JP7172427B2 - belts and harnesses - Google Patents

Description

The present invention relates to a belt and a safety belt using the same.

Fibers such as polyester fibers and polyamide fibers can satisfy the performance required for belts, such as high strength, high bending strength, elongation recovery, impact resistance, abrasion resistance, weather resistance, and chemical resistance. It is a fiber and is widely used as construction materials such as sling belts, connecting belts, safety belts on poles, civil engineering materials, secondary materials such as belts for bags.

Many of these are used outdoors, and their physical properties deteriorate due to the effects of sunlight, wind and rain, seawater, cement, etc. Especially, due to the influence of moisture, the synthetic fibers hydrolyze and their physical properties deteriorate, and the adhesion of sewage can reduce their physical properties. In order to solve the problem of dirt, mold, and deterioration due to freezing of absorbed water in cold regions, and the problem that water permeates the rope, making it heavy and difficult to handle. Patent Document 1 discloses a method in which 1 to 3.0% by weight of a perfluoroalkyl group-containing compound is applied together with a spinning oil agent, the fibers are used to weave a belt, and then a heat treatment is performed at a temperature of 130 to 200°C. there is In the invention described in Patent Document 1, the individual fibers constituting the belt have water-repellent properties due to the above configuration, so that the belt does not become dirty due to adhesion of sewage or mold. It is also described that a belt can be obtained in which moisture does not permeate inside due to capillary action, and workability is not reduced due to weight increase and deterioration due to freezing is less likely to occur.

By the way, in Patent Document 2, a fibrous structure in which the surface of a single fiber is coated with a resin film containing an organic fluorine compound via a resin film containing a triazine ring-containing compound or a resin film containing an organic fluorine compound and a triazine ring-containing compound. It has excellent durability of water repellency, oil repellency and antifouling property, and it is described that it can be effectively used for sports clothing, uniform clothing, casual clothing, general clothing, bedding, interior, etc. ing.

JP-A-07-305274 WO2007-083596

For example, in the field of civil engineering and construction, when various painting operations are carried out using a safety belt composed of a belt, if paint adheres to the belt, the paint will permeate the interior of the belt over time, causing the belt to harden and improve workability. Besides, there are problems such as deterioration of aesthetics, shortening of product life, and need of frequent replacement work.

The belt described in Patent Document 1 can impart a water-repellent effect to the inside of the high-density belt due to its structure, but since the perfluoroalkyl group-containing compound is only imparted in the spinning process, paint such as paint adheres to the belt. Since the paint penetrates between the fibers constituting the belt and solidifies, the belt hardens and the paint adhering between the fibers cannot be removed.

In addition, the fiber structure described in Patent Document 2 is excellent in both water repellency and oil repellency, and is also excellent in washing durability. Although it is difficult for paint to adhere to the surface, when exposed to repeated rubbing, the film structure is destroyed, and the paint adheres to the affected area and solidifies.

Accordingly, the present invention provides a belt having excellent workability and durability, which has antifouling and water-repellent effects, does not easily get wet with water, and is capable of preventing the penetration of adhered paint into the interior of the belt. An object of the present invention is to provide a safety belt using

In order to solve the above problems, the present invention employs the following means.

(1) A belt made of a single fiber surface coated with a resin film containing an organic fluorine compound via a resin film containing a triazine ring-containing compound or a resin film containing an organic fluorine compound and a triazine ring-containing compound. A belt having a water repellency of grade 3 or higher and an oil repellency of grade 4 or higher after 2000 times of the hexagonal bar pressing abrasion test specified in the seat belt standard JIS D 4604 (2006).

(2) The belt according to (1), wherein the resin coating containing the triazine ring-containing compound or the resin coating containing the organic fluorine-containing compound and the triazine ring-containing compound has a thickness of 5 to 100 nm.

(3) The belt according to (1) or (2), wherein the organic fluorine compound-containing resin coating contains a triazine ring-containing compound and/or an isocyanate compound.

(4) The belt according to any one of (1) to (3), wherein the fibers have a tensile strength of 3.0 cN/dtex or more and a total fineness of 500 dtex or more.

(5) The belt according to any one of (1) to (4), which has a breaking strength of 15.0 kN or more.

(6) The belt according to any one of (1) to (5), which is made of woven fabric and has a cover factor of 2800 or more.

(7) A safety belt using the belt according to any one of (1) to (6).

The belt of the present invention has antifouling and water-repellent effects, does not easily get wet with water, is capable of preventing permeation of adhering paint to the inside of the belt, and has excellent workability and durability. In addition, safety belts that use this material can prevent hardening of the belt due to paint that adheres to it, making it easy to adjust the position of the buckle and providing excellent workability. Become.

The present invention relates to a belt comprising a single fiber surface coated with a resin film containing an organic fluorine compound via a resin film containing a triazine ring-containing compound or a resin film containing an organic fluorine compound and a triazine ring-containing compound. The fiber structure has a water repellency of grade 3 or higher and an oil repellency of grade 4 or higher after 2000 times of the hexagonal bar pressing abrasion test specified in the seat belt standard JIS D 4604 (2006). It's a belt.

Examples of fibers used in the present invention include synthetic fibers such as polyester fibers, polyamide fibers, polyolefin fibers and polyvinyl alcohol fibers. Aromatic polyester fibers, aromatic polyamide fibers, highly oriented polyolefin fibers, highly oriented polyvinyl alcohol fibers, and the like, which are contained in these fibers, are also suitably used.

As the polyester fiber, a fiber containing polyethylene terephthalate as a main component can be preferably used. Among others, polyester fibers made of polyethylene terephthalate homopolymer or copolymerized polyester obtained by copolymerizing a third component to such an extent that the properties of polyethylene terephthalate are not impaired can also be used.

As for polyamide fibers, fibers containing nylon 6, nylon 66, nylon 46, etc. as the main component can be preferably mentioned. Among others, it is possible to use a polyamide fiber made of a copolymerized nylon such as a nylon 6 copolymer, a nylon 66 copolymer, or a nylon 46 copolymer in which a third component is copolymerized to such an extent that the properties are not impaired.

Fibers containing polyethylene terephthalate as a main component are particularly preferably used from the viewpoints of belt mechanical properties, dyeability, and cost. In particular, the repeating unit of ethylene terephthalate constituting polyethylene terephthalate is preferably 98 mol % or more, more preferably 100 mol %.

The fibers used in the present invention include matting agents such as titanium oxide, calcium carbonate, kaolin and clay, pigments, dyes, lubricants, antioxidants, heat-resistant agents, heat-resistant agents, light-resistant agents, ultraviolet absorbers, antistatic agents and Flame retardants and the like can be included.

In the fiber used in the present invention, the single fiber fineness is not particularly limited as long as it satisfies the properties specified in the present invention, but the single fiber fineness can be exemplified as a preferable range of 2 dtex or more, and 4 to 25 dtex. can be exemplified as a more preferable range. When the monofilament fineness satisfies the above range, it is advantageous in terms of abrasion resistance, and is preferable in terms of excellent durability in preventing permeation of adhering paint into the interior of the belt.

In addition, in the fiber used in the present invention, the total fineness is not particularly limited as long as it satisfies the properties specified in the present invention. can be exemplified as a more preferable range. When the total fineness satisfies the above range, it is preferable from the viewpoint of being excellent in durability to prevent permeation of adhering paint into the interior of the belt.

Furthermore, the cross-sectional shape of the fibers used in the present invention is not particularly limited, and fibers having various cross-sections such as flat cross-sections, hollow cross-sections, and core-sheath composite cross-sections are used for the purpose of thinning, improving rigidity, and improving design. can do.

In the present invention, the fiber used preferably has a tensile strength of 2.5 cN/dtex or more from the viewpoint of durability to prevent the adhered paint from penetrating into the inside of the belt. Among them, the tensile strength is more preferably 3.0 cN/dtex or more, more preferably 3.5 cN/dtex or more. If the tensile strength of the fiber is too low, it is not preferable because when used as a belt, yarn breakage is likely to occur not only due to external force in the pulling direction, but also due to abrasion. The upper limit is preferably 12 cN/dtex or less from the viewpoint of flexibility of the belt.

In addition, it is preferable that the breaking elongation of the fiber is about 20 to 70% because it has impact relaxation properties for belt applications.

Next, the method for producing the fiber used in the present invention is not limited as long as it can produce the belt defined in the present invention. Take melt spinning as an example. The present invention is not limited to this, and other ordinary spinning methods can be employed as long as the belt defined by the present invention can be obtained.

The intrinsic viscosity (IV) of the polyester used in the present invention is preferably in a specific range from the viewpoint of controlling the breaking strength. In the case of polyethylene terephthalate, the intrinsic viscosity is in the range of 0.8 to 1.3. It is preferably 0.9 to 1.2, more preferably 0.9 to 1.2. Polyethylene terephthalate resin chips having a repeating unit of 98 mol % or more of ethylene terephthalate filled in a hopper in a nitrogen atmosphere are melted and kneaded with an extruder, introduced into a spinning pack, and discharged from a spinneret. . When adding the aforementioned additives, etc., there is a method of directly mixing them with an extruder, or a method of preparing polyethylene terephthalate resin master chips containing additives, etc. at a high concentration in advance and blending the chips before melting. can be adopted.

The melt spinning temperature can be appropriately changed depending on the intrinsic viscosity, the type of polymer, etc., but is preferably 270 to 320°C. If spinning is carried out at less than 270°C, sufficient fluidity may not be obtained when the polymer is melted, and if the temperature exceeds 320°C, the polymer may decompose and the polyester fiber of the present invention may not be obtained. have a nature. Immediately below the spinneret, the upper end is 0 to 15 cm from the spinneret surface, and the range of 5 to 30 cm from the upper end is surrounded by a heating cylinder and/or a heat insulating cylinder, and the spun yarn is passed in a high temperature atmosphere of 250 to 350°C. An undrawn yarn having a low degree of orientation of the amorphous portion can be obtained by passing the yarn for a short period of time. If the degree of orientation of the amorphous part is high, the elongation is low and the secondary rising stress is steep, so the above conditions are preferable.

The unstretched yarn that has passed through the high-temperature atmosphere is then preferably cooled and solidified by blowing air at 10 to 100°C, preferably 15 to 75°C. If the temperature of the cooling air is less than 10° C., a large-sized cooling device is required in addition to the normal device, which is not preferable. If the temperature of the cooling air exceeds 100° C., the swaying of the single fibers increases during spinning, and collisions between the single fibers occur, making it difficult to produce fibers with good reeling properties. The air cooling device may be of a horizontal blowing type (uniflow type) or of an annular blowing type. Moreover, when a high cooling effect is required like a monofilament, a cooling method such as water cooling can be adopted.

The undrawn yarn that has been cooled and solidified is then oiled with an oiling device. The oil may be either water-based or non-aqueous. It is preferable to use an oil composition containing a smoothing agent as a main component, including a surfactant, an antistatic agent, an extreme pressure agent component, etc., and excluding an active component for the polyester resin. For example, a non-aqueous oil obtained by diluting an alkyl ether ester as a smoothing agent component, an alkylene oxide adduct of a higher alcohol as a surfactant component, and an organic phosphate salt as an extreme pressure agent component with mineral oil is more preferable.

The unstretched filament to which the oil agent has been applied is wound around a take-off roller and taken off. The surface speed of the take-up roller, that is, the take-up speed is preferably 2000 to 6000 m/min, more preferably 2500 to 5000 m/min. When the take-up speed is less than 1000 m/min, the yield stress of the SS curve is low, the amount of energy that can be absorbed in the constant stress elongation region is small, and sufficient energy absorption is not performed, and it is necessary to elongate to the region where stress rises. As a result, the stress applied to the human body or the like increases. If the take-up speed exceeds 6000 m/min, the yield stress becomes high in the SS curve, and the load applied to the human body or the like during impact absorption becomes large.

After being taken up at the above take-up speed, the undrawn yarn is preferably heat-treated at a draw ratio of 1 to 1.35 times, more preferably 1 to 1, after being taken up once, or continuously without being taken up. 0.3 times, more preferably 1 to 1.25 times. When the draw ratio exceeds 1.35 times, the slope of the secondary rising stress after the constant stress elongation region becomes steep, so when a fiber product is subjected to an impact that requires a large amount of energy absorption, it is sharp. There is concern that a large amount of load may be applied to the human body.

For example, as a drawing method, similar to the take-up roller (hereinafter sometimes abbreviated as 1FR), a yarn feeding roller (hereinafter sometimes abbreviated as 2FR) is a Nelson roller having two rollers as one unit, A first drawing roller (hereinafter sometimes abbreviated as 1DR), a heat set roller (hereinafter sometimes abbreviated as 2DR) and a relaxation roller (hereinafter sometimes abbreviated as RR) are arranged side by side, and the yarn is sequentially drawn. The film is wound and subjected to stretching heat treatment under the above conditions. At this time, the number of stages of stretching, the number of rollers, and the stretching ratio between rollers are not particularly limited. Stretching is usually performed between the take-up roller and the yarn supply roller to bundle the yarn. The stretch rate is preferably in the range of 1-5%. The take-off roller is heated to 50-90° C. to preheat the take-off yarn and send it to the next drawing process.

Drawing is performed between a yarn supplying roller and a heat set roller, the temperature of the yarn supplying roller is set to 70 to 120°C, and then the yarn is drawn by the first drawing roller (100 to 140°C) at a draw ratio of 90 to 98%. Then, heat setting is performed while the yarn is drawn at 1 to 5% of the total draw ratio with heat set rollers. The reason why the yarn is drawn by the first drawing roller at a drawing ratio of 90 to 98% is that the drawing is performed in a fluid state in which the molecules are not crystallized, thereby enhancing the drawing effect and promoting the orientation. be. The stretched yarn is heat-set at 130 to 170° C. with a heat-setting roller, and then 0-7%, preferably 0-5%, more preferably 0-7% between the heat-setting roller and the relaxation roller. It is subjected to 3% relaxation treatment and wound up by a winder. In the relaxation treatment, it is possible not only to remove the strain caused by the hot drawing, but also to fix the structure achieved by the drawing, relax the orientation of the amorphous region, and reduce the thermal shrinkage. A non-heated roller or a roller heated to 150° C. or lower is used as the relaxation roller.

Further, in order to obtain a high-quality polyester fiber by reducing the generation of fluff, a high-pressure fluid is sprayed on the fiber yarn between the yarn supplying roller and the first drawing roller to entangle the yarn constituting the fiber. may be applied, and the yarn may be drawn while being bundled. As the entangling device for entangling and bundling the yarn, an entangling nozzle that is usually used for entangling and bundling the yarn just before winding the yarn can be used. It is effective to use the entangling device during the first stage of drawing, but in addition to the first stage, the entangling device may also be used during the second and third stages of drawing. The degree of entanglement (CF value) applied to polyester fibers is preferably 5-70, more preferably 10-60. If the degree of entanglement is less than 5, it is not preferable because the process passability in high-order processing is deteriorated. On the other hand, if the degree of entanglement is greater than 70, loops are likely to occur, making it difficult to stably perform high-order processing.

The feature of the polyester fiber of the present invention is that the upper end is 0 to 15 cm from the spinneret surface, the range of 5 to 30 cm from the upper end is surrounded by a heating cylinder and / or a heat insulating cylinder, and the spun yarn is heated to a high temperature of 250 to 350 ° C. After passing through the atmosphere for a short period of time, wind of 10 to 100° C., preferably 15 to 75° C. is blown to rapidly cool and solidify the polyester fiber, and the molecular chains are aligned at a take-up speed of 1000 to 2500 m/min. , Oriented, further stretched at a low magnification of 1 to 1.35 times, applied heat in the vicinity of the crystallization start temperature (100 to 120 ° C.) for a long period of time, and further heat set at a low temperature of 130 to 170 ° C. It can be obtained by combining

Next, a method for manufacturing the belt of the present invention will be described, but the manufacturing method is not limited to this as long as it satisfies the provisions of the present invention.

A belt base fabric can be obtained by weaving fibers such as the synthetic fiber multifilament produced as described above using a loom such as a needle loom under the following conditions.

For example, synthetic fiber multifilament made of normal circular cross-section yarn is used for weft, and fiber with fineness of 880 to 1760 dtex and number of single fibers of 35 to 880 is used for base fabric of belt as warp. It is also possible to use desired fibers in each of the vertical and horizontal directions.

As long as the range defined by the present invention is satisfied, the weave density is not limited and can be changed as appropriate.

In addition, there is no particular rule for the weave structure at this time, and plain weave, twill weave, satin weave, or a weave structure combining them can be adopted. is preferred.

The thickness of the belt is not specified as long as it satisfies the stipulations of the present invention, but it is preferably in the range of 2.0 to 3.0 mm. If the thickness of the belt exceeds 3.0 mm, there is a problem of poor storability, and if the thickness of the belt is less than 2.0 mm, there is a concern that the belt will break when an impact is applied to it. have.

The cover factor of the fabric constituting the belt is not particularly limited, but is preferably 2,800 or more, preferably 2,800 to 5,500, and more preferably 3,000 to 5,000. If the cover factor is smaller than the above range, the durability of preventing the penetration of the adhered paint into the inside of the belt tends to decrease, and if the cover factor is large, the belt becomes hard and wearability decreases do. Here, the cover factor is a numerical value indicating the proportion of fibers in the unit area of the belt, and is calculated by the following formula.
Cover factor = [(fineness of warp yarn) (dtex)] ^1/2 × (density of warp yarn) (thread/2.54 cm) + [(fineness of weft yarn) (dtex)] ^1/2 × (weft yarn density) (book/2.54 cm)

The belt may be dyed if necessary. Dyeing may be performed by a conventional dyeing method, for example, a method of immersing the fabric in a dyeing bath and then treating it at 170 to 220° C. for 1 to 5 minutes can be used. The treatment temperature and time are appropriately adjusted according to the sublimation temperature of the dye. If the temperature is lower than the above range or if the treatment time is short, the dyeing of the fibers will be insufficient and the fastness will be lowered. On the other hand, when the temperature is higher than the above range or the treatment time is long, the sublimation fastness is also lowered. Usual polyester dyes such as anthraquinone dyes, azo dyes, nitrodigenylamine dyes, methine dyes and naphthoquinone dyes can be used as dyes. Desirable colors can also generally be obtained by combining red, blue and yellow dyes.

Furthermore, when dyeing, dispersion and level dyeing represented by ethoxylated dioctylphenol, anionic nonionic surfactants, alkyl alcohol polyglycol ethers, sulfate ester salts, etc., as long as the effects of the present invention are not impaired. In addition to agents, wetting agents, additives such as anti-migration agents, pH adjusters, UV absorbers and antioxidants may be added to the dye solution.

In the present invention, a triazine ring-containing compound-containing resin coating or an organic fluorine compound and triazine ring-containing compound-containing resin coating is formed on the surface of the single fibers constituting the belt. That is, a resin coating containing a triazine ring-containing compound as an essential component or a resin coating containing an organic fluorine compound and a triazine ring-containing compound as essential components is formed on the surface of a single fiber.

The triazine ring-containing compound used in the present invention is a compound containing a triazine ring and having at least two polymerizable functional groups, and examples thereof include those represented by the following general formula.

In the formula, R0 to R2 are
-H, -OH, _{-C6H5 ,}
-C _n0 H _2n0+1 (n0 is 1 to 2),
-COOC _n1 H _2n1+1 (n1 is 1 to 20),
-CONR3R4 or -NR3R4 (provided that R3 and R4 are -H, -OC _n3 H _2n3+1 , -OC _n3 H _2n3+1 , -CH ₂ COOC _n3 H _2n3+1 (n3 is 1 to 20), -CH ₂ OH, —CH ₂ CH ₂ OH, —CONH ₂ , —CONHCH ₂ OH—O—(X—O) _n4 —R5, where X is C ₂ H ₄ , C ₃ H ₆ or C ₄ H ₈ where n4 is 1 to 1500 and R5 is —H, —CH ₃ or —C ₃ H ₇ ).)

In addition to those represented by the above general formula, ethylene urea copolymer compounds, dimethylol urea copolymer compounds, dimethylol thiourea copolymer compounds, acid colloid compounds, and the like of the above compounds can also be used.

The method of forming the triazine ring-containing compound-containing resin coating or the organic fluorine compound and triazine ring-containing compound-containing resin coating (hereinafter referred to as "triazine ring-containing compound-containing resin coating") used in the present invention is as follows.

After the water-based liquid containing the monomer for forming the resin coating and the catalyst is applied onto the fibers, heat treatment is performed to polymerize the fibers.

Examples of such catalysts include catalysts for polymerizing monomers for forming a resin film, such as acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, maleic acid, phthalic acid, sulfuric acid, persulfuric acid, hydrochloric acid, and phosphoric acid. Acids and their ammonium salts, sodium salts, potassium salts, magnesium salts and the like, and one or more of these can be used. Among them, ammonium persulfate and/or potassium persulfate can be preferably used as a catalyst. The amount of such catalyst is preferably 0.1 to 20% by weight based on the amount of monomer used.

The heat treatment for such polymerization is preferably a dry heat treatment and/or a steam heat treatment at a temperature of 50 to 180° C. for 0.1 to 30 minutes. It is easy to form a smooth film, and the texture after film formation is soft. Such a steaming treatment preferably uses saturated steam or superheated steam at a temperature of 80 to 160°C, more preferably saturated steam at 90 to 130°C in the case of saturated steam, or superheated steam at a temperature of 110 to 160°C. Yes, all of which take a few seconds to a few minutes. After such steaming treatment, in order to remove unreacted monomers and catalysts and ensure color fastness, hot water washing at a temperature of 50 to 95 ° C., or washing using a nonionic surfactant or sodium carbonate. It is preferable to The adhering amount of the resin containing the triazine ring-containing compound or the like is preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight, based on the weight of the fiber.

In the present invention, when a resin coating containing an organic fluorine compound and a triazine ring-containing compound is formed on the surface of a single fiber, the coating is formed by performing the same treatment as described above using a mixed solution of a triazine ring-containing compound and an organic fluorine compound. can be formed. The mixing weight ratio of the triazine ring-containing compound and the organic fluorine compound (triazine ring-containing compound/organic fluorine compound) is preferably 1/0.001-1. However, when drying and heat treatment are performed after forming the film, the water repellency is grade 3 or less, preferably grade 2, so as not to impede the wettability and permeability of the treatment agent when treating with an organic fluorine-containing compound after such treatment. It is preferable to determine the mixing ratio so as to be as follows.

The organic fluorine compound may be of the same type as the fluorine compound used for the organic fluorine compound-containing resin film after the treatment, or may be a different type of fluorine compound. Usually, the film forming treatment, as described above, is treated with saturated steam or superheated steam, and a temperature of 50 to 95 ° C. is used to remove unreacted monomers and catalysts and to ensure color fastness. Wash with hot water or wash with a nonionic surfactant or sodium carbonate and dry. When further heat treatment is performed thereafter, the water repellency of the fluorine compound derived from the previously treated resin film containing the triazine ring-containing compound or the like develops on the surface of the base fabric of the belt. In this case, if the water repellency of the organic fluorine compound in the resin film containing the triazine ring-containing compound or the like is too high, the water repellency of the film increases. There is a concern that the pick-up rate of the containing aqueous solution may become too low, resulting in a decrease in workability. Therefore, the water repellency after drying and heat treatment is preferably class 3 or lower, more preferably class 2 or lower. When the water repellency after drying and heat treatment falls within the above range, it is preferable to use the same kind of compound from the viewpoint of workability. may be used to adjust the water repellency after drying and heat treatment.

The triazine ring-containing compound-containing resin film used in the present invention is obtained by cutting out the single fiber cross section after treatment with a microtome or the like, and measuring the film thickness of the resin film at three locations with a transmission electron microscope at a magnification of 100,000. and is preferably 5 to 100 nm.

A film having such a film thickness can be formed by using the above forming method. In the present invention, inorganic particles can be contained in the resin film containing the triazine ring-containing compound or the like.

Examples of the inorganic particles include aluminum oxide, silicon oxide, titanium oxide, kaolinite, talc, calcium carbonate, calcium silicate, and magnesium oxide, and these can be used alone or in combination of two or more.

The particle diameter of the above particles is preferably 5 to 400 nm, more preferably 10 to 100 nm, in terms of number average particle size measured by a light scattering method in the state of aqueous dispersion. The inorganic particles used in the present invention are preferably used in the form of an aqueous dispersion. The inorganic particles used in the present invention can be used by mixing with an aqueous solution of the polymerizable monomer for the resin coating, and the weight mixing ratio with the polymerizable monomer is preferably 0.03-1. 0, more preferably 0.05 to 0.5. By mixing the particles, the formability of the resin film containing the triazine ring-containing compound, etc. is improved, and a tough film can be formed, so that the durability can be further enhanced.

In the present invention, other compounds such as water absorbents, moisture absorbents, ultraviolet absorbers, light stabilizers, lubricants, anti-friction agents, organic particles, antistatic agents, and extinguishers are used within the range that does not impede the effects of the present invention during film formation. Odorants, antibacterial agents, flame retardants, coloring agents, deepening agents, water repellent agents, oil repellent agents, antifouling agents and the like may be added.

In the present invention, a resin film containing an organic fluorine compound is formed on the above-mentioned resin film containing a compound containing a triazine ring. As the organic fluorine compound, an acrylate compound containing a perfluoroalkyl group represented by the following general formula is preferably exemplified.

In the formula, R1 represents a hydrogen atom or a lower alkyl group, and Rf represents a group having a perfluoroalkyl group represented by CmF2m+1 and containing at least one group selected from a hydroxyl group and an unsaturated group. Note that m is an integer of 1 to 20, and n is an integer of 10 to 200.

Examples of such organic fluorine compounds include polymers or copolymers composed of one or more compounds represented by the above general formulas, or other polymerizable compounds such as acrylic acid, methacrylic acid, styrene, and vinyl chloride compounds. , and copolymers with polyethylene glycol.

As a method for processing the organic fluorine compound-containing resin film, the fiber structure with the triazine ring-containing compound film formed is immersed in a water-based liquid or a solvent-based liquid, and squeezed with a mangle or the like so that the target adhesion amount is obtained. , preferably dried at a temperature of 100 to 150 ° C., preferably heat-treated at a temperature of 160 to 190 ° C., or immersed in a diluted solution at a temperature of 60 to 130 ° C. and adsorbed on the fiber surface. can be used, but is not limited to this method.

The adhered amount of the organic fluorine compound-containing resin is preferably 0.1 to 8% by weight, more preferably 0.5 to 4% by weight, based on the fiber weight.

The organic fluorine compound preferably contains at least one of a triazine ring-containing compound and an isocyanate compound to form a coating layer.

As the triazine ring-containing compound, the same type as that used for forming the film may be used, or a different type may be used. As the isocyanate-based compound, a compound having two or more isocyanate groups obtained by blocking the isocyanate group with an oxime-based compound such as sodium sulfite and methyl ethyl ketone noxime can be used.

Furthermore, other compounds, such as water absorbents, moisture absorbents, ultraviolet absorbers, light stabilizers, lubricants, antifriction agents, inorganic particles, organic particles, antistatic agents, deodorants, as long as they do not impair the effects of the present invention. , antibacterial agents, flame retardants, coloring agents, deepening agents, water repellent agents, oil repellent agents, antifouling agents, and the like can be added.

The belt of the present invention thus obtained can achieve grade 3 or higher in water repellency and grade 4 or higher in oil repellency after 2000 times of the hexagon bar press abrasion test specified in the seat belt standard JIS D 4604 (2006). is.

In the present invention, by adopting the embodiment as described above, the organic fluorine-based compound is not directly fixed to the fiber by itself, but is fixed through a resin film such as a triazine ring-containing compound, or the organic fluorine-based compound is further fixed to the fiber. Since the system compound is contained in the resin film together with the triazine ring-containing compound and fixed to the single fiber, the structure of the formed resin film is not fatally damaged by abrasion, so the belt is durable against abrasion. After 2,000 times of the hexagonal bar press abrasion test specified in the seat belt standard JIS D 4604 (2006), it exhibits high performance such as water repellency of grade 3 or higher and oil repellency of grade 4 or higher.

Furthermore, the film thickness of the resin film containing the triazine ring-containing compound etc. is preferably 5 to 100 nm, more preferably 10 to 100 nm. Here, the resin film containing a triazine ring-containing compound or the like is obtained by cutting out a single fiber cross section after treatment with a microtome or the like and measuring the film thickness of the resin film at three locations with a transmission electron microscope at a magnification of 100,000. show. In the case of having such a thin film structure, the single fibers have a degree of freedom when subjected to friction, and are not locally subjected to friction. In addition, even when subjected to bending, the thin film structure on the single fiber is less likely to crack or peel off due to the thin film structure, so even after the abrasion test, the penetration of water into the belt and the It is possible to prevent penetration of paint such as paint. Such an excellent effect is effective for any of water-based, solvent-based, and inorganic-based paints. By appropriately adjusting the ratio (triazine ring-containing compound/organic fluorine compound), the amount of the organic fluorine compound used can be optimized, and the processing cost can be reduced.

The belt of the present invention obtained by the above method is particularly suitable for use as a safety belt. For example, it can be used for a safety belt composed only of the polyester fiber of the present invention and a shock absorber type safety belt, but the usage is not particularly limited to this.

The shock absorber referred to in the present invention refers to a device for mitigating the impact that occurs when preventing a fall, and is a high-strength synthetic belt consisting of the belt of the present invention in the short part and normal circular cross-section thread in the long part. Examples include those composed of fiber multifilament fabrics. In the shock absorber type safety belt, the polyester fiber of the present invention used in the short portion begins to stretch and gradually absorbs the impact, and the long portion prevents the safety belt from breaking. With this configuration, at the beginning of the elongation of the short portion, the constant stress elongation region of the polyester fiber of the present invention absorbs a large amount of energy with a small impact on the human body, etc., reducing the load on the human body, etc. At the fully stretched stage, the long portion exerts its shock absorbing ability, and breakage of the safety belt can be suppressed.

Since the belt of the present invention is required to have high safety, the breaking strength of the belt is preferably within the following range. More preferably, it is 20.0 kN or more. It is preferably 60.0 kN or less from the point of handleability and wearability.

The belt obtained by the above method has excellent water and oil repellency even after abrasion, so even if paint or the like adheres to the belt during use, it can be prevented from penetrating into the interior of the belt, preventing the belt from hardening. product life can be extended.

Next, the present invention will be specifically described based on examples. However, the present invention is not limited only to these examples. Various modifications and modifications are possible without departing from the technical scope of the present invention. Methods for measuring various properties used in the present examples are as follows.

[Total fineness]
Based on JIS L1013 (1999) 8.3.1a) A method, using a measuring machine manufactured by Nakayama Electric Industry Co., Ltd., an initial load of display fineness × 0.45 mN / dtex was applied and measured, and the total fineness and did.

[Single fiber fineness]
It was calculated by dividing the total fineness by the number of single fibers. Here, the number of single fibers was calculated according to JIS L1013 (1999) 8.4.

[Breaking elongation and breaking strength of fiber]
It was determined from the SS curve (elongation-strength characteristics) obtained under the conditions of a sample length of 10 cm and a tensile speed of 30 cm/min using a "Tensilon" tensile tester manufactured by Orientec Co., Ltd.

[Intrinsic viscosity]
The relative viscosity η of a solution prepared by dissolving 8 g of a sample in 100 mL of orthochlorophenol was measured at 25° C. using an Ostwald viscometer, and was obtained by the approximate expression IV=0.0242 η+0.2634.

[Belt breaking strength]
Using Shimadzu Corporation's precision universal testing machine "Autograph AG-Xplu", it was determined from the SS curve (elongation-strength characteristics) obtained under the conditions of a sample length of 60 cm and a tensile speed of 60 cm/min.

[Thickness of Resin Coating Containing Triazine Ring-Containing Compound etc.]
A sample was cut out with a microtome, and the film thickness (nm) of the triazine ring-containing compound-containing resin film was measured by observing the single fiber cross section at 100,000 magnifications using a transmission electron microscope (TEM). The thickness of the resin film was measured at three locations, and the average value was calculated as the thickness.

[Belt thread density]
A loupe directly counted the number of warp and weft threads per 2.54 cm.

[Belt cover factor]
The cover factor of the belt is calculated by the following formula.
Cover factor = [(warp fineness) (dtex)] ^1/2 x (weft density) (thread/2.54cm) + [(warp fineness) (dtex)] ^1/2 x (weft thread density) (book/2.54 cm)
Here, the density of the warp yarn and the weft yarn is measured by the method described in [Thread density of the belt]. The warp yarn density of is the sum of the density of the warp yarn on the front side and the warp yarn on the back side.

The fineness of the warp yarn and the weft yarn is calculated by the following procedure from a cross-sectional photograph of the belt taken with a scanning electron microscope.
(a) Twenty single fibers constituting one multifilament are randomly selected, binarized by image processing, and the average cross-sectional area is calculated. Here, as the image software, "ImageJ", which is general free software and is open to the public, is used.
(b) Here, the fiber diameter was calculated from the cross-sectional area on the assumption that the cross section of the single fiber was a perfect circle.
(c) Since the fineness (dtex) is the weight (g) of a 10,000 m fiber length, the single fiber fineness was calculated from the single fiber diameter with the general density of 1.38 g/cm ³ for polyester. .
(d) The number of single fibers that make up one multifilament is counted from the cross-sectional photograph, and the product of the single fiber fineness calculated in (c) and the number of single fibers is taken as the total fineness of the yarn, which is used to calculate the cover factor. board.

[Water repellency]
The obtained belt was measured by the spray method specified in JIS L 1092 "Testing method for waterproofness of textile products" (1998).

[Oil repellency]
It was measured by the method specified in AATCC TM-1966.

[Confirmation of anti-penetration effect of paint]
A 5 cm×5 cm hole is made in the center of a 1 mm thick metal plate about 5 cm wider than the belt width. In addition, a metal plate with the same width and without holes is also prepared. At the four corners of the metal plate, holes are drilled for fixing with M4 screws. The belt is sandwiched between two metal plates and fixed with M4 screws. Pour 3 g of Bonflon GT (AGC Coatec Co., Ltd.) fluorine-based paint for metal into the hole of 5 cm x 5 cm in the metal plate, scrape off the paint with a stick coated with fluorine resin, and apply the paint to the belt surface. . The applied material is allowed to air dry at room temperature for one week. After air-drying, the belt is visually checked from the reverse side of the painted surface for the presence or absence of paint strike-through. In addition, the paint-applied portion is folded in the longitudinal direction of the belt, and the bending hardness is sensory-evaluated in the following three stages.
◯: It has the same bending hardness as the belt before paint application.
Δ: Slight curing is observed, but when the belt is held with both hands and slightly bent, the coated portion can be bent as the vertex of the bend.
×: The paint strikes through and hardens, and the applied part cannot be bent with the top.

Moreover, the abrasion test method implemented in the present Example is as follows.

[Abrasion test]
The belt is worn 2000 times under the conditions conforming to the hexagon bar pressing abrasion test method specified in the seat belt standard JIS D 4604 (2006).

(Example 1)
[Manufacturing of polyester fiber]
A polyethylene terephthalate polymer having an intrinsic viscosity of 1.23 manufactured by Toray Industries, Inc. was continuously supplied to a single-screw extruder type extruder at 295° C. and melted continuously. Molten polymer is kneaded with an 8-stage static mixer through a pipe at 295°C, weighed with a gear pump so that the total fineness is 1400 dtex, introduced into a spinning pack at 295°C, and passed through a 10 micron cut filter inside the pack. The material was extruded and spun from a spinneret having 108 round single holes with a hole diameter of 0.6 mm and a hole length of 0.78 mm. After passing the spun yarn through a heating cylinder with a length of 7 cm and an atmospheric temperature of 285°C, which is provided under the spinneret, cold air at 40°C is blown at a speed of 30 m/min using an annular chimney to solidify the yarn. An oil agent (Sanyo Kasei Co., Ltd.: Sun Oil F) was applied with an oil agent roller. The yarn to which the oil solution was applied was wound at 1 FR (70° C.) having a surface speed of 4000 m/min, and then subjected to a drawing step continuously.

2FR at a speed of 4120m/min (90°C), 1DR at a speed of 1920m/min (120°C), 2DR at a speed of 5120m/min (140°C), 5120m/min at a speed of 5120m/min. The stretching was carried out by continuously subjecting to RR (unheated) of The entanglement device is installed between 2FR and 1DR (EC-Y23 manufactured by Toray Industries, Inc.) and between RR and winding roller (PP3500 manufactured by Heberline), and jets high-pressure air of 0.5 MPa and 0.6 MPa, respectively. to obtain a polyester fiber. The resulting polyester fiber had a breaking strength of 3.65 cN/dtex and a breaking elongation of 56%.

[Belt weaving and dyeing]
Using the polyester fibers obtained here as warp and weft yarns, a belt having a width of 51 mm and a plain weave structure having a warp density of 80 threads/2.54 cm and a weft density of 20 threads/2.54 cm was formed. The obtained belt is scouring by an open soaper type continuous scouring machine at a temperature of 95.degree. Next, a liquid containing a disperse dye was applied by padding, squeezed by a mangle, pre-dried, and thermosol dyeing was performed at 200°C. Further, excess dye was washed away using an alkali and a reducing agent, and then dried at 130° C. to obtain a belt dyed black. The breaking strength of the dyed belt was 15.2 kN.

[Surface coating treatment for belt]
(a) Amidia M-3 (manufactured by DIC Corporation, triazine ring-containing compound, trimethoxymethylol-type melamine, solid content: 80%) (sometimes referred to as resin (a))
The belt was immersed in an aqueous liquid containing 40 g/L of resin (a) and 3 g/L of ammonium persulfate as a catalyst, and squeezed with a mangle so that the adhesion amount of the aqueous liquid was 15% by weight. Processing was performed for 5 minutes in the atmosphere.

Then, it was washed with hot water at a temperature of 70°C, washed with water, and dried at a temperature of 130°C.

Observation with a transmission electron microscope revealed that the film thickness of the resin film containing the triazine ring-containing compound, etc. after the surface coating treatment was 23 nm.

[Treatment of Belt with Organic Fluorine-Containing Compound]
(1) Asahi Guard AG-700D (Meisei Chemical Co., Ltd. fluorine compound solid content 20%) (hereinafter referred to as organic fluorine-containing compound (1))
Organic fluorine-containing compound (1) 150 g/L, resin (a) 18 g/L, Amidia Accelerator ACX (manufactured by DIC Corporation, catalyst solid content 35%) (hereinafter sometimes referred to as catalyst) 3 g/L, aqueous Isopropyl alcohol (special reagent grade manufactured by Nacalai Tesque Co., Ltd.) 10 g / L for the purpose of improving the permeability of the liquid, and AG Stabilizer 54Z (antifoaming agent manufactured by Meisei Chemical Co., Ltd.) for the purpose of suppressing foaming of the liquid (hereinafter referred to as The surface-coated belt is immersed in an aqueous liquid in which 1 g/L of an antifoaming agent is dissolved, squeezed with a mangle so that the adhesion amount of the aqueous liquid is 15% by weight, and dried at 130 ° C. After that, heat treatment was performed at 170°C. Both after processing and after the abrasion test, it had good water and oil repellency, and was also excellent in the effect of preventing paint penetration. The thread density of the belt after resin processing was 81 threads/2.54 cm in the vertical direction, 21 threads/2.54 cm in the horizontal direction, 1423 dtex in total fineness, and 15.8 kN in breaking strength.

(Example 2)
The same procedure as in Example 1 was performed except that the concentration of the resin (a) in [Surface coating treatment for belt] was changed to 20 g/L. Observation of the film thickness of the resin film after the surface coating treatment with a transmission electron microscope revealed that it was 9 nm. Both after processing and after the abrasion test, it had good water and oil repellency, and exhibited a good effect of preventing paint penetration. The thread density of the belt after resin processing was 81 threads/2.54 cm in the vertical direction, 20 threads/2.54 cm in the horizontal direction, 1399 dtex in total fineness, and 15.9 kN in breaking strength.

(Example 3)
The treatment was carried out in the same manner as in Example 1, except that the concentration of the organic fluorine-containing compound (1) in [Treatment of belt with organic fluorine-containing compound] was changed to 100 g/L. Both after processing and after the abrasion test, it had good water and oil repellency, and was also excellent in the effect of preventing paint penetration. The thread density of the belt after resin processing was 81 threads/2.54 cm in the vertical direction, 20 threads/2.54 cm in the horizontal direction, a total fineness of 1432 dtex, and a breaking strength of 15.7 kN.

(Example 4)
Change the concentration of resin (a) in [Surface coating treatment to belt] to 20 g/L, and change the concentration of organic fluorine-containing compound (1) in [Treatment of organic fluorine-containing compound to belt] to 100 g/L. Processing was performed in the same manner as in Example 1. Both after processing and after the abrasion test, it had good water and oil repellency, and was also excellent in the effect of preventing paint penetration. The thread density of the belt after resin processing was 80 threads/2.54 cm in the vertical direction, 21 threads/2.54 cm in the horizontal direction, the total fineness was 1432 dtex, and the breaking strength was 15.3 kN.

(Example 5)
The treatment was carried out in the same manner as in Example 1, except that the concentration of the resin (a) in [Treatment of belt with organic fluorine-containing compound] was changed to 10 g/L. Both after processing and after the abrasion test, it had good water and oil repellency, and was also excellent in the effect of preventing paint penetration. The thread density of the belt after resin processing was 81 threads/2.54 cm in the vertical direction, 20 threads/2.54 cm in the horizontal direction, a total fineness of 1411 dtex, and a breaking strength of 15.7 kN.

(Comparative example 1)
After the [surface coating treatment on the belt] was performed in the same manner as in Example 1, [treatment of the belt with an organic fluorine-containing compound] was not performed. Both after processing and after the abrasion test, the oil repellency and paint penetration prevention effect were poor. The thread density of the belt after resin processing was 81 threads/2.54 cm in the vertical direction, 21 threads/2.54 cm in the horizontal direction, 1432 dtex in total fineness, and 15.4 kN in breaking strength.

(Comparative example 2)
Without performing [surface coating treatment on the belt], and in the [treatment of the belt with an organic fluorine-containing compound] in Example 1, the concentration of the organic fluorine-containing compound (1) was set to zero (not used). processed. Both after processing and after the abrasion test, the oil repellency and paint penetration prevention effect were poor. The thread density of the belt after resin processing was 80 threads/2.54 cm in the vertical direction, 21 threads/2.54 cm in the horizontal direction, a total fineness of 1422 dtex, and a breaking strength of 15.5 kN.

(Comparative Example 3)
[Surface coating treatment for belt] was not performed, and in [Treatment for organic fluorine-containing compound for belt] in Example 1, processing was performed with an aqueous liquid containing resin (a) at a concentration of 40 g/L. Observation of the cross section of the belt after processing revealed that no film was formed on the single fibers, and lumps of resin adhered between the single fibers and at the yarn crossing points of the fabric were observed. The fibers were hardened by the fixing resin. After processing, it had good water and oil repellency and was also excellent in preventing paint penetration. , Paint strike-through occurred from the cracked part, and the penetration prevention effect was inferior. The thread density of the belt after the resin treatment was 81 threads/2.54 cm in the vertical direction, 22 threads/2.54 cm in the horizontal direction, a total fineness of 1456 dtex, and a breaking strength of 15.7 kN.

(Comparative Example 4)
A polyester fiber manufactured by Toray Industries, Inc. having a total fineness of 84 dtex and a filament number of 48 is used as the fiber constituting the belt. The polyester had a breaking strength of 3.11 cN/dtex and a breaking elongation of 45%. Four of these fibers were aligned and plied with a loose twist of 150 turns/m to obtain a total fineness of 336 dtex. A warp double weave belt was woven at a weft density of 40/2.54 cm with a front warp density of 165/2.54 cm and a back warp density of 110/2.54 cm. Then, it was dyed black in the same manner as in Example 1. The breaking strength of the dyed belt was 12.2 kN.

The dyed belt was subjected to the same treatment as in Example 1 [Surface coating treatment for belt]. The pickup of the aqueous liquid was 65% by weight, and the film thickness of the resin film after the surface coating treatment was observed with a transmission electron microscope to be 49 nm.

Further, the same treatment as in Example 1 [Treatment of belt with organic fluorine-containing compound] was performed. The aqueous liquid pickup was 55% by weight.

After processing, the belt had good water and oil repellency, and was also excellent in preventing paint penetration. I couldn't stand it. In addition, the oil repellency of the worn portion was not sufficient, and when the paint was applied, the paint penetrated into the inside of the belt through the cut fiber portion. The thread density of the belt after the resin treatment was 112 threads/2.54 cm in the longitudinal density on the front and back, 41 threads/2.54 cm in the transverse direction, 321 dtex in total fineness, and 12.4 kN in breaking strength.

Table 1 below shows the concentration of the aqueous liquid in [surface coating treatment on the belt] and [treatment of the belt with an organic fluorine-containing compound] in Examples 1 to 4 and Comparative Examples 1 to 4, and after processing and after the abrasion test. Sensory evaluation results of water and oil repellency and paint penetration prevention effect were summarized.

The present invention provides an antifouling belt having antifouling properties, water repellency, resistance to water wetting, prevention of penetration of adhered paint into the belt, excellent workability, and durability. It is suitable for use in painting sites, civil engineering, construction-related safety belts, and the like.

Claims (7)

A belt comprising a single fiber surface coated with a resin film containing an organic fluorine compound via a resin film containing a triazine ring-containing compound or a resin film containing an organic fluorine compound and a triazine ring-containing compound, said belt comprising: A belt having a water repellency of grade 3 or higher and an oil repellency of grade 4 or higher after 2000 times of the hexagon bar pressing abrasion test specified in the seat belt standard JIS D 4604 (2006). 2. The belt according to claim 1, wherein the resin coating containing the triazine ring-containing compound or the resin coating containing the organic fluorine-containing compound and the triazine ring-containing compound has a thickness of 5 to 100 nm. 3. The belt according to claim 1, wherein said organic fluorine compound-containing resin film contains a triazine ring-containing compound and/or an isocyanate compound. The belt according to any one of claims 1 to 3, wherein the fibers have a tensile strength of 3.0 cN/dtex or more and a total fineness of 500 dtex or more. The belt according to any one of claims 1 to 4, which has a breaking strength of 15.0 kN or more. 6. The belt according to any one of claims 1 to 5, wherein the belt is made of woven fabric and has a cover factor of 2800 or more. A safety belt using the belt according to any one of claims 1 to 6.