and the fiber surface has a diameter of 0.
1 to 1.0 μm fine particles are fixed, the surface coverage of the single fiber with the fine particle-like fluororesin is 35% or more, the core is a plied yarn of the fluororesin-coated fiber, and the sheath is polyester fiber. Or a fiber rope-like material characterized by being braided with nylon fibers. 6. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a rope-shaped material having a core-sheath structure containing a fiber coated on a surface of a fluororesin, the fluororesin is dried at a temperature of 80 to 130 ° C., and then the melting point of the fluororesin ± Heat treated in a temperature range of 60 ° C and the fiber surface has a diameter of 0.
It is fixed to fine particles of 1 to 1.0 μm, the surface coverage of a single fiber with the fine particle fluororesin is 35% or more, the fluororesin coated fiber is aligned in the core, and the sheath is polyester fiber or A fiber rope-like material characterized by being braided with nylon fibers. 7. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a rope-like material having a double-coated core-sheath structure containing fibers coated with a fluororesin on the fiber surface, the fluororesin is dried at a temperature of 80 to 130 ° C., and then the fluororesin is dried. Is heat-treated in a temperature range of the melting point of ± 60 ° C., and is fixed on the fiber surface in the form of fine particles having a diameter of 0.1 to 1.0 μm. The inner coating layer is made of the fluororesin-coated fiber, the core is aligned, the inner coating layer is braided,
A fiber rope-like article characterized in that the outer coating layer is formed by braiding polyester fibers or nylon fibers. 8. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a rope-like material having a double-coated core-sheath structure containing fibers coated with a fluororesin on the fiber surface, the fluororesin is dried at a temperature of 80 to 130 ° C., and then the fluororesin is dried. Heat-treated at a melting point of ± 60 ° C. to be fixed to the fiber surface in the form of fine particles having a diameter of 0.1 to 1.0 μm. The surface coverage of the single fiber with the fine particle-like fluororesin is 35% or more. A fibrous rope-like article characterized in that the fluororesin-coated fibers are aligned and the inner coating layer and the outer coating layer are braided with polyester fibers or nylon fibers. 9. A fiber having a pyrolysis temperature of 230 ° C. or higher,
In a rope-shaped material having a core-sheath structure containing a fiber coated on a surface of a fluororesin, the fluororesin is dried at a temperature of 80 to 130 ° C., and then the melting point of the fluororesin ± Heat treated in a temperature range of 60 ° C and the fiber surface has a diameter of 0.
1 to 1.0 μm fixed in the form of fine particles, the single-fiber surface coverage by the fine-particle fluorine-based resin is 35% or more, and the core is twisted with the fluorine-based resin-coated fiber with a twist coefficient of 0.4 to 10.0. A fibrous rope-like material, which is a ply-twisted yarn and a sheath portion is made of resin. 10. A rope having a core-sheath structure containing fibers having a pyrolysis temperature of 230 ° C. or higher and coated on the fiber surface with a fluororesin, wherein the fluororesin is: After being dried at a temperature of 80 to 130 ° C., it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C. and fixed to the fiber surface in fine particles having a diameter of 0.1 to 1.0 μm. A fiber rope-shaped article having a fiber surface coverage of 35% or more, a core portion formed by braiding the fluororesin-coated fiber, and a sheath portion formed of resin. 11. A rope having a core-sheath structure comprising a fiber having a pyrolysis temperature of 230 ° C. or higher and a fiber coated with a fluororesin on its surface, wherein the fluororesin is: After being dried at a temperature of 80 to 130 ° C., it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C. and fixed to the fiber surface in fine particles having a diameter of 0.1 to 1.0 μm. A fiber rope-like material having a fiber surface coverage of 35% or more, a core portion made of the fluororesin-coated fibers, and a sheath portion made of resin. 12. A rope having a double sheathed core-sheath structure comprising a fiber having a thermal decomposition temperature of 230 ° C. or higher, and a fiber coated with a fluororesin on the surface of the fiber.
After the fluororesin is dried at a temperature of 80 to 130 ° C.,
Heat-treated at a temperature range of the melting point of the fluorine-based resin ± 60 ° C. and fixed to the fiber surface in the form of fine particles having a diameter of 0.1 to 1.0 μm. A fiber rope-shaped article, wherein the portion is made of the fluororesin-coated fibers, the inner coating layer is braided with the fluororesin-coated fibers, and the outer coating layer is a resin. 13. A rope having a core-in-sheath structure comprising a fiber having a thermal decomposition temperature of 230 ° C. or higher and a fiber coated on the fiber surface, wherein the fluorine-based resin is After being dried at a temperature of 80 to 130 ° C., it is heat-treated at a temperature range of the melting point of the fluororesin ± 60 ° C. and fixed to the fiber surface in fine particles having a diameter of 0.1 to 1.0 μm. A fiber rope-like material having a fiber surface coverage of 35% or more, a core portion made of resin-coated fibers obtained by coating the fluororesin-coated fibers with a resin, and a sheath portion made of resin.