JPH0683731B2 - Synthetic fiber gut for racket and method of manufacturing the same - Google Patents

Description

The present invention relates to a synthetic fiber gut for a racket used for hard tennis, soft tennis, badminton, squash, etc., which reversibly discolors with ultraviolet rays or visible light, and the production thereof. Regarding the method.

[Prior Art] Synthetic fiber guts for rackets used for hard tennis, soft tennis, badminton, squash, etc. are not colored, but users' preferences are diversified.
In recent years, those colored in various colors are preferred. This colored gut is generally dyed with a fiber dye in the final step of the gut manufacturing process.

However, with the recent preference for colors, there is a growing demand for using, in addition to the dyed gut, a gut which is rich in variability that the color of the synthetic resin gut for a racket changes with time. In addition, a gut in which the color of the gut changes with temperature (thermotropic) has been proposed (Japanese Utility Model Publication No. 2-45772).

[Problems to be Solved by the Invention] However, in the prior art such as the above-mentioned actual Kaihei, generally, the temperature change during sports time is not so large, and as a result, the width of the hue change changes narrowly. The color was non-uniform, not satisfactory, and the color of discoloration was not sufficient.

In order to solve the above-mentioned problems of the prior art, it is an object of the present invention to provide a synthetic fiber gut for a racket that reversibly changes with ultraviolet rays or visible rays and is highly variable.

[Means for Solving the Problems] In order to achieve the above object, the synthetic fiber gut for a racket of the present invention is composed of a plurality of filament fibers made of synthetic resin and a coating resin that integrates the filament fibers. A gut made of at least a synthetic fiber for a racket, wherein a photochromic material is present in the coating resin.

Further, the method of the present invention is a method for producing a synthetic fiber gut for a racket by applying a coating resin to a filament fiber made of a plurality of synthetic resins to integrate them, and adding a photochromic material to the coating resin component. It is characterized by

[Operation] According to the above-described configuration of the present invention, since the photochromic material is present in the coating resin in which the filament fibers made of a plurality of synthetic resins are integrated, the color changes when irradiated with ultraviolet rays or visible light. It is possible to use a synthetic fiber gut for a racket that changes reversibly and is highly variable.

According to the method of the present invention, since the photochromic material is added to the resin component for coating, the gut of the present invention can be efficiently and rationally produced.

[Examples] The present invention will be described in more detail with reference to the following examples.

The gut made of synthetic fiber in the present invention means, for example, a plurality of monofilament fibers twisted together and integrated with a coating resin. More specifically, it is composed of, for example, a core yarn and a leather yarn, and the core yarn is a monofilament of 1,000 to 20,000 denier (d), and usually 1,000 d to
The one with 10,000d is used.

The constituent component (material) of the monofilament is a filament made of a fiber-forming resin such as polyamide, polyester, polyethylene, polyurethane, polyphenylene sulphite, polyether ether ketone, polyvinyl alcohol, polyolefin, polystyrene and polyacrylonitrile. These are polymer elastic resin such as urethane resin, acrylic resin,
It can be applied even if it is impregnated or coated with a silicone-based resin or a fluorine-based resin, or if it is a composite of two-component system and three-component system (conjugate system). Moreover, it does not matter even if it contains an antioxidant in advance.

The winding yarn is a filament yarn of 30 to 1,000 d and has the same constituent components as the core yarn. The commonly used thickness is 50 to 800 d, and is determined by the number of core yarns, the number of winding yarns, and their ratio depending on the outer thickness of the gut.

And when using core yarn and winding yarn, 50 ~ 20,0
Composed of 00d monofilament or flat film. It does not matter if it is hollow in itself.

The resin in the resin processing of the present invention is not particularly limited in the present invention as long as it can effectively fix the twisting of the twisted yarn. It is desirable to use an ultraviolet curable resin for quick fixation. The ultraviolet curable resin may be any one containing a photopolymerizable prepolymer and a photoinitiator, and additionally, a sensitizer, a filler, an inert organic polymer, a leveling agent, a thixotropic agent, a thermal polymerization inhibitor, a solvent. It does not matter even if it contains.

As the photopolymerizable prepolymer, polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate,
Examples thereof include alkyd acrylate and polyol acrylate, and polyester acrylate, polyurethane acrylate, or epoxy acrylate is preferable.

The various acrylates are preferable because they are hardened in a short time by irradiation with ultraviolet rays and exhibit excellent adhesiveness with nylon, which is a polyamide-based synthetic fiber.

As the photoinitiator, sulfur compounds, acetophenones,
Carbonyl compounds such as benzophenone may be mentioned.

In addition, as a method for curing the resin, for example, dry heat,
Examples include steaming, high frequency, and radiation, but ultraviolet rays and electron beams are preferable in the sense that they are cured in an extremely short time to firmly fix the twist of each fiber.

The thickness of the resin layer is about 50 to 500 μm, though it depends on the ratio of the gut, core yarn, and leather yarn to be used.

Further, as another bonding method, a nylon resin having good adhesiveness is used so that the mono (multi) filaments and the leather threads are sufficiently fixed. Nylon adhesives are, for example, nylon resins that are dissolved in a solvent such as phenol or formic acid, and if necessary diluted with a solvent such as trichlorethylene, perchlorethylene or ethane dichloride, and are extremely adhesive. .

As a coating method, for example, a method of melting and adhering to form a film. This layer can prevent fiber fatigue during stretching and hitting, improve durability, wear resistance, and the like, and improve quality. Nylon, urethane and the like are preferable as the above resin from the viewpoint of water resistance and abrasion resistance.

The photochromic material used in the present invention is a photochromic compound such as naphthoxazine-based, fluquid-based, spirooxazine-based, and spiropyran-based, and is colorless or light blue to dark blue (i.e., ultraviolet light, 300 to 400 μm) upon irradiation with light (for example, ultraviolet light, 300 to 400 μm). Such as those that reversibly change color to red purple. Generally, it is used by being microencapsulated with melamine resin, urea, gelatin, inorganic silica, etc. and encapsulated in capsules. In addition, it may be copolymerized with a coating resin.

As an example of the photochromic material, the structural formula of the fluquid compound is shown in formula (I), and the structural formula of the spirooxazine compound is shown in formula (II). However, in the formulas (I) and (II), R is a methyl group.

The concentration of the photochromic material used in the present invention is
Depending on the thickness of the racket and gut, it is 0.01 to 50% by weight, preferably 0.1 to 1 based on the coating resin used.
It is 0% by weight.

The method of applying to the racket gut using the photochromic material used in the present invention, the method of applying in the bath of the coating resin to which the photochromic material is added, the method of squeezing and drying with an appropriate mangle to the gut, the photochromic material was added. Dipping the coating resin in the gut and then squeezing it with a suitable mangle, then steaming, immersing it in the gut and then squeezing it with a suitable mangle, and then heating it with high frequency, adding it to molten nylon resin and applying it to the gut, acrylic, urethane, etc. Examples of the method include a method in which the resin is added to the resin and added to the gut, and a method in which the resin is added to the molten nylon resin is recommended from the viewpoint of durability. However, the resin is not limited to the application method as long as it can apply the resin that reversibly changes with light to the surface of the gut.

Next, the drawings will be described. FIG. 1 is a cross-sectional model view of the gut 1 according to the first embodiment. The resin coating layer 3 on the surface is shown in FIG.
And the photochromic material is present in the resin layer impregnated in the layer between the multifilaments 2 inside.

Next, FIG. 2 is a cross-sectional model view of the gut 4 of Examples 2 to 4, and shows a gut composed of a thick filament 5 as an inner layer, a thin filament 6 on the surface thereof, and a resin coating layer 3. In this case, in Example 2, the inner thick filament 5 was used.
It is an example of coating with a resin to which a photochromic material is added, and Examples 3 to 4 are examples of adding a photochromic material to the coating layer 3.

Further, FIG. 3 shows an example in which another filament layer 8 is further provided on the thin filament layer 6 shown in FIG. 2, and the whole is coated with the resin 3 to which the photochromic material is added.

Next, FIG. 4 is a partial cross-sectional perspective view of the gut 4 of FIG.

Next, FIG. 5 shows an example of the method of the present invention. A gut is taken out from a supply gut 11 in which a plurality of monofilaments are twisted to a large number (in the present invention, this is referred to as a plurality), and twisted in a twist zone 10 and guided. Through resin coating tank
Lead to twelve. In the resin coating tank 12, a coating solution 15 containing at least a coating resin component and a photochromic material component is prepared. If necessary, pigments, various stabilizers, additives, solvents for viscosity adjustment, etc. may be added. The resin coating tank 12 is provided with guide rolls 13 and 13 and a mangle 14 for liquid drawing. The gut exiting the mangle 14 is guided to the dryer 16, dried and finally wound up into a take-up gut 17.

A specific experimental example will be described below.

Example 1 A nylon multifilament having a single filament fineness of 6d and a single yarn number of 1350 was twisted at a twist number of 100 turns / m while being resin-coated. The coating material is a polyurethane acrylate obtained by reacting a polyester of 1,6-hexanediol and adipic acid with tolylene diisocyanate and 2-hydroxyacrylate, and adding trimethylol and propanol acrylate as photopolymerizable monomers. Further, an ultraviolet curable resin obtained by adding benzophenone as a photoinitiator was added, and this was irradiated with ultraviolet rays using a high pressure mercury lamp. Further, 0.03% by weight of a photochromic material "Photorome 14" (trade name, manufactured by Nippon Chemix Co., Ltd., spironaphthoxazine type), which is discolored by ultraviolet rays, was added to and mixed with nylon-6. Then attach this coating material to the gut,
It was passed through a nozzle with a diameter of 1.1 mm. It was made into a film and coated. The coating temperature was 240 ° C.

The linear body thus obtained had a diameter of 1.14 mm.

In addition, as a comparison, a sample was prepared without the photochrome 14 at the time of coating (Comparative Example-1).

Example 2 A nylon resin was dissolved in dichloroethane, diluted with phenol to 50%, and a resin Photorome 15 (manufactured by Nippon Chemix Co., Ltd.) which was discolored by ultraviolet rays was dissolved in toluene, and then dissolved in the nylon resin. 0.1% by weight,
Immerse 0.8 mm diameter nylon 6-monofilament,
Squeeze to 80% by weight with a mangle and then 160d nylon 6-
The monofilament was wound and dried.

After that, the core yarn and the leather yarn were formed into a film and coated with the melted nylon-6 resin.

In addition, as a comparison, a core thread in which the resin Photorome 15 (manufactured by Nippon Chemix Co., Ltd.) that is discolored by ultraviolet rays was not prepared was prepared (Comparative Example 2).

Example 3 Nylon resin was dissolved in dichloroethane, diluted with phenol to 50%, and a nylon 6-monofilament having a diameter of 0.8 mm was immersed therein as a core thread.
%, And 160d nylon 6-monofilament previously dyed under the following conditions was wound and dried.

Next, in the same manner as in Example 1, a resin photochrome 14 that changes color by ultraviolet rays was added, and a film was formed and coated.

In addition, as a comparison, a sample was prepared in which the resin Photorome 14 (manufactured by Nippon Chemix Co., Ltd.), which is discolored by ultraviolet rays during coating, was not included (Comparative Example 3). The dyeing conditions (% represents% to the yarn weight) were as follows.

Kayacryl Rhodamin FB 0.5% (Nippon Kayaku) Acetic acid (90%) 0.5% / L Treated at 80 ° C for 20 minutes-washed with water, treated at room temperature for 20 minutes.

Example 4 Nylon resin was dissolved in dichloroethane, diluted with phenol to 50%, and nylon 6-monofilament having a diameter of 0.8 mm was immersed therein as a core yarn, and the mixture was mixed with 80 mangles.
% And nylon 6-monofilament having a diameter of 0.2 mm was wound on it and dried.

Next, 50 parts of this urethane resin (Samprene SP-25, Sanyo Kasei Co., Ltd.), 25 parts of ethyl acetate, 25 parts of dimethylformamide, and 0.1 part of a resin photorome 14 which is preliminarily dissolved in toluene to change its color by ultraviolet rays It was dipped in the melted solution and squeezed to 80% with mangle to dry.

In addition, as a comparison, one in which the resin Photorome 14 (manufactured by Nippon Chemix Co., Ltd.) which is discolored by ultraviolet rays during resin processing was not prepared was prepared (Comparative Example 4).

The results are shown in Table 1.

All samples passed the Fade Grade 3 irradiation.

As shown in Table 1, in Examples 1 to 4, the color changed well when exposed to sunlight, and the light fastness was good because the color changed due to the light even after irradiation of the third grade fade.

As described above, according to the embodiments of the present invention, it is possible to provide a gut for a synthetic fiber racket used for hard tennis, soft tennis, badminton, squash, etc., in which the color changes outdoors and indoors. This gut is highly durable and changes its color in a very short time by ultraviolet rays, so that the user can enjoy the change in discoloration.

[Effects of the Invention] As described above, according to the present invention, the photochromic material is present in the coating resin in which the filament fibers made of a plurality of synthetic resins are integrated. Was reversibly changed, and it was possible to obtain a synthetic fiber gut for rackets, which was highly variable.

Further, according to the method of the present invention, since the photochromic material is added to the coating resin component, the gut of the present invention can be efficiently and rationally produced.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a gut according to an embodiment of the present invention, and FIG.
FIG. 3 is a schematic sectional view of a gut according to another embodiment of the present invention, FIG. 3 is a schematic sectional view of a gut according to another embodiment of the present invention, and FIG. 4 is a partial sectional perspective view of the gut shown in FIG. FIG. 5 is a process chart showing an embodiment of the method of the present invention. 1,4,7 ... Gut, 2 ... Filament, 3 ... Resin coating layer, 5 ... Inner layer thick filament, 6,8 ...
… Thin filament, 10 …… twisting zone, 11 …… Supply gut, 12 …… Resin coating tank, 13 …… Guide roller, 14 …… Mangle, 15 …… Coating solution, 16 ……
Dryer, 17 ... Roll-up gut.

Front Page Continuation (72) Inventor Shigeaki Takahashi 306 Bakugaya, Tojo-cho, Kato-gun, Hyogo Prefecture GOSEN R & D Center Co., Ltd.

Claims (2)

[Claims] 1. A synthetic fiber gut for a racket comprising at least a filament fiber made of a plurality of synthetic resins and a coating resin integrating the filament fibers, wherein a photochromic material is contained in the coating resin. A gut made of synthetic fiber for a racket characterized by being present. 2. A method for producing a synthetic fiber gut for a racket by applying a coating resin to filament fibers made of a plurality of synthetic resins and integrating them, wherein a photochromic material is added to the resin component for coating. A method for producing a synthetic fiber gut for a racket, comprising: