JP2008038285A - Rope - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rope which uses polylactic acid fibers, has improved hydrolysis resistance, and can especially suitably be used for industry. <P>SOLUTION: This rope uses the polylactic acid fibers whose terminal carboxyl groups are partially or wholly blocked with at least one glycidyl group-containing triazine skeleton compound represented by the general formula (I) (wherein, at least one of R<SB>1</SB>to R<SB>3</SB>is a glycidyl group, and the remainders are each a group selected from H, 1-10C alkyl groups, hydroxyl group, and allyl group) as at least a part of rope-constituting elements. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a rope using polylactic acid fiber, and relates to a rope that solves the problem of easily hydrolyzable, which has been a problem with conventional ropes using polylactic acid fiber.

  In recent years, polylactic acid resin has attracted attention as a resin having a small environmental load even if it is burned or discarded. The reason why polylactic acid is said to be an environmentally friendly material is that it is obtained from non-petroleum raw materials such as plants and has biodegradability. The biodegradation mechanism of polylactic acid is generally known to start with biodegradation by microorganisms after the molecular weight is reduced by hydrolysis, and it is also well known that the hydrolysis rate is fast.

  Polylactic acid fiber using this polylactic acid resin does not accumulate in the natural environment even after being discarded and has a unique texture, so it can be used for ship ropes such as mooring lines, taglines, boat halls, Studies are underway for practical use as land ropes such as ropes and ranger ropes.

  However, for industrial ropes that are often used mainly outdoors or underwater, it is required to maintain strength over a certain period of time, so the “fast hydrolysis rate” of polylactic acid is a problem. However, the current situation is that it has not become a substitute for other materials until recently.

Among the prior arts, technologies for obtaining polylactic acid fibers that are excellent in hydrolysis resistance and suitable for industrial use are described in Patent Documents 1 to 3 and the like. In Patent Document 1, a carbodiimide compound is added. Techniques for suppressing the hydrolysis of polylactic acid are disclosed, and Patent Documents 2 and 3 disclose techniques for suppressing hydrolysis of polylactic acid by adding an oxazoline compound and an epoxy compound, respectively.
JP 2004-332166 A JP 2001-323056 A JP 2001-335626 A

  However, when the carbodiimide compound described in Patent Document 1 is added to obtain a polylactic acid fiber, in the polylactic acid fiber manufacturing process, the isocyanate derived from the carbodiimide compound generates a bad odor and the working environment is deteriorated. In addition, the carbodiimide has a problem of increasing the viscosity of the polymer and deteriorating the yarn forming property. In addition, when the present inventors re-examined the methods described in Patent Documents 2 and 3, the reactivity between the compound and the carboxyl group terminal was poor, and the normal spinning method showed that the carboxyl group terminal blockage was insufficient. It was a result.

  Then, this invention makes it a subject to solve the degradation problem by the hydrolysis which became a big problem with the rope using the conventional polylactic acid fiber, and to provide a rope excellent in hydrolysis resistance.

  As a result of intensive studies on the above-mentioned problems by the present inventors, at least a component of a polylactic acid fiber represented by the general formula (I) in which part or all of the carboxyl group ends are blocked with at least one compound is provided. It was found that a rope as a part of the problem solved the above-mentioned problem.

(Here, at least one of R _{1 to} R ₃ is a glycidyl group, and the rest represents a group selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and an allyl group.)

In addition, the rope of this invention makes the following (1)-(4) a preferable form, and expresses the best effect, when it is suitable for the use as a ship rope and a land rope.
(1) The carboxyl group terminal concentration of the polylactic acid fiber is 20 equivalent / t or less,
(2) The addition amount of the compound represented by the general formula (I) is 0.1 to 5% by weight of the whole polylactic acid fiber,
(3) The compound represented by the general formula (I) is at least one selected from diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and triglycidyl isocyanurate,
(4) The entanglement degree of the polylactic acid fiber is 5 to 70.

  According to the present invention, it is possible to solve the degradation problem due to hydrolysis, which has been a big problem in ropes using polylactic acid fibers.

  The polylactic acid fiber used in the rope of the present invention is obtained from a polylactic acid resin obtained by polymerizing lactic acid mainly composed of L-lactic acid and / or D-lactic acid, and the molecular weight of the polylactic acid resin is not particularly limited. However, if the molecular weight is too high, the spinning property may be deteriorated. If the molecular weight is too low, the necessary strength as a fiber may not be obtained. Therefore, the weight average molecular weight (Mw) is 100,000 to 500,000. It is preferable to be in the range. Moreover, as a more preferable range of Mw, a range of 150,000 to 300,000 can be exemplified.

  The polylactic acid resin may be a copolymer of a component copolymerizable with lactic acid. Examples of the copolymer mainly composed of polylactic acid include the lactic acid, cyclic lactones such as ε-caprolactone, α-oxyacids such as α-hydroxyisobutyric acid and α-hydroxyvaleric acid, ethylene glycol, 1,4 Examples thereof include those obtained by copolymerizing one or more monomers selected from diols such as butanediol and dicarboxylic acids such as succinic acid and sebacic acid. The proportion of copolymerization is not particularly limited, but the monomer to be copolymerized is preferably 100 parts by weight or less, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of lactic acid.

  Further, the polylactic acid fiber of the present invention may be blended with a polylactic acid resin and a blendable thermoplastic polymer, and as a blendable thermoplastic polymer, polycaprolactone, polybutylene succinate, and An aliphatic polyester polymer such as polyethylene succinate can be exemplified.

  Furthermore, inorganic fine particles and organic compounds can be added to the polylactic acid fiber of the present invention as necessary, such as a matting agent, a flame retardant, a heat resistance agent, a light resistance agent, an ultraviolet absorber, and a color pigment. However, in view of recent environmental problems, avoid blends of petroleum-based polymers, copolymerization of the components as much as possible, and various additives are compounds that are expected to be a concern as well as heavy metal compounds and environmental hormone substances. It is preferable that none of the above is used.

  In addition, the polylactic acid fiber of the present invention preferably contains at least one kind of colorant in advance in order to avoid strength reduction and environmental contamination due to the dyeing process. The colorant added to the polylactic acid fiber used in the rope of the present invention is a specific inorganic, organic pigment and dye suitable for the polylactic acid fiber, specifically titanium oxide, carbon black, cyanine, styrene, Examples include, but are not limited to, phthalocyanine, anthraquinone, perinone, isoindolinone, anthraquinone, berylone, isoindolinone, quinophthalone, quinocridone, and thioindigo compounds. It is not a thing. The content of the colorant is preferably 0.01 to 4% by weight. When the addition amount of the colorant is less than 0.01% by weight, the color tone is insufficient, and when it exceeds 4% by weight, it is difficult to obtain the required strength. The addition amount of the colorant is more preferably from 0.1 to 0.6% by weight based on the polymer, and still more preferably from 0.3 to 0.5%.

  The polylactic acid fiber of the present invention contains 0.1 to 5% by weight, more preferably 0.5 to 3% by weight of fatty acid bisamide and / or alkyl-substituted fatty acid monoamide in order to improve wear resistance. May be. If it is less than 0.1% by weight, the effect of improving the wear resistance cannot be sufficiently obtained, and if it exceeds 5% by weight, it is difficult to obtain the required strength. By setting the content of the fatty acid bisamide and / or the alkyl-substituted fatty acid monoamide in the above range, the slipperiness of the fiber surface can be improved and excellent wear resistance can be imparted. Fatty acid bisamide refers to a compound having two amide bonds in one molecule such as saturated fatty acid bisamide, unsaturated fatty acid bisamide, aromatic bisamide, etc., for example, methylene biscaprylic amide, methylene biscapric amide, methylene bisamide. Lauric acid amide, methylene bis myristic acid amide, methylene bis palmitic acid amide, methylene bis stearic acid amide, methylene bis isostearic acid amide, methylene bis behenic acid amide, methylene bis oleic acid amide, methylene bis erucic acid amide, ethylene bis Caprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bismyristic acid amide, ethylene bispalmitic acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid Amide, Ethylene bis behenic acid amide, Ethylene bis oleic acid amide, Ethylene bis erucic acid amide, Butylene bis stearic acid amide, Butylene bis behenic acid amide, Butylene bis oleic acid amide, Butylene bis erucic acid amide, Hexamethylene Bistearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bisoleic acid amide, hexamethylene biserucic acid amide, m-xylylene bisstearic acid amide, m-xylylene bis-12-hydroxystearic acid amide, p- Xylylene bis-stearic acid amide, p-phenylene bis-stearic acid amide, p-phenylene bis-stearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, N, N′- Giole Luadipic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-distearyl isophthalic acid amide, N, N′-distearyl terephthalic acid amide, methylene bishydroxystearic acid amide, ethylene bishydroxystearic acid amide , Butylene bishydroxystearic acid amide, hexamethylene bishydroxystearic acid amide, etc., and alkyl-substituted fatty acid monoamides are compounds having a structure in which amide hydrogen such as saturated fatty acid monoamides and unsaturated fatty acid monoamides are replaced with alkyl groups. For example, N-lauryl lauric acid amide, N-palmityl palmitic acid amide, N-stearyl stearic acid amide, N-behenyl behenic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N- Examples include oleyl stearic acid amide, N-stearyl erucic acid amide, and N-oleyl palmitic acid amide. The alkyl group may have a substituent such as a hydroxyl group introduced into its structure, for example, methylol stearamide, methylol behenic acid amide, N-stearyl-12-hydroxystearic acid amide, N-oleyl-12-hydroxystearic acid amide and the like are also included in the alkyl-substituted fatty acid monoamide of the present invention. Of these, fatty acid bisamides can be more preferably used because they are less reactive with polylactic acid because of the lower reactivity of amides, and are high in heat resistance and difficult to sublimate because of their high molecular weight. The fatty acid bisamide and the alkyl-substituted fatty acid monoamide may be added singly or a plurality of components may be mixed and used.

  The polylactic acid fiber used in the rope of the present invention needs to be partially or entirely blocked with at least one compound represented by the general formula (I). Part or all of the carboxyl group ends of the polylactic acid fiber used for the rope are blocked with at least one compound represented by the general formula (I), thereby dramatically improving the hydrolysis resistance of the rope of the present invention. improves.

The compound represented by the general formula (I) is a 1-3 functional glycidyl-modified compound having a triazine skeleton, and among the compounds represented by the general formula (I), at least one of R _{1 to} R ₃ is a glycidyl group. Need to be. When the triazine skeleton has 1 to 3 glycidyl groups, it reacts with carboxyl end groups with high efficiency even in spinning of polylactic acid fibers molded at a relatively low temperature. Moreover, since it does not thicken like a carbodiimide compound, it shows excellent mechanical properties and yarn-forming properties even after end-capping without hindering the orientation of the molecular chain in the melt spinning or drawing process. Further, the compound has high heat resistance, and there is no problem of coloring even if it is molded at a high temperature, and there is no generation of odor that deteriorates the working environment if the addition amount suggested in the present invention.

In addition, among R < ₁ > -R < ₃ >, Preferably a glycidyl group is 1-2 pieces, More preferably, it is one piece. Of course, a plurality of compounds having different numbers of glycidyl groups may be mixed (usually, a mixture having 1 to 3 glycidyl groups is distributed in the synthesis step of the general formula (I)).

Moreover, among R _{1 to} R ₃ , groups other than the glycidyl group are groups selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and an allyl group. Here, the number of carbon atoms in the alkyl group should be small, and it is preferably 1 to 5 carbon atoms. Among the above, diallyl monoglycidyl isocyanurate (hereinafter referred to as DAMGIC), monoallyl diglycidyl isocyanurate (hereinafter, referred to as DAMGIC) as the compound represented by the general formula (I) in terms of excellent end capping properties and fiber mechanical properties. In the following, MADGIC) and triglycidyl isocyanurate (hereinafter referred to as TGIC) are preferably used.

  The polylactic acid fiber used in the rope of the present invention has a low carboxyl group terminal concentration because part or all of the carboxyl group at the terminal of the polylactic acid resin is blocked with the compound of the general formula (I). It is. Here, the carboxyl group terminal concentration means not only the carboxyl group terminal of the polymer but also the total carboxyl group terminal concentration including those derived from residual oligomers and monomers. In the present invention, in order to provide sufficient hydrolysis resistance, the carboxyl group terminal concentration is preferably 20 equivalent / t or less, more preferably 15 equivalent / t or less, still more preferably 10 equivalent / t or less, particularly Preferably it is 0-5 equivalent / t or less.

In order to maintain the hydrolysis resistance, it is preferable to leave the unreacted compound represented by the general formula (I). By designing in such a manner, the terminal end of the carboxyl group newly formed by hydrolysis is also blocked. The carboxyl group terminal concentration can be controlled by the amount of the compound represented by the general formula (I). Here, the addition amount of the compound of the general formula (I) is preferably 1.05 times or more equivalent to the total carboxyl group terminal concentration of the polylactic acid fiber as an epoxy group equivalent. Therefore, although the addition amount of the compound depends on the total carboxyl group terminal concentration of the polylactic acid resin as a raw material, the addition amount of the compound represented by the general formula (I) is usually 0. 1 to 5% by weight. In addition, among R _{1 to} R ₃ of the compound represented by the general formula (I), when the number of glycidyl groups is 2 to 3, the Mw / Mn of the polymer is decreased by chain connection or crosslinking reaction of the polylactic acid resin. It tends to grow. On the other hand, if the unreacted material is excessive, it is discharged out of the fiber system in the melt spinning or rope manufacturing process and is not used for its original purpose. Therefore, the addition amount of the compound represented by the general formula (I) is preferably 0.2 to 5% by weight, and more preferably 0.3 to 3% by weight with respect to the whole polylactic acid fiber. More preferably, it is 0.4-2 weight%.

  In addition to the compound represented by the above general formula (I), a compound having an oxazoline group, a carbodiimide group, an aziridine group, an imide group and an isocyanate group that are reactive with the carboxyl group terminal is used in combination. Also good. Specific examples of such a compound include diisopropylphenylcarbodiimide and phenylenebisoxazoline.

  Further, in order to efficiently react the compound represented by the general formula (I) with the carboxyl terminal group, a metal salt of carboxylic acid, particularly an alkali metal compound, an alkaline earth metal compound, a tertiary amine compound, Examples include imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium salts, phosphate esters, organic acids, Lewis acids, and specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, Sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, Sodium phenyl borohydride, sodium benzoate Lithium, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, Alkali metal compounds such as potassium, lithium and cesium salts, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, acetic acid Alkaline earth metal compounds such as barium, magnesium acetate, strontium acetate, calcium stearate, magnesium stearate, strontium stearate, triethylamine, tributylamine, trihexylamine, triamylamine Triethanolamine, dimethylaminoethanol, triethylenediamine, dimethylphenylamine, dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, dimethylaniline, pyridine, picoline, 1,8-diazabicyclo (5,4,0) undecene-7 Tertiary amines such as 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, imidazole compounds such as 4-phenyl-2-methylimidazole, tetramethylammonium chloride, tetraethylammonium Chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tripropylbenzylammonium chloride Quaternary ammonium salts such as rholide, N-methylpyridinium chloride, phosphine compounds such as trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenyl Phosphonium salts such as phosphonium bromide, triphenylbenzylphosphonium bromide, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, Octyl diphenyl phosphate , Phosphoric acid esters such as tri (p-hydroxy) phenyl phosphate, tri (p-methoxy) phenyl phosphate, organic acids such as oxalic acid, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, Examples thereof include Lewis acids such as boron fluoride, aluminum tetrachloride, titanium tetrachloride, and tin tetrachloride, and these can be used alone or in combination. Among them, it is preferable to use an alkali metal compound, an alkaline earth metal compound, a phosphine compound, and a phosphate ester, and in particular, an alkali metal or an organic salt of an alkaline earth metal can be preferably used. Particularly preferred compounds are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and magnesium acetate. Further, an organic salt of an alkali metal or alkaline earth metal having 6 or more carbon atoms is preferable, and adding a catalyst such as sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate can increase the reaction efficiency. This is preferable. It is also preferable to use a catalyst based on lactic acid such as sodium lactate, calcium lactate and magnesium lactate because of its good compatibility with polylactic acid. In addition, a catalyst having a relatively large molecular weight such as a metal stearate can be used alone or in combination for the purpose of preventing the heat resistance of the resin from being lowered by the addition of the catalyst. In addition, it is preferable to add 5-2000 ppm with respect to a fiber, when the addition amount of this catalyst controls dispersibility and reactivity. More preferably, it is 10-1000 ppm, More preferably, it is 20-500 ppm.

  Moreover, the cross-sectional shape of the polylactic acid fiber used for the rope of the present invention is not limited at all. A cross section or a combination thereof can be employed. By making the cross-sectional shape an atypical cross section, it is possible to impart softness, swelling, bulkiness, lightness, heat retention, and the like.

  The polylactic acid fiber used for the rope of the present invention can adopt monofilament, multifilament, slit yarn and the like. There is no particular limitation on the fineness, and the fineness may be appropriately changed according to the application. The range of the total fineness that can be used is 20 to 10000 dtex, preferably 300 to 3000 dtex, and the single yarn fineness range is 0.02 to 10,000 dtex, preferably 0.1 to 3000 dtex. it can. When the total fineness is less than the above range, the productivity is poor, and when the total fineness is more than the above range, for example, there is a possibility that the cooling ability is insufficient during melt spinning and the spinning performance is deteriorated.

  The polylactic acid fiber used for the rope of the present invention has a strength of 1.5 cN / dtex or more, more preferably 2.5 cN / dtex or more, and further preferably 3.0 cN / dtex from a practical viewpoint. On the other hand, the upper limit of the strength is 9.0 cN / dtex or less from the viewpoint that the present technology can be stably manufactured. Moreover, what is necessary is just to select elongation suitably by need as needed, for example, the range of 10 to 300% can be illustrated. Furthermore, if it is 10 to 100% as a preferable range, it is possible to obtain a rope having high strength and excellent dimensional stability, and if it is 100 to 300%, flexibility can be imparted to the rope. A boiling water shrinkage of the polylactic acid fiber (hereinafter sometimes abbreviated as “boiling”) of 0 to 20% is preferable because the rope has good dimensional stability. The above-described fiber properties can be controlled by spinning temperature, spinning speed, stretching temperature, stretching ratio, and the like.

  The polylactic acid fiber used for the rope of the present invention as described above can be produced by the production method described below.

  The production method of the polylactic acid resin used as the raw material for the polylactic acid fiber is not particularly limited, and is a method described in JP-A-6-65360 (direct dehydration condensation method) or a method described in JP-A-7-173266. (Method of copolymerizing and transesterifying at least two kinds of homopolymers in the presence of a polymerization catalyst), a method described in US Pat. No. 2,703,316 (dehydrating lactic acid once, For example, an indirect polymerization method in which ring-opening polymerization is performed after forming the polymer can be employed.

  For example, in the case of TGIC, the compound represented by the above general formula (I) can be produced by reacting isocyanuric acid and epichlorohydrin under a catalyst. Note that the smaller the amount of residual epichlorohydrin in the TGIC, the less the volatilization during melt molding, which is preferable. The concentration of epichlorohydrin in TGIC is preferably 0 to 1000 ppm, more preferably 0 to 500 ppm, and still more preferably 0 to 200 ppm.

  An example of a typical direct melt spin drawing process is shown in FIG. 1 in order to detail the method for producing polylactic acid fibers. The process of FIG. 1 is a “pre-stretch-three-stage stretch-relax” method, but of course, as long as the above requirements are satisfied, the method for producing polylactic acid fibers used in the rope of the present invention is not limited to this process. A method of temporarily winding an undrawn yarn and then subjecting it to a drawing step, a high-speed spinning method, or the like can be freely employed.

The polylactic acid resin whose carboxyl group ends are blocked by the compound represented by the above general formula (I) is added to the polylactic acid resin and mixed in a molten state or a solution state. And, for example, a method in which the compound represented by the general formula (I) is added and stirred and reacted in the molten state immediately after the completion of the polycondensation reaction of the polylactic acid resin, A method in which a compound represented by the general formula (I) is added to a polylactic acid resin chip and mixed, and then melted and kneaded in a reaction vessel or an extruder, etc., and the liquidated into a polylactic acid resin with an extruder A method in which a compound represented by the general formula (I) is continuously added and melted and kneaded to react, a polylactic acid resin containing a high concentration of the compound represented by the general formula (I) The blend chips obtained by mixing a Homochippu master chip and polylactic acid resin, can be carried out by a method of kneading and reacting the like extruder during spinning.
When the master chip is produced, the amount of the compound represented by the general formula (I) is preferably 1 to 40% by weight, and 3 to 20% by weight based on the total amount with the polylactic acid resin. It is more preferable that

  Moreover, when using for melt spinning, it is preferable that the water content of the polylactic acid resin is 200 ppm or less in order to suppress hydrolysis of the polylactic acid resin.

  The spinning temperature depends on the melting point of the polylactic acid resin to be used, but it is preferable from the viewpoint of spinning property that spinning is performed at a temperature that is at least 20 ° C. higher than the melting point of the high melting point resin.

  Hereafter, the manufacturing method of the polylactic acid fiber of this invention is demonstrated concretely with reference to FIG.

  Polylactic acid fiber is melt-kneaded with an extruder (2) equipped with a twin-screw extrusion kneader, and introduced into a spinning pack (3) in a nitrogen atmosphere in a hopper (1). It can be obtained by a method of discharging from the spinneret (4). When adding the above-mentioned pigment, a method of directly mixing with an extruder or a method of previously preparing a polylactic acid resin master chip containing a high concentration of pigment and blending the chips before melting can be employed.

  Immediately below the spinneret, the upper end is 0 to 15 cm from the spinneret surface, and a range of 5 to 100 cm from the upper end is surrounded by a heating tube and / or a heat insulating tube, and the spinning yarn is placed in a high temperature atmosphere of 200 to 280 ° C. It is preferable to let it pass. The orientation of the spun yarn is relaxed by cooling it through the slow cooling zone (5) in a high temperature atmosphere surrounded by the heating tube and / or the heat insulating tube without immediately cooling the spun yarn. And uniformity of molecular orientation between single fibers can be improved. On the other hand, if it cools immediately without letting it pass in a high temperature atmosphere, the orientation of an undrawn yarn will increase and the orientation degree distribution between single fibers will become large. When such an unstretched yarn is hot-drawn, there is a possibility that a high-strength composite fiber cannot be obtained as a result.

  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. in the cooling device (6). When the cooling air is less than 10 ° C., a large cooling device is required separately from the normal device, which is not preferable. In addition, when the cooling air exceeds 100 ° C., the single fiber sway during spinning becomes large, so that the single fibers collide with each other, making it difficult to produce the fibers with good spinning properties. The cooling device (6) may be a horizontal blowing type or 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 unstretched yarn that has been cooled and solidified is then applied with an oil agent by an oil supply device (7). The oil agent may be aqueous or non-aqueous, but contains a smoothing agent as a main component, includes a surfactant, an antistatic agent, an extreme pressure agent component, and the like, and removes an active component in the polylactic acid resin. It is preferable to use an oil agent composition. For example, the emulsified component contained in the water emulsion has an action of changing the fiber structure of the polylactic acid fiber, and easily works to generate surface irregularities during stretching. Therefore, it is preferable to use a non-aqueous oil agent. Further, a preferred oil agent composition is, for example, a non-aqueous oil agent 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 a mineral oil. .

  The unstretched yarn to which the oil is applied is wound around the take-up roller (1FR) (8) and taken up. The surface speed of 1FR, that is, the take-up speed is preferably 300 m / min or more, more preferably 500 m / min or more. Polylactic acid fibers can be obtained even at a take-off speed of less than 300 m / min, but are difficult to adopt because of low production efficiency. Although there is no particular upper limit to the take-up speed, the take-up speed is preferably 5000 m / min or less, more preferably 3000 m / min or less in the case of industrially stable production.

  The undrawn yarn taken up at the take-up speed is drawn once or continuously without being taken up. As with 1FR, a Nelson type roller having two rollers as one unit is a take-up roller (2FR) (9), stretching rollers (1DR) (10), stretching rollers (2DR) (11), stretching rollers (3DR ) (12) and the relaxation roller (RR) (13) are arranged side by side, and the yarn is sequentially wound to perform a drawing heat treatment. Usually, stretching is performed between 1FR and 2FR to focus the yarn. A preferred stretch ratio is in the range of 1 to 7%, more preferably 1 to 5%. 1FR is heated to 50 to 80 ° C., preferably 50 to 70 ° C., and the take-up yarn is preheated and sent to the next drawing step.

  The first stage stretching is performed between 2FR and 1DR, the temperature of 2FR is 80 to 120 ° C, preferably 80 to 110 ° C, and the temperature of 1DR is 90 to 120 ° C, preferably 100 to 120 ° C. When the number of drawing stages is 3, the first stage draw ratio is 20 to 90%, preferably 20 to 50% of the total draw ratio, and when the total draw stage number is 2, the first stage draw ratio is It is set in the range of 30 to 90%, preferably 50 to 90% of the total draw ratio.

  The second stage stretching is performed between 1DR and 2DR, and 2DR is 110 to 160 ° C, preferably 115 to 145 ° C. In the case of two-stage stretching, the remaining stretching of the first-stage stretching ratio is performed between the total stretching ratios. In the case of three-stage stretching, the remaining stretching ratio is divided into two stages. The temperature of 3DR when performing three-stage stretching is 120 to 160 ° C, preferably 130 to 150 ° C. The yarn that has finished the two-stage drawing or the three-stage drawing is subjected to a relaxation treatment of 0 to 10%, preferably 0 to 7%, more preferably 0.5 to 5% with the RR, and is caused by heat drawing. In addition to taking the strain, the highly oriented structure achieved by stretching can be fixed, the orientation of the amorphous region can be relaxed, and the thermal shrinkage rate can be lowered. RR uses a non-heated roller or a roller heated to 160 ° C. or less.

  The basic properties of the polylactic acid fiber used in the rope of the present invention can be obtained by the above method. However, in order to obtain a high-quality polylactic acid fiber with less generation of fluff, a high-pressure fluid is sprayed on the fiber yarn between 2FR and 1DR where one-stage drawing is performed, and the yarn constituting the fiber Stretching may be performed while confounding the yarn and converging the yarn. The entanglement imparting device (14) for entwining and converging the yarn can use an entanglement nozzle that is used to impart entanglement to the yarn and condense it immediately before winding the yarn. It is effective to apply the entanglement during the first stage stretching, but it may be performed during the second stage and third stage stretching in addition to the first stage. The degree of entanglement applied to the polylactic acid fiber is preferably 5 to 70, and more preferably 10 to 60. When the degree of entanglement is less than 5, it is not preferable because process passability in high-order processing is deteriorated. If the degree of entanglement is greater than 70, loops are likely to occur, making it difficult to perform high-order processing stably. Thereafter, the polylactic acid fiber is wound up by a winding device (15).

  The polylactic acid fiber used for the rope of the present invention can thus be obtained.

  In the rope of the present invention, it is essential that the polylactic acid fiber derived from the non-petroleum raw material is at least a part of the constituent elements from the viewpoint of reducing the environmental load. Further, the rope according to the present invention includes 10 to 100% by weight of polylactic acid fibers in which part or all of the carboxyl ends are blocked with at least one compound represented by the general formula (I), thereby reducing environmental load. From the viewpoint of A more preferred range is 30 to 100% by weight, and a more preferred range is 50 to 100% by weight.

  The rope production method of the present invention can be made by using a conventionally known method. The polylactic acid fibers used in the present invention are combined, and the yarn process and the strand process are sequentially performed, and the obtained strand is closed or knitted. Netting into a rope with a rope. Thereafter, in order to stabilize the shape, quality, and performance, it is preferable to perform the heat treatment step in the range of 60 to 160 ° C. If the heat treatment temperature is 160 ° C. or lower, a good-quality rope can be obtained without causing fusion between polylactic acid fibers, and if it is 60 ° C. or higher, the desired heat setting effect can be obtained. The range of the preferable heat setting temperature is 80 to 150 ° C, more preferably 100 to 140 ° C. There are various methods of heat treatment such as resin processing, steam, hot water, electric heat, etc., but since the rope diameter is usually large, it is preferable to use high-frequency radio waves that generate heat from the inside in order to uniformly heat the outside and the inside. .

  Although it does not specifically limit as a twisting method, JIS-L2701 (1992), JIS-L2703 (1992), JIS-L2704 (1992), JIS-L2705 (1992), JIS-L2706 (1992) etc. are illustrated. A method can be appropriately selected and used.

  The number of twists is not particularly limited. Usually, for example, the lower twist is 30 to 500 times / m, preferably 50 to 300 times / m, and the upper twist number is about 20 to 200 times / m, 20 to 100 times / m. More preferred.

  The rope structure may be a structure suitable for the application. For example, twisted ropes such as three-punch, four-punch, six-punch, and eight-punch, braided ropes and braids such as stone-punch, twill-punch, twelve-pipe, and sixteen-punch, or Such specially constructed ropes are possible. However, in order to make the best use of the high strength and high elastic modulus of the fiber, it is preferable to select one having a small number of twists.

  Further, when twisting or knitting, it is effective to add a sizing agent, an oil agent, and a surface treatment agent to the filament as necessary. Moreover, you may perform these processes, after manufacturing a rope once. Such surface treatment is effective in reducing the physical properties due to friction and wear between the fibers that make up the rope, as well as in wear and weather resistance due to contact with other materials such as ropes and fiber metals during rope manufacturing and use. Since it has, it is preferable.

  Thus, the rope of the present invention can be obtained.

  As the rope of the present invention, for example, suitable for marine ropes such as mooring lines, tag lines, boat holes, guy ropes, strong ropes, land ropes such as sails, range ropes, leads, etc., but not limited to these uses It can be adopted without any problem.

  Hereinafter, embodiments of the present invention will be described in more detail by way of examples. The definition and measurement method of the characteristics used in the specification text and examples are as follows.

(1) Weight average molecular weight of polylactic acid Tetrahydrofuran was mixed with the chloroform solution of the sample to prepare a measurement solution. This was measured by gel permeation chromatography (GPC-150C manufactured by Waters), and the weight average molecular weight Mw and the number average molecular weight Mn were calculated in terms of polystyrene, and the degree of dispersion Mw / Mn was determined.

(2) Concentration of carboxyl group terminal A precisely weighed sample (1 g) was immersed in 20 ml of o-cresol (5% water) and dissolved at 145 ° C. for 10 minutes, and an appropriate amount of dichloromethane was added to this solution. Was determined by titration with a KOH methanol solution. At this time, an oligomer such as lactide, which is a cyclic dimer of lactic acid, is hydrolyzed to generate a carboxyl group terminal, so that all of the carboxyl group terminal of the polymer, the monomer-derived carboxyl group terminal, and the oligomer-derived carboxyl group terminal are totaled. The carboxyl group terminal concentration obtained is obtained.

(3) Amount of lactide 1 ml of dichloromethane containing 10000 ppm of 2,6-dimethyl-γ-pyrone and 18 ml of dichloromethane were added to 1 g of the sample and stirred and dissolved. 1 ml of this solution was weighed and mixed with 3 ml of acetone, and then 16 ml of cyclohexane solution was added. The obtained solution was filtered with a syringe filter having a diameter of 13 mm and a pore diameter of 0.45 mm, and then measured by a gas chromatography method using 5890 Series II Plus manufactured by Hewlett-Packard Company. As the column, BPX50 manufactured by Shimadzu Corporation having an inner diameter of 0.25 mm, a length of 30 m, and a film thickness of 0.25 mm was used. The sample injection amount was measured by using hydrogen as a carrier gas of 1 ml, raising the temperature from an initial temperature of 50 ° C. to 325 ° C. at a rate of 25 ° C./min, and measuring by an absolute calibration method.

(4) Melting point The temperature which gives the extreme value of the melting endotherm curve obtained by measuring 20 mg of a sample at a heating rate of 5 ° C./min using a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer Co., Ltd. ).

(5) Total fineness and fineness of filament JIS L1013 8.3.1 Positive fineness a) Measured according to method A at 5 mN / tex × number of displayed tex and 90 m as the predetermined yarn length.

(6) Single fiber fineness The value which divided the total fineness measured according to said (5) by the number of single fibers which comprise a polylactic acid fiber was employ | adopted.

(7) Fiber Strength and Elongation The sample was measured with Orientec Co., Ltd. “TENSILON” UCT-100 under the constant speed elongation conditions shown in the JIS L1013 8.5.1 standard time test. At this time, the holding interval was 25 cm, the tensile speed was 30 cm / min, and the number of tests was 10 times. The elongation at break was determined from the elongation at the point showing the maximum strength in the SS curve.

(8) Spinnability With respect to yarn breakage per 1t of single yarn when obtaining polylactic acid fiber yarns, the spinnability was evaluated according to the following criteria.
◎: Thread breakage less than 1 time, ◯: Thread breakage 1 time or more and less than 3 times, △: Thread breakage 3 times or more and less than 5 times, X: Thread breakage 5 times or more

(9) Strength retention rate As an acceleration test for hydrolysis resistance, 10 g of a weighed rope was fixed so as not to shrink (fixed to a metal frame), and placed in a sealable container together with 3000 ml of water, and then the temperature rising rate was 4 ° C. After heating the container so that the water temperature in the container becomes 130 ° C., hold it at that temperature for 40 minutes, and subsequently cool it at a rate of temperature decrease of 4 ° C./minute. It took out, washed with water, and the strength retention before and after the heat treatment was calculated by the following formula.
Strength retention (%) = T0 / T1 × 100
T1: Tensile strength before heat treatment T0: Tensile strength after heat treatment

(10) Entanglement degree (CF value)
A 100 g load is applied to a sample of 1 m length, a 6 g hook is lowered at a descending speed of 1 to 2 cm / sec, and calculated by the formula: Entanglement (CF value) = 100 (cm) / Descent distance (cm) Asked. An average value of 10 trials was adopted.

[Production Example 1] (Production of polylactic acid resin)
Polymerization of lactide produced from L-lactic acid having an optical purity of 99.5% in the presence of bis (2-ethylhexanoate) tin catalyst (lactide to catalyst molar ratio = 10000: 1) at 180 ° C. for 230 minutes in a nitrogen atmosphere. The resin P1 was obtained. The resulting polylactic acid had a weight average molecular weight of 221,000.

[Production Example 2] (Production of polylactic acid resin containing 10% by weight of DAMGIC)
P1 and diallyl monoglycidyl isocyanuric acid (hereinafter referred to as DAMGIC) manufactured by Shikoku Kasei Co., Ltd. are dried and then supplied to a twin-screw kneading extruder so that P1: DAMGIC = 90: 10 (weight ratio). Kneading at a temperature of 200 ° C. gave Resin P2.

[Production Example 3] (Production of polylactic acid resin containing 10% by weight of MADGIC)
After drying P1 and monoallyl diglycidyl isocyanuric acid (hereinafter referred to as MADGIC) manufactured by Shikoku Kasei Co., Ltd., it is supplied to a twin-screw kneading extruder so that P1: MADGIC = 90: 10 (weight ratio). The resin P3 was obtained by kneading at a cylinder temperature of 200 ° C.

[Production Example 4] (Production of polylactic acid resin containing 10% by weight of TGIC)
P1 and triglycidyl isocyanuric acid (hereinafter referred to as TGIC) manufactured by Nissan Chemical Industries, Ltd. are dried and then supplied to a twin-screw kneading extruder so that P1: TGIC = 90: 10 (weight ratio). The resin P4 was obtained by kneading at a temperature of 200 ° C.

[Production Example 5] (Production of polylactic acid resin containing 10% by weight of polycarbodiimide)
After drying P1 and Nisshinbo Co., Ltd. polycarbodiimide “carbodilite” HMV-8CA (hereinafter referred to as PCI), it was supplied to a twin-screw kneading extruder so that P1: PCI = 90: 10 (weight ratio). The resin P5 was obtained by kneading at a cylinder temperature of 200 ° C.

[Example 1]
P1 and P4 were dried at 105 ° C. for 12 hours using a vacuum dryer. P1: P4 was blended in a chip state so as to be 9: 1 (final TGIC concentration: 1% by weight) and supplied to the spinning hopper. The blended chips were melt-spun at 220 ° C. using a spinning machine with a twin screw extruder. The polymer melted by the extruder is guided to a spinning pack, filtered through a 20 μm metal nonwoven fabric filter, weighed with a gear pump so as to have the fineness shown in Table 1, and spun from a 144-hole base with a hole diameter of 0.6φ. I put it out.

  A 15 cm heating cylinder and a 15 cm heat insulation cylinder were attached 3 cm below the base surface, and heated so that the in-cylinder atmosphere temperature was 250 ° C. Here, the in-cylinder atmosphere temperature is an air layer temperature in a central portion of the heating cylinder length and a portion 1 cm away from the inner wall.

  An annular blow-off chimney was attached directly under the heating cylinder, and cold air at 30 ° C. was blown onto the yarn at a rate of 30 m / min to cool and solidify, and then an oil agent was applied to the yarn. The oil used was an emulsion of “TRN-4627” manufactured by Takemoto Yushi Co., Ltd., which was emulsified 18% using ion-exchanged water.

  The unstretched yarn provided with the oil agent was wound around 1 FR rotating at a surface speed of 375 m / min. Next, the take-up yarn was continuously wound without being wound once and stretched 1.5% between the take-up roller and 2FR, and subsequently subjected to three-stage heat stretching to obtain 1.5% After giving relaxation, it was wound up at a speed of 3000 m / min. Direct spinning drawing was performed using the process shown in FIG. 1FR was 60 ° C, 2FR was 100 ° C, 1DR was 115 ° C, 2DR was 140 ° C, 3DR was 140 ° C, and RR was not heated. The number of times the yarn was wound around the roller was 3, 4, 4, 4, 5, and 4, respectively. An entanglement nozzle was installed between the RR and the winder to entangle the fibers. Entangling was performed by injecting 2 kg / cm 2 of high-pressure air in a direction substantially perpendicular to the running yarn in the entanglement imparting device to obtain polylactic acid fibers. The obtained fiber properties were evaluated and shown in Table 1. The first stage draw ratio was 34% of the overall draw ratio, the second stage draw ratio was 33%, and the third stage draw ratio was set to 33%.

  Six of the 1000 dtex polylactic acid fibers obtained were combined to give a 50 t / m twisted yarn, and 10 twisted yarns were further twisted at 40 t / m to obtain a 60000 dtex strand. Three strands were used to produce a rope having a diameter of 11 mm and a 180,000 dtex using three strands. The properties of the obtained rope were evaluated, and the results are shown in Table 1.

[Example 2]
Polylactic acid fibers were produced in the same manner as in Example 1 except that P3 was used instead of P4, and the properties of the ropes obtained by producing the ropes were evaluated. The results are shown in Table 1.

[Example 3]
The resin P2 is used instead of the resin P4, the resin P1 and the resin P2 are blended so that the final concentration of DAMGIC is 0.4% by weight, and the base described in Example 1 of JP-A-2005-240219 That is, in the same manner as in Example 1 except that a polylactic acid fiber having a hollow ratio of 40% was obtained using a die having a slit width of 0.35 mm, a slit diameter of 1.8 mm, and 48 holes with 4 slits. Polylactic acid fibers were produced, and the properties of the ropes produced were evaluated. The results are shown in Table 1.

[Example 4]
A polylactic acid fiber was produced in the same manner as in Example 1 except that P2 was used in place of P4 and P1 and P2 were blended so that the final concentration of DAMGIC was 7% by weight, and a rope was obtained. The characteristics of the rope were evaluated and the results are shown in Table 1.

[Examples 5 and 6]
A polylactic acid fiber can be produced and a rope can be produced in the same manner as in Example 1 except that the pressure of the high-pressure air jetted onto the yarn in the entanglement imparting device is changed so as to achieve the entanglement degree shown in Table 1. The properties of the obtained rope were evaluated and the results are shown in Table 1.

[Comparative Example 1]
Polylactic acid fibers were produced in the same manner as in Example 1 except that P5 was used in place of P4, and the properties of the rope obtained by producing the rope were evaluated. The results are shown in Table 1.

[Comparative Example 2]
Polylactic acid fibers were produced in the same manner as in Example 1 except that only P1 was used, and the characteristics of the ropes obtained by producing the ropes were evaluated. The results are shown in Table 1.

  As is clear from Table 1, the ropes of the present invention described in Examples 1 to 6 are much more resistant to hydrolysis than the polylactic acid of Comparative Example 2 in which the carboxyl group ends of the polylactic acid fibers are not blocked. It was an excellent rope. In addition, the present invention does not impair the effect even if it is a modified cross-section fiber as in Example 3, and it is lightweight and can add added value such as reducing the burden on the operator when installing the rope. It was.

  On the other hand, when the carboxyl group terminal of polylactic acid is blocked using a compound other than the general formula (I) disclosed in the present invention as described in Comparative Example 1, the reactivity between polylactic acid and the compound is poor. In addition to the occurrence of poor spinning performance, which is considered to be caused, there was a problem that the working environment deteriorated due to the generation of malodor during spinning.

It is a spinning process figure of an example of an embodiment of the present invention.

Explanation of symbols

1: Hopper 2: Extruder 3: Spin pack 4: Spinneret 5: Slow cooling zone 6: Cooling device 7: Refueling device 8: 1 FR
9: 2FR
10: 1DR
11: 2DR
12: 3DR
13: RR
14: Entangling device 15: Winding device

Claims (6)

A rope characterized in that a polylactic acid fiber represented by the following general formula (I) in which a part or all of the carboxyl group ends are blocked with at least one compound is at least a part of the constituent elements.

(Here, at least one of R _{1 to} R ₃ is a glycidyl group, and the rest represents a group selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and an allyl group.)   The rope according to claim 1, wherein the carboxyl group terminal concentration of the polylactic acid fiber is 20 equivalent / t or less.   The rope according to claim 1 or 2, wherein the amount of the compound represented by the general formula (I) is 0.1 to 5% by weight of the whole polylactic acid fiber.   The compound represented by the general formula (I) is one or more selected from diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and triglycidyl isocyanurate. The described rope.   The entanglement degree of polylactic acid fiber is 5-70, The rope in any one of Claims 1-4 characterized by the above-mentioned.   The rope according to any one of claims 1 to 5, wherein the rope is used as at least one selected from a marine rope and a land rope.

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