JP2008121125A - Sheath-core type conjugated monofilament - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monofilament which is excellent in dimensional stability, a filament shaving-controlling effect, a pirn contraction-preventing effect, printing characteristics, dyeability, antistaticity and the like, has a halation-preventing effect, and has a fine fineness, a high strength and a high modulus which enables high mesh. <P>SOLUTION: This sheath-core type conjugated monofilament using a polymer having an intrinsic viscosity of ≥0.70 dL/g as a core component and a specific polyester having an intrinsic viscosity of 0.40-0.65 dL/g as a sheath component. The monofilament is formed by specifying the number of knotted filament portions, a modulus at an elongation of 5%, a breaking elongation, the free contraction rate of the inner most layer, when the product is wound up, an imparted oil amount, and a coefficient of dynamic friction due to the impartation of the oil. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a core-sheath type composite monofilament having a modified surface. In more detail, core-sheath type composite monofilaments useful as raw yarn for ropes, nets, tegus, tarpaulins, tents, screens, paragliders and sailcloths, especially advanced mesh fabrics for screen printing, production of printed wiring boards, etc. The present invention relates to a core-sheath type composite monofilament suitable for obtaining a high mesh and high modulus screen wrinkle which requires high precision.

  Monofilaments are widely used not only in the clothing field but also in the industrial material field. In particular, examples of the latter application in the industrial material field include monofilaments as raw yarns for tire cords, ropes, nets, tegus, tarpaulins, tents, screens, paragliders and sailcloths.

  The properties required for such monofilaments are becoming increasingly severe in recent years, and improvements such as adhesion to rubber, fatigue resistance, dyeability, abrasion resistance, and knot strength are being urged. In particular, the degree of integration is increasing in recent printing in the field of electronic circuits, and the screen flaws used therefor are demands for improving printing density and printability, that is, hydrolysis resistance, ultraviolet absorption Along with improvements in functionality such as anti-static properties, the demand for high strength, high modulus, and high mesh is becoming increasingly strong. Therefore, the raw yarn is required to have finer, high strength, high modulus and improved characteristics.

  In general, in order to obtain a monofilament having high strength and high modulus, unoriented raw yarns may be hot-drawn at a high draw ratio in the production stage to be highly oriented and crystallized. However, in order to meet the demands of high meshes in the process of screen cocoon manufacturing, warps are warped and woven at a high density, and as a result, severer repeated friction is caused between the yarn and the cocoon. become. For this reason, whisker-like or powdery thread shaving occurs, and as a result, the productivity as well as the quality of the product deteriorate due to warp breakage due to defective opening.

As countermeasures against this, Japanese Patent Application Laid-Open No. 1-132829 (Patent Document 1) proposes a composite filament having a core-sheath structure in which nylon is arranged in the sheath portion, thereby suppressing yarn shaving. . Japanese Patent Application Laid-Open No. 2-289120 (Patent Document 2) proposes a method in which thread shaving is suppressed by disposing a polyester copolymerized with polyethylene glycol in a sheath portion. Further, JP-A-2003-213520 (Patent Document 3), JP-A-2003-213527 (Patent Document 4), JP-A-2004-232182 (Patent Document 5), and the like include a copolymer as a sheath portion. It is proposed that non-polyester polymers can also be used. For example, in Patent Document 4, when both the core and sheath components are polyethylene terephthalate, the intrinsic viscosity of the core component polymer is X, and the intrinsic viscosity of the sheath component polymer is Y, XY ≧ 0.25. A polyester monofilament for screen wrinkles characterized by being satisfactory and having a breaking strength of 6.5 cN / dtex or more is disclosed.
However, when these monofilaments were actually used for screens, it was found that their performance was not satisfactory.

Japanese Patent Laid-Open No. 1-132829 JP-A-2-289120 Japanese Patent Laid-Open No. 2003-213520 JP 2003-213527 A JP 2004-232182 A

  The present invention has excellent dimensional stability and yarn-scraping suppression effect that could not be obtained with conventional polyester composite monofilaments for screen wrinkles. An object of the present invention is to provide a composite monofilament with high fineness, high strength and high modulus. A further object of the present invention is to provide a composite monofilament having improved surface properties in addition to the above advantages.

  According to the present invention, the following core-sheath type composite monofilament is provided as a monofilament for achieving the above-mentioned problems.

1. The core component is a fiber-forming polymer having an intrinsic viscosity of 0.70 dL / g or more, and the sheath component is a polyester having an intrinsic viscosity of 0.40 to 0.65 dL / g or a composition containing the same as a main component, Conditions (A) to (E):
(A) The weight ratio of the core component is 50 to 90%,
(B) The number of node yarn portions having a diameter of 1.1 times or more with respect to the average fiber diameter of the monofilament is 1 or less per 100,000 meters in the fiber longitudinal direction;
(C) a monofilament having a fineness of 15 dtex or less, a modulus at an elongation of 5% satisfying 3.0 cN / dtex or more and a breaking elongation of 40% or less,
(D) The free shrinkage of the innermost layer portion measured over 10 days from the next day after product winding is 0.3% or less, and
(E) The adhesion amount of the oil agent (non-aqueous component) applied to the surface of the monofilament with respect to the fiber weight is 0.1 to 0.4% by weight, and the dynamic friction coefficient of the monofilament is 0.2 to 0 by the oil agent. .35 adjusted,
A core-sheath type composite monofilament characterized by satisfying

  2. The oil agent applied to the monofilament is an aliphatic ester compound of 50 to 80% by weight and an alcohol having 8 to 18 carbon atoms and 1 to 10 partial phosphate ester salts of ethylene oxide and / or propylene oxide 0 to 10 mol adduct. 2. The core-sheath type composite monofilament according to the above 1, characterized in that the oil agent is contained by weight%.

  3. 3. The core-sheath type composite as described in 1 or 2 above, wherein the core component and the sheath component are both polyester, and the polyester is a hydrolysis-resistant aromatic polyester having a terminal carboxyl group concentration of 15 eq / 106 g or less. Monofilament.

  4). The polyester constituting the core component and the sheath component is a hydrolysis-resistant aromatic polyester containing 3 to 50 ppm of a phosphoric acid ester represented by the following general formula in terms of phosphorus atom content. The core-sheath type composite monofilament according to 3 above.

  5. 3. The core-sheath type composite monofilament according to 1 or 2 above, wherein the polyester of the sheath component is an ultraviolet absorbing polyester containing 0.01 to 5.0% by weight of an organic ultraviolet absorber with respect to the polymer.

  6). The organic UV absorber is at least one UV absorber selected from the group consisting of a benzotriazole UV absorber, a benzophenone UV absorber, a triazine UV absorber, and a benzoxazine UV absorber. 5. The core-sheath type composite monofilament described in 5 above.

  7. 3. The core-sheath type composite monofilament according to the above 1 or 2, wherein the polyester of the sheath component is an easily dyeable polyester copolymerized with 0.5 to 2.5 mol% of a sulfonic acid phosphonium salt.

  8). 8. The core-sheath type composite monofilament according to 7 above, wherein the phosphonium sulfonate salt is a sulfonic acid phosphonium salt represented by the following formula.

  9. The sheath component contains 0.2 to 30 parts by weight of a polyoxyalkylene polyether per 100 parts by weight of the aromatic polyester and 0.05 to 10 parts by weight of an organic ionic compound substantially nonreactive with the polyester. 3. The core-sheath type composite filament according to 1 or 2 above, comprising an electroconductive polyester composition.

  10. 10. The core-sheath type composite filament according to 9 above, wherein the organic ionic compound is a sulfonic acid metal salt represented by the following general formula.

  11. An aromatic polyester having a core component made of a fiber moldable polymer having an intrinsic viscosity of 0.70 dL / g or more and a sheath component having an intrinsic viscosity of 0.50 to 0.65 dL / g, and a polyoxyalkylene type per 100 parts by weight of the aromatic polyester 11. The above 9 or 10 comprising a polyester composition containing 0.2 to 30 parts by weight of a polyether and 0.05 to 10 parts by weight of an organic ionic compound substantially nonreactive with the polyester. Core-sheath type composite monofilament.

Hereinafter, the core / sheath component constituting the composite monofilament of the present invention as described above will be described in more detail.
In the composite monofilament of the present invention, at least a specific aromatic polyester or a composition mainly composed of it is used as a sheath component. The aromatic polyester as used in the present invention is mainly composed of aromatic dicarboxylic acid represented by terephthalic acid as a main acid component, and at least one glycol, preferably at least selected from ethylene glycol, trimethylene glycol, and tetramethylene glycol. A polyester mainly composed of one kind of alkylene glycol as a main glycol component is mainly used. The aromatic polyester may be a copolyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and the glycol other than the main component may be part of the glycol or other It may be a copolyester replaced with a diol component.

  Here, examples of the bifunctional aromatic carboxylic acid other than terephthalic acid that can be used for copolymerization include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 2,6. -Naphthalenedicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone Dicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4, 4'-p-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, β-hydroxy ester Carboxymethyl benzoic acid, p- hydroxybenzoic acid, and diphenoxyethanedicarboxylic acid and the like. Two or more of these difunctional aromatic carboxylic acids may be used in combination. Furthermore, isophthalic acid having a metal sulfonate group such as 5-sodium sulfoisophthalic acid may be used as a copolymerization component as long as the effects of the present invention are substantially achieved. In this case, the amount used is changed to the terephthalic acid component. On the other hand, it is desirable to limit the amount to less than 1.0 mol%. In addition, if the amount is small enough not to impair the properties of the aromatic polyester, these difunctional aromatic carboxylic acids and bifunctional aliphatic carboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, cyclohexane One type or two or more types of bifunctional alicyclic carboxylic acids such as dicarboxylic acids may be used in combination.

  Examples of diol compounds include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and trimethylene glycol, 1,4- Preferable examples include alicyclic diols such as cyclohexanedimethanol and mixtures thereof. If the amount is small, polyoxyalkylene glycol having both ends or one end unblocked can be copolymerized with these diol compounds.

  Furthermore, a polycarboxylic acid such as trimellitic acid and pyromellitic acid, and a polyol such as glycerin, trimethylolpropane, and pentaerythritol can be used in combination as long as the aromatic polyester is substantially linear.

  Specific examples of preferred aromatic polyesters in the present invention include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyhexylene terephthalate and other homopolyesters, polyethylene isophthalate, Mention may be made of copolyesters such as terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate. Polyethylene naphthalate (PEN), polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, and the like can also be used. Among these aromatic polyesters, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) having a good balance of melt spinnability, fiber physical properties and the like are particularly preferable.

  Such aromatic polyester is synthesized by any method. For example, for polyethylene terephthalate (PET), terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid is used. The first stage reaction of reacting ethylene oxide with ethylene oxide to produce a glycol ester of terephthalic acid and / or a low polymer thereof, and then heating the product under reduced pressure until the desired degree of polymerization is achieved. It is easily produced by carrying out the second stage reaction for condensation reaction.

  The monofilament of the present invention is a core-sheath type composite filament (composite fiber), the core component is made of a fiber moldable polymer having an intrinsic viscosity of 0.70 dL / g or more, and the sheath component has a lower intrinsic viscosity than the core component. , An aromatic polyester in the range of 0.50 to 0.65 dL / g or a polyester composition containing the aromatic polyester as a main component, and the core component is covered with a sheath component in the cross section, and the core component is the surface It is a core-sheath type composite monofilament arranged so as not to be exposed. That is, here, the “core-sheath type” is a generic term for a core component that is completely covered with the sheath component, and the core component and the sheath component are not necessarily arranged concentrically in the fiber cross section. .

  In the composite monofilament of the present invention, the intrinsic viscosity of the polyester of the sheath component needs to be 0.40 to 0.65 dL / g, and preferably 0.45 to 0.60 dL / g. Usually, a monofilament having a high modulus property and a fineness of 15 dtex or less causes surface shaving. In the present invention, in order to suppress this, the intrinsic viscosity of the sheath portion is set to 0.40 to 0.65 dL / g. The thread shaving is suppressed by selecting to. However, if the intrinsic viscosity is less than 0.40 dL / g, not only the liquid feeding viscosity is too low and discharge during melt spinning becomes unstable, but it also has an adverse effect on the formation of the core-sheath structure, and the core part is on the surface. Risk of exposure. On the other hand, if the intrinsic viscosity exceeds 0.65, the effect of the core-sheath structure cannot be obtained, and yarn shaving occurs.

  On the other hand, the core component polymer is a polymer that can be composite-spun into the above-described aromatic polyester of the sheath component and a core-sheath type, and has an intrinsic viscosity of 0.7 dL / g or more, preferably 0.75 to 0.95 dL / g., a fiber-forming polymer. The type of polymer is not limited to polyester, and for example, polyethylene, polypropylene, polyamide, acrylic, and the like can be used, and may be a blend of two or more polymers as long as the above conditions are satisfied. Especially, since aromatic polyester has favorable affinity with the aromatic polyester used for a sheath side, it is especially preferable.

  Specific examples of polymers suitable as the core component include aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polytetramethylene terephthalate (PTT). Among these, PET is most suitable in terms of operability and cost when performing melt spinning. However, when the intrinsic viscosity of the core component polymer is less than 0.70 dL / g, the physical properties of the monofilament are deteriorated.

In the present invention, it is necessary for the composite monofilament to satisfy all the following conditions.
(A) The weight ratio of the core component is 50 to 90%;
(B) The number of node yarn portions having a diameter of 1.1 times or more with respect to the average fiber diameter of the monofilament is 1 or less with respect to 100,000 meters in the fiber longitudinal direction;
(C) In a monofilament having a fineness of 15 dtex or less, a modulus at an elongation of 5% satisfies 3.0 cN / dtex or more and a breaking elongation of 40% or less;
(D) the free shrinkage of the innermost layer portion measured over 10 days from the next day after product winding is 0.3% or less; and
(E) The amount of the oil agent (non-aqueous component) applied to the surface of the monofilament is 0.1 to 0.4% by weight with respect to the fiber weight, and the oil agent has a coefficient of friction between the fibers of the monofilament. It is adjusted to 0.2-0.35.

  That is, the weight ratio of the core component in the composite monofilament of the present invention is 50 to 90%, preferably 60 to 70%, based on the fiber (monofilament) weight. When the core component is less than 50% by weight, the influence of the sheath component on the fiber properties becomes remarkable, and it is difficult to achieve high strength and high modulus. On the other hand, when the core component exceeds 90% by weight, the thickness on the sheath side becomes very thin, about 5% of the fiber diameter, and when the outflow fluctuation of the liquid feeding due to viscosity fluctuation occurs, the thickness changes. There is a risk of exposure to the fiber surface.

  The composite monofilament of the present invention is further characterized in that the number of nodes having a diameter of 1.1 times or more with respect to the average fiber diameter per 100,000 meters in the fiber longitudinal direction is 1 or less. Examples of the generation factor of the nodal portion in the monofilament include unmelted foreign matters contained in the polymer and deterioration of the polymer itself. About the unmelted foreign material in a polymer, the discharge | emission can be suppressed or disperse | distributed by forming a filtration layer from a spinning pack inlet_port | entrance to a nozzle | cap | die discharge port. The filtration layer preferably has an opening of about 10 to 15% of the monofilament diameter, and if it is 10% or less, abnormal pressure is applied in the pack, leading to breakage of the parts in the pack and the pack body. If the amount of openings exceeds 15%, unmelted foreign matter that is the main cause of knots is contained in the yarn as coarse particles, and the risk of occurrence of knots increases. On the other hand, regarding the deterioration of the polymer itself, with regard to molten polymer feeding, the pipe bending is reduced, the time from the introduction of the pack to the discharge is within one minute, and the amount of heat received by the polymer is reduced as much as possible to reduce the risk of occurrence of nodes. be able to.

  Furthermore, in the composite monofilament of the present invention, the free shrinkage of the monofilament of the innermost layer portion of the package (pan) measured over 10 days from the next day after product winding is 0.3% or less, preferably 0.20 to 0.28%, It has the characteristic of being. Here, the innermost layer portion refers to a portion within 500 m after starting winding of a monofilament package (pan) wound up on a bobbin or the like. In general, monofilaments with high modulus properties are prone to panic sinks due to the effects of fiber structure distortion within the yarn. In order to reduce this, it is important to take up the product in a state in which the distortion in the product is sufficiently relaxed.

  In the composite monofilament of the present invention, after performing the 0.3 to 0.5% relaxation treatment after stretching, the condition is set so that the relaxation time of 0.05 seconds or more is taken from the final roller to winding. The free shrinkage rate of the innermost layer portion is 0.3% or less, and panic sinks can be suppressed. Further, if the relaxation treatment is 0.3 to 0.5%, the structural strain inside the fiber is alleviated without impairing the 5% elongation stress (modulus) (hereinafter referred to as “5% LASE”). be able to.

  In such a composite monofilament of the present invention, a monofilament having a fineness of 15 dtex or less, particularly 10 dtex or more and 14 dtex or less is suitable as a high mesh screen yarn suitable for precision printing. Those having fineness exceeding the above range are unsuitable as high mesh screen yarns. The 5% LASE is 3.0 cN / dtex or more (particularly 3.5 cN / dtex or more and 4.5 cN / dtex or less), and the elongation is 40% or less (particularly 15% or more and 35% or less). preferable. If the 5% LASE or the elongation is out of the above range, it is difficult to obtain a filament suitable for the high-mesh screen wrinkle targeted by the present invention.

  In the composite monofilament of the present invention, an oil agent in which a partial phosphate ester salt of a specific alkylene oxide addition ester is blended in an ester base is adopted as an oil agent to be applied at the spinning stage, and the fiber-metal and fiber-fiber inter-fibers are used. It was found that by adjusting the friction coefficient, the process passage stability after stretching was excellent. The oil agent is usually applied at the time of spinning in order to obtain excellent process passability with very little thread shaving in the weaving process, but it also has a great influence on the process pass stability after stretching.

  The oil agent imparted to the monofilament in the present invention mainly comprises an aliphatic ester compound (a) as a first oil agent component and an alkylene oxide addition ester (b) as a second oil agent component. The aliphatic ester compound (a), which is the first oil component, is used to reduce frictional resistance and suppress the generation of fluff due to abrasion, and includes fatty acid monoalkyl esters, aliphatic dicarboxylic acid dialkyl esters, fats A compound having a molecular weight in the range of 250 to 550 is preferred. When the molecular weight of the ester is less than 250, the smoothness of the resulting monofilament tends to be reduced because heat volatilization is likely. On the other hand, when the molecular weight exceeds 550, the smoothness of the resulting monofilament is insufficient, which is not preferable. Preferred aliphatic esters include, for example, fatty acid monoalkyl esters such as octyl octanoate, octyl stearate, isotridecyl laurate, isotridecyl oleate, lauryl oleate and aliphatic dicarboxylic acid dialkyl esters such as diisooctyl adipate. Is mentioned. Examples of mono- or multi-fatty acid esters of aliphatic polyhydric alcohols include, but are not limited to, trimethylolpropane trioctanoate. Of these, fatty acid monoalkyl esters are preferred.

  The alkylene oxide addition ester (b), which is the second oil component, is used to prevent yarn scraping due to abrasion between yarns during weaving by lowering the coefficient of dynamic friction between fibers. The component of the present invention is an ester compound obtained by reacting a glyceride having one or more hydroxyl groups in the molecule with an alkylene oxide, a dibasic acid component, and, if necessary, a monobasic acid component. Here, as the glyceride having one or more hydroxyl groups in the molecule, triglyceride is particularly preferable, and examples thereof include triglycerides such as ricinoleic acid and 12-hydroxystearic acid, and representative examples thereof include castor oil. Examples of the alkylene oxide added to the triglyceride include ethylene oxide, propylene oxide, and butylene oxide, and ethylene oxide is particularly preferable. The added mole number of alkylene oxide is 5 to 50 mol, preferably 10 to 30 mol. The addition method of alkylene oxide may be a conventional method, and when two or more types are added, they may be added randomly or in blocks.

The oil agent in the present invention contains both of the above components (a) and (b) as essential components, but other components such as esters, nonionic surfactants, anionic surfactants as necessary. An agent, an antioxidant, a compatibilizer, and a stability improver may be added as long as the object of the present invention is not impaired.
According to the study by the present inventors, when an oil agent other than the above is used, it is difficult to adjust the friction coefficient to the above specific range, the monofilament yarn scraping suppressing effect is small, and the scum of Since the occurrence is also seen, it is not preferable.

An arbitrary method can be adopted when the oil agent having the composition described above is adhered to the monofilament. For example, an emulsion obtained by emulsifying and dispersing an oil agent component in water may be used, or a straight oil agent may be used as it is for a monofilament.
That is, the oil agent is generally applied at the time of spinning in order to obtain very good process passability with very little yarn shaving in the weaving process. In the present invention, generally known arbitrary means can be applied to the monofilament to the monofilament. In particular, in the melt spinning process, an amount of the oil agent measured through an oiling nozzle with low resistance to the yarn is used. The imparting method is a more preferable method.

  The adhesion amount (OPU) of the oil agent to the monofilament needs to be 0.1 to 0.4% by weight as the amount of the active ingredient (non-aqueous component) relative to the fiber weight. When the adhesion amount (OPU) is less than 0.1% by weight, the smoothness becomes insufficient and the yarn is scraped and causes troubles such as scum. On the other hand, even if the adhesion amount (OPU) exceeds 0.4% by weight, the improvement of the yarn scraping suppression effect is small, and conversely, the occurrence of scum on the heel is caused, and an excessive oil agent contaminates the yarn guide and the like. This is not an industrial solution as it will also cause new problems.

  The composite monofilament of the present invention as described above has a reduced coefficient of dynamic friction between fibers and is reinforced with an oil film. And can pass through the weaving process satisfactorily.

  As a preferred method for producing such a monofilament of the present invention, a fiber moldable polymer having an intrinsic viscosity of 0.70 dL / g or more, an aromatic polyester having an intrinsic viscosity of 0.50 to 0.65 dL / g, or a main component thereof are used. The core-sheath type is such that the above-described fiber moldable polymer becomes the core component and the polyester or the composition becomes the sheath component, and the ratio of the core-sheath (weight ratio) is 50:50 to 90:10. To form a monofilament having a diameter of 1.1 times or more with respect to the average fiber diameter of 1 or less per 100,000 meters of fiber length, and after stretching, 0.3 to After 0.5% relaxation treatment, a method for setting conditions so that the relaxation time is 0.05 seconds or more from the last roller to winding can be adopted.

  At this time, the unmelted foreign matter in the polymer can be suppressed or dispersed by forming a filtration layer from the pack inlet to the die outlet. The filtration layer is preferably a filtration layer having an opening amount of about 10 to 15% of the diameter of the monofilament to be manufactured. In order to reduce deterioration of the polymer itself, the bending of the molten polymer feed pipe is reduced, The residence time from the introduction of the pack to the discharge is within 1 minute, and the amount of heat received by the polymer is reduced as much as possible, so that the risk of occurrence of nodes can be reduced, and the diameter is 1.1 times the average fiber diameter or more. It is possible to obtain a monofilament in which the number of node yarn portions is 1 or less per 100,000 meters of fiber length.

  The monofilament produced by the above method has a coefficient of dynamic friction between fibers lowered to 0.2 to 0.35, and is reinforced with an oil film. The weaving process can be satisfactorily passed without causing thread cutting or scum. If the coefficient of dynamic friction between the fibers is less than 0.2, thread shaving, scum, etc. increase and the product quality and processability deteriorate, making it difficult to achieve the object of the present invention.

  The core-sheath type composite monofilament of the present invention has finer, higher strength, higher modulus and improved characteristics. Therefore, in order to meet the demands of high mesh in the process of screen cocoon manufacturing, even if warp is severely repeated between the yarn and the heel when weaving, forming warp with high density and weaving, Since no cutting occurs and warp breakage due to defective opening does not occur, the productivity of the weaving process is improved and the quality of the product is improved. This core-sheath type composite monofilament is useful as a raw yarn for ropes, nets, tegus, tarpaulins, tents, screens, paragliders, sailcloths, etc., especially for the production of mesh fabrics for screen printing, printed wiring boards, etc. It is suitable for obtaining high mesh and high modulus screens requiring high precision.

  Next, specific embodiments of the present invention will be described. The present invention mainly includes a first embodiment related to a composite monofilament excellent in hydrolysis resistance (moisture heat resistance), a second embodiment related to a composite monofilament resistant to ultraviolet light, and a dark color in atmospheric boiling water. A third embodiment related to a composite monofilament that can be dyed and a fourth embodiment related to a composite monofilament having antistatic properties are included. Hereinafter, each embodiment will be described in detail mainly focusing on characteristic portions of each embodiment.

<About the first embodiment>
The first embodiment of the present invention relates to a composite monofilament that is excellent in heat-and-moisture resistance and has a small decrease in strength during use.
In the first embodiment of the present invention, an aromatic polyester having an intrinsic viscosity of 0.70 dL / g or more, preferably 0.75 to 0.95 dL / g is used as a core component, and 0.40 to 0.65 dL / g. In addition, an aromatic polyester having an aromatic polyester of 0.45 to 0.60 dL / g as a sheath component and a terminal carboxyl group concentration of both core-sheath components of 15 eq / 10 ⁶ gg or less is used. By using the oil agent to which the reinforcing component is applied, a monofilament is provided that is superior to conventional monofilaments, has excellent wet heat durability, and is also effective in thread shaving.

That is, the monofilament uses an aromatic polyester having a terminal carboxyl group concentration of 15 eq / 10 ⁶ g or less for both the core component and the sheath component, and the intrinsic viscosity of the polymer of the core component is 0.70 dL / g or more, And the intrinsic viscosity of the polyester of the sheath component is in the range of 0.40 to 0.65 dL / g, and is a core-sheath type composite monofilament having an intrinsic viscosity difference in the core sheath, and further satisfies the following (A) to (G) It is a monofilament characterized by doing.
(A) The weight ratio of the core component is 50 to 90%;
(B) The number of nodes of 1.1 times or more per fiber diameter per 100,000 meters in the fiber longitudinal direction of the monofilament is 1 or less;
(C) A monofilament having a fineness of 15 dtex or less satisfies a modulus at an elongation of 5% of 3.0 cN / dtex or more and a breaking elongation of 40% or less;
(D) the free shrinkage of the innermost layer portion measured over 10 days from the next day after product winding is 0.3% or less; and
(E) Oil containing 50 to 80% by weight of an aliphatic ester compound and 1 to 10% by weight of a partial phosphate ester salt of ethylene oxide and / or propylene oxide 0 to 10 mol adduct in an alcohol having 8 to 18 carbon atoms Is attached to 0.1 to 0.4% by weight based on the fiber weight, so that the fiber-fiber dynamic friction coefficient of the monofilament is adjusted to 0.2 to 0.35.

で表されるリン酸エステルをリンの含有量に換算して３〜５０ｐｐｍ含有している耐加水分解性の優れた芳香族ポリエステルが好ましい。 In the first embodiment, the polyester used in both the core component and the sheath component of the composite monofilament is an aromatic polyester having a terminal carboxyl group concentration of 15 eq / 10 ⁶ g or less, and General formula

An aromatic polyester excellent in hydrolysis resistance containing 3 to 50 ppm of the phosphoric acid ester represented by the formula (1) is preferable.

  In the first embodiment of the present invention, when a product is used repeatedly by using a polymer having excellent dimensional stability and yarn scraping suppressing effect which is not obtained by a conventional monofilament and having a small carbo end. Provided is a monofilament with little fineness, high fineness, high strength, and high modulus that can be made into a high mesh.

  Incidentally, as a method for increasing the hydrolysis resistance of the polyester filament, a method for decreasing the terminal carboxyl group concentration of the polyester in advance is known, and as a method for adding an epoxy compound for this purpose, Japanese Patent Publication No. 44-27911 is known. JP-A-54-6051 describes a method of adding a certain epoxy compound to reduce the terminal carboxyl group concentration of the polyester. However, these methods have a problem that the reactivity of the epoxy compound is low, the effect thereof is small, and the bending wear resistance is low even as a monofilament. In addition, as a method for enhancing the bending wear resistance of the polyester filament, a method of attaching metal particles (JP-A-3-76813), a method of coating a fiber surface with a silicon compound (JP-A-3-249273), polyester, There have been proposed methods for forming a core-sheath composite yarn with nylon (Japanese Patent Laid-Open No. 2-145894) and the like. Although these methods can provide a monofilament having a somewhat improved bending wear resistance, In addition to the low decomposability, there was a problem that the belt contact portion such as the roller surface was worn.

  Further, a method for producing a monofilament by reducing the terminal carboxyl group concentration by a melt polymerization method (JP-A-8-120520) has been proposed. In this method, the yarn surface is highly oriented and crystallized. . However, in order to meet the demand for high meshes in the process of manufacturing screen wrinkles, warps are formed at high density and woven. At that time, severe and repeated wear is caused between the yarn and the reed, and shaving or powdering occurs, and the quality of the product is lowered as well as productivity due to warp breakage due to defective opening.

The monofilament according to the first embodiment of the present invention has both terminal carboxyl group concentrations of polyester having an intrinsic viscosity of 0.70 dL / g or more as a core component and polyester of 0.40 to 0.65 dL / g as a sheath component. By using an aromatic polyester having less terminal carboxyl groups, which is 15 eq or less per 10 ⁶ g of polymer, it is superior to conventional monofilaments in terms of wet heat durability and by using an oil agent with an oil film reinforcing agent. The present invention provides a monofilament that is also effective in machinability.

  In the first embodiment of the present invention, the intrinsic viscosity of the polyester of the sheath component is 0.40 to 0.65 dL / g. Usually, monofilaments having a high modulus property and a fineness of 15 dtex or less cause surface shaving. In the present invention, in order to suppress this, thread shaving can be suppressed by setting the intrinsic viscosity of the sheath portion to 0.40 to 0.65 dL / g, particularly 0.45 to 0.60 dL / g. However, if the intrinsic viscosity is less than 0.40 dL / g, not only does the feeding viscosity become too low, the ejection during spinning becomes unstable, but it also adversely affects the formation of the core sheath, and the core portion is exposed to the surface with the filament. There is a risk of doing. When the intrinsic viscosity exceeds 0.65, the effect of the core-sheath structure cannot be obtained, and thread cutting occurs.

Fine mesh filaments of 15 dtex or less, particularly 10 to 15 dtex, are used for high mesh screens (300 to 400 mesh) suitable for precision printing.
The filament for woven fabric needs to have dimensional stability sufficient to suppress the occurrence of deterioration of weaving property and elongation of cocoon. As a substitute characteristic for obtaining the dimensional stability, it is often discussed in terms of the stress generated in the low elongation region. Generally, the performance can be evaluated by the stress at 5% elongation (5% ASE). It is common. The monofilament for screen wrinkles of the present invention can be increased in strength by using a high intrinsic viscosity polymer having an intrinsic viscosity of 0.7 dL / g or more, particularly 0.70 to 0.90 dL / g, as the core component. % Modulus is 3.0 cN / dtex or more, and elongation at break is 40% or less.

The polymer used for the core component and the sheath component used in this embodiment is polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6 naphthalate, or the like, or a hydrolysis-resistant aromatic polyester mainly composed of these, The terminal carboxyl group concentration of the aromatic polyester is 15 eq / 10 ⁶ g or less, preferably 10 eq / 10 ⁶ g or less.

  Further, in the first embodiment of the present invention, the phosphate ester contained in the aromatic polyester is a compound represented by the following formula.

In R1 to R3, the alkoxide group is preferably an alkoxide group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, specifically, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , -OC ₄ H _9, and _OC 5 _{H 11} and the like. Examples of allyloxide include phenoxide (—O—C ₆ H ₅ ) and toluoxide (—O—C ₆ H ₄ —CH ₃ ).

で表され、ここで、Ｒ４は炭素数２〜６、好ましくは炭素数２〜４のアルキレン基であり、ｎは２〜２５、好ましくは２〜１０の範囲である。 The phosphoric acid ester of the general formula (I) is characterized in that at least one of R1 to R3 is a polyoxyalkylene glycol group. Such polyoxyalkylene glycol groups are represented by the formula

Wherein R 4 is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and n is in the range of 2 to 25, preferably 2 to 10.

  The polyester used in the present invention not only lowers the terminal carboxyl group, but also uses a specific phosphate ester and further specifies the catalyst species and the amount thereof as necessary, thereby limiting the intrinsic viscosity under wet heat conditions. It becomes an aromatic polyester excellent in heat resistance and hydrolysis resistance, in which degradation of the resin and terminal carboxyl group concentration are suppressed. Of course, in order to improve the hydrolysis resistance, it is also important to reduce the terminal carboxyl group concentration as known from the past. For that purpose, optimization of the polymerization process of polyester, high intrinsic viscosity by solid phase polymerization and You may add well-known low carbating agents, such as low terminal carboxyl group concentration and various epoxy compounds, by arbitrary methods. Moreover, you may contain additives, such as a stabilizer and a coloring agent, as needed.

  However, with ordinary polyethylene terephthalate having no hydrolysis resistance, for example, the strength is maintained even when ordinary polyethylene terephthalate having an intrinsic viscosity of 0.72 dL / g for the core portion and an intrinsic viscosity of 0.56 dL / g for the sheath portion is used. The rate drops to about 35%, and a good screen wrinkle targeted in this embodiment cannot be obtained.

  As already described, the composite monofilament of the present invention is a core-sheath type composite monofilament arranged so that the core component is covered with the sheath component and the core component is not exposed on the surface in the cross section. As for the cross-sectional shape, it is easy to obtain stable yarn-making and high-order workability, to prevent halation that occurs when the emulsion after weaving is coated and exposed to light, the stability of the screen wrinkles, etc. For this reason, a round cross section is preferred.

  In the monofilament of the present invention, the weight ratio of the core component (ratio to the whole fiber) is 50 to 90%, preferably 60 to 70%. When the core component is less than 50% by weight, the influence of the sheath component becomes significant as the yarn physical properties, and it is difficult to achieve high strength and high modulus. On the other hand, if it exceeds 90% by weight, the thickness of the sheath component becomes about 5% of the fiber diameter and becomes very thin. If the outflow fluctuation of the liquid feeding due to viscosity fluctuation occurs, the thickness changes. There is a risk that the components are exposed on the yarn surface.

  As described above, the monofilament has a feature that there are no more than one node having a diameter of 1.1 times or more of the fiber diameter per 100,000 m in the longitudinal direction of the fiber. As a cause of the generation of the node portion, there are unmelted foreign matters contained in the polymer and deterioration of the polymer itself. About the unmelted foreign material in a polymer, the discharge | emission can be suppressed or disperse | distributed by forming a filtration layer from a pack entrance to a nozzle | cap | die discharge port. The filtration layer preferably has an opening of about 10 to 15% of the diameter of the monofilament, and if it is less than 10%, abnormal pressure is applied in the pack, leading to breakage of the parts in the pack and the pack body. If it exceeds 15%, unfused foreign matter that is the main cause of knot yarn is contained in the yarn as coarse particles, and the risk of knot generation increases. In addition, with regard to the deterioration of the polymer itself, with regard to polymer feeding, the bending of the pipe is reduced, the time from introduction of the pack to discharge is within 1 minute, and the amount of heat received by the polymer is reduced as much as possible to reduce the risk of occurrence of nodes be able to.

  Further, the monofilament has a free shrinkage of 0.3% or less at the innermost layer portion measured over 10 days from the next day after the product is wound. Here, the innermost layer portion refers to a portion within 500 m after starting winding of the monofilament wound up on a bobbin or the like. A monofilament having a high modulus property such as that of the present invention tends to cause panic sinks due to the influence of the fiber structure distortion inside the yarn. In order to reduce this, it is important to take up the product in a state in which the distortion in the product is sufficiently relaxed. In the present invention, after stretching, 0.3-0.5% relaxation treatment is performed, and by setting the conditions so as to have a relaxation time of 0.05 seconds or more from the final roller to winding, the panic sink is suppressed. can do. Further, if the relaxation treatment is 0.3 to 0.5%, the structural strain inside the fiber can be alleviated without impairing 5% ASE.

  As described above, the monofilament according to the first embodiment of the present invention employs an oil agent (finishing agent) in which a partial phosphate ester salt of a specific alkylene oxide addition ester is blended in the base of a fatty acid ester compound, By adjusting the static friction between the metal and the fiber and the fiber within the specific range as described above, the process passage stability after stretching is excellent. The oil agent is applied at the time of spinning in order to obtain very good process passability with very little thread shaving in the weaving process.

  As described above for each oil component, the aliphatic ester compound as component (a) is used to reduce frictional resistance and suppress the generation of fluff due to abrasion, and includes fatty acid monoalkyl esters and aliphatic dicarboxylic acids. It refers to compounds such as acid dialkyl esters and mono- or multi-fatty acid esters of aliphatic polyhydric alcohols, and those having a molecular weight in the range of 250 to 550 are preferred. When the molecular weight of the ester is less than 250, the smoothness of the resulting monofilament tends to be reduced because heat volatilization is likely. On the other hand, when it exceeds 550, the smoothness of the obtained monofilament becomes insufficient, which is not preferable. Preferred aliphatic esters include, for example, fatty acid monoalkyl esters such as octyl octanoate, octyl stearate, isotridecyl laurate, isotridecyl oleate, lauryl oleate and the like, and as aliphatic dicarboxylic acid dialkyl esters And diisooctyl adipate. Examples of mono- or multi-fatty acid esters of aliphatic polyhydric alcohols include trimethylolpropane trioctanoate. Of these, fatty acid monoalkyl esters are preferred.

  Further, the alkylene oxide addition ester as the component (b) is used for preventing yarn abrasion due to abrasion between yarns during weaving by lowering the coefficient of dynamic friction between fibers. This component is an ester compound obtained by reacting a glyceride having one or more hydroxyl groups in the molecule with an alkylene oxide, a dibasic acid component and, if necessary, a monobasic acid component. Here, as the glyceride having one or more hydroxyl groups in the molecule, triglyceride is particularly preferable, and examples thereof include triglycerides such as ricinoleic acid and 12-hydroxystearic acid, and representative examples thereof include castor oil. Examples of the alkylene oxide added to the triglyceride include ethylene oxide, propylene oxide, and butylene oxide, and ethylene oxide is particularly preferable. The added mole number of alkylene oxide is 5 to 50 moles, preferably 10 to 30 moles. The addition method of alkylene oxide may be a conventional method, and when two or more types are added, they may be added randomly or in blocks.

  The oil agent in the present invention is based on the above-mentioned components, but other components such as esters, nonionic surfactants, anionic surfactants, antioxidants, compatibilizers as necessary. You may add an agent and a stability improver in the range which does not impair the objective of this invention. When attaching the oil agent demonstrated above to a monofilament, the emulsion emulsified in water may be used, a stock solution may be used as it is, and arbitrary methods are employable.

  In general, any known means can be used to apply the oil agent (non-aqueous component) to the composite monofilament, but in particular, it is measured through an oiling nozzle that reduces resistance to the yarn in the melt spinning process. A more preferable method is a method of providing the same amount.

  The adhesion amount (OPU) of the oil to the monofilament needs to be in the range of 0.1 to 0.4% by weight as an active ingredient (non-aqueous ingredient) with respect to the fiber. When the adhesion amount is less than 0.1% by weight, the smoothness becomes insufficient and the yarn is scraped and causes troubles such as scum. On the other hand, even if it exceeds 0.4% by weight, the improvement of the yarn scraping suppression effect is small, and on the contrary, excessive oil generation of scum on the heel will contaminate the yarn guide and the like, causing a new problem. It is not industrially profitable. The monofilament obtained by using the above method has a low fiber-fiber static coefficient of friction and is reinforced with an oil film, and is good without repetitive rubbing such as wrinkles and without shaving or scum. Can pass through the weaving process.

<About the second embodiment>
The second embodiment of the present invention relates to a composite monofilament having ultraviolet absorptivity. Specifically, high precision such as production of monofilaments useful as raw yarn for ropes, nets, tegus, tarpaulins, tents, screens, paragliders and sailcloths, especially mesh fabrics for screen printing, printed wiring boards, etc. This monofilament is suitable for obtaining the required high mesh and high modulus screen wrinkles. It has UV absorption characteristics to reduce the occurrence of halation, and less thread shaving than by strengthening the oil film on the surface of the oil. This relates to the characteristic monofilament.

  It is very important to control the ultraviolet exposure process in the manufacturing process of the screen bottle. If the exposure amount is small, the photosensitive film may not be sufficiently cured and may fall off during development. On the other hand, if the amount is too large, the photosensitive resin may be lost during development, and the texture may be distorted. Regardless of the intensity of the ultraviolet rays, the ultraviolet rays are irregularly reflected on the yarn surface, and so-called halation occurs in which the portions that do not need to be exposed are exposed and cured, resulting in a drastic change in printing design and accuracy.

  In order to suppress such halation, there is a method of dyeing screen wrinkles. However, there is a limit to the performance of halation suppression by dyeing, which is not sufficient, and a dyeing process is required after weaving. Damage due to wet heat.

  In addition, there is a method of kneading inorganic particles that block ultraviolet rays, such as titanium oxide, but it is difficult to obtain a stable blocking performance because the inorganic particles easily aggregate and are difficult to uniformly disperse. Furthermore, the agglomerates may cause threading.

  A polyester monofilament in which an organic ultraviolet absorber is contained in a polyester yarn in an amount of 0.1% by weight or more has already been proposed (Japanese Patent Laid-Open No. 59-150110). However, since the breaking strength is lowered by directly kneading the organic ultraviolet absorber, it is not possible to obtain a target monofilament having high strength and high modulus.

  In addition, a method of physically covering the warp and weft of the polyester screen ridge with an ultraviolet antireflection film has been proposed (Japanese Patent Laid-Open No. 2003-19875). However, the number of steps for coating the protective film is increased and special equipment is required, which leads to a large cost increase.

  In order to obtain high breaking strength at a low cost, a core-sheath type composite monofilament has been proposed (Japanese Patent Laid-Open No. 2004-262007). However, when using a polymer containing an organic compound-based UV absorber directly on the sheath side like this composite monofilament, in the required high mesh screen manufacturing process, a high mesh is required. It is necessary to form a warp in the density and weave it. As a result, it will be subjected to severe repeated friction between the yarn and the kite, which causes shavings or powders to be scraped off, resulting in a decrease in productivity as well as productivity due to warp breakage due to defective opening. .

  In the second embodiment of the present invention, an ultraviolet absorber is blended only in the sheath component on the surface, and the generation of halation is reduced by having ultraviolet absorption characteristics, and the oil film of the oil agent adhered to the yarn surface is reinforced to reduce thread shaving. Fewer monofilaments are provided.

Such a monofilament uses a polymer having an intrinsic viscosity of 0.70 dL / g or more as a core component, and a 0.40 to 0.65 dL / g polyester containing 0.01 to 5.0% by weight of an organic ultraviolet absorber. It is a core-sheath type composite monofilament configured by being used as a sheath component, and is a composite monofilament satisfying all the following conditions (A) to (F).
(A) The weight ratio of the core component is 50 to 90%;
(B) The polyester used for the sheath component is at least one ultraviolet ray whose ultraviolet absorber is selected from the group consisting of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, and benzoxazine ultraviolet absorbers. The absorbent is 0.01 to 5.0% by weight;
(C) The length of the monofilament fiber is 100,000 meters and the number of knots is 1.1 or more times the fiber diameter;
(D) A monofilament having a fineness of 15 dtex or less satisfies a modulus at an elongation of 5% of 3.0 cN / dtex or more and a breaking elongation of 40% or less;
(E) The free shrinkage of the innermost layer portion measured over 10 days from the next day after the product is rolled up is 0.3% or less; and (F) the aliphatic ester compound is 50 to 80% by weight and the carbon number is 8 to 18 By adding 0.1 to 0.4% by weight of an oil agent containing 1 to 10% by weight of a partial phosphate ester salt of ethylene oxide and / or propylene oxide 0 to 10 mol adduct to the alcohol of The monofilament fiber-fiber dynamic friction coefficient is adjusted to 0.2 to 0.35.

  As described above, the second embodiment of the present invention has excellent dimensional stability, yarn scraping suppression, and yarn saving suppression effects that could not be obtained with conventional monofilaments, and improved halation suppression by using an ultraviolet absorbing polymer. In addition, a monofilament having a fineness, a high strength, and a high modulus that can be made into a high mesh is provided.

  That is, in this monofilament, a fiber-forming polymer having an intrinsic viscosity of 0.70 dL / g or more is used as a core component, and an organic ultraviolet absorber is contained in an amount of 0.01 to 5.0% by weight. By using 0.65 dL / g aromatic polyester as a sheath component, it is superior in UV absorption compared to conventional monofilaments, and by using an oil agent with oil film reinforcement on the yarn surface, thread shaving is also improved. The present invention provides a monofilament characterized by being effective.

  In this embodiment, it is preferable to use a high-definition filament having a high mesh screen (300 to 400 mesh) suitable for precision printing of 15 dtex or less, particularly 10 to 15 dtex. The filament for woven fabric needs to have dimensional stability sufficient to suppress the occurrence of deterioration of weaving property and elongation of cocoon. As a substitute characteristic for obtaining the dimensional stability, it is often discussed in terms of the stress generated in the low elongation region. Generally, the performance is evaluated by the stress at 5% elongation (modulus, hereinafter 5% LASE). It is common to do. Also in the second embodiment of the present invention, the monofilament for screen wrinkles can be strengthened by using a high intrinsic viscosity polymer of 0.7 dL / g or more as the core component, and the modulus at 5% elongation is 3.0 cN. / Dtex or more and the elongation at break can be 40% or less.

  In this embodiment, the type of the core component polymer is not limited to polyester, and examples thereof include polyethylene, polypropylene, polyamide, acrylic, etc., and core-sheath composite spinning is possible, and if the intrinsic viscosity is 0.7 dL / g or more, Without limitation, it can be used. Of these, polyester is particularly preferred because of its good affinity with the ultraviolet-absorbing polyester used on the sheath side. Examples of the polyester used include aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Among these, PET is an operation for performing melt spinning. It is also optimal in terms of performance and cost.

  The intrinsic viscosity of the UV-absorbing polyester serving as the sheath component is 0.40 to 0.65 dL / g. Usually, a thin monofilament having a high modulus property and a fineness of 15 dtex or less causes surface shaving at the yarn making stage and the processing stage. In order to suppress this, in the present invention, thread shaving is suppressed by setting the sheath portion to 0.40 to 0.65 dL / g. If the intrinsic viscosity is less than 0.40 dL / g, not only the liquid feeding viscosity is too low, the ejection during spinning becomes unstable, but also the core sheath formation is adversely affected, and the core portion may be exposed to the surface. . On the other hand, if the intrinsic viscosity exceeds 0.65, the effect of the core-sheath structure cannot be obtained, and yarn shaving tends to occur.

  As the ultraviolet absorber added to the sheath component polymer, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a benzoxazine ultraviolet absorber or a benzophenone ultraviolet absorber is used.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl). ) -5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2- (3'-tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis (4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3 ', 5'-bi) (Α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, 2- (3 ′, 5′-di-tert-amyl-2′-hydroxyphenyl) benzotriazole, 5-trifluoromethyl-2- (2 -Hydroxy-3- (4-methoxy-α-cumyl) -5-tert-butylphenyl) -2H-benzotriazole and the like.

  Among them, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl) -5′-methylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3 '-Tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole is preferred, and 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole is more preferred.

  As the triazine-based ultraviolet absorber, hydroxyphenyltriazine-based registered trademark “Tinuvin 400” (manufactured by Ciba Specialty Chemicals) is preferable.

  Examples of the benzoxazine-based ultraviolet absorber include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazine-4-one, 2-phenyl-3,1-benzoxazine -4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2,2 ′ -Bis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one, 2,2'-m-phenylenebis (3,1- Benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-naphthalene) ) Bis (3,1-benzoxazin-4-one) 1,3,5-tris (3,1-benzoxazin-4-on-2-yl) benzene and the like, among others, 2,2′-p-phenylenebis (3,1-benzoxazine-4 -On) is preferred.

  Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and the like can be mentioned, among which 2-hydroxy-4-n-octoxybenzophenone is preferable. These ultraviolet absorbers may be used alone or in combination of two or more.

  The content of these ultraviolet absorbers is 0.01 to 5.0% by weight, preferably 0.02 to 3.0% by weight, particularly preferably 0 to 100% by weight of the aromatic polyester. 0.05 to 2.0% by weight. If it is less than 0.01% by weight, the ultraviolet absorption performance is insufficient, and if it exceeds 5.0% by weight, the hue of the resin may be deteriorated.

  In addition, when normal aromatic polyester which does not have an ultraviolet-absorbing characteristic in a sheath part is used, printing performance will be 3 points | pieces or less by evaluation mentioned later, and the target screen wrinkle in this embodiment cannot be obtained.

  The monofilament of the present embodiment is a core-sheath type composite monofilament arranged so that the core component is covered with the sheath component and the core component is not exposed on the surface in the cross section. The cross-sectional shape is round due to the fact that stable yarn-making and high-order processability are easily obtained, halation that occurs when the emulsion after weaving is exposed to light, and the stability of the opening of the screen wrinkles. A cross section is preferred.

  The monofilament has a core component weight ratio of 50 to 90%, as in the first embodiment already described. Preferably it is 60 to 70%. When the core component is less than 50% by weight, the influence of the sheath component becomes significant as fiber properties, and it is difficult to achieve high strength and high modulus. On the other hand, if it exceeds 90% by weight, the thickness on the sheath side becomes about 5% of the fiber diameter and becomes very thin, and when the outflow fluctuation of the liquid feeding due to viscosity fluctuation occurs, the thickness changes. Risk of exposure to the surface.

  Further, the number of node portions is 1.1 times or more with respect to the fiber diameter per 100,000 meters in the fiber longitudinal direction of the monofilament. Examples of the generation factor of the node in the monofilament include unmelted foreign matters contained in the polymer and deterioration of the polymer itself. About the unmelted foreign material in a polymer, the discharge | emission can be suppressed or disperse | distributed by forming a filtration layer from a pack entrance to a nozzle | cap | die discharge port. The filtration layer preferably has an opening of about 10 to 15% of the monofilament diameter, and if it is 10% or less, abnormal pressure is applied in the pack, leading to breakage of the parts in the pack and the pack body. If it is 15% or more, unmelted foreign matters that are the main cause of knotting are contained in the yarn as coarse particles, and the risk of knotting increases. In addition, with regard to the deterioration of the polymer itself, with regard to polymer feeding, the bending of the pipe is reduced, the time from introduction of the pack to discharge is within 1 minute, and the amount of heat received by the polymer is reduced as much as possible to reduce the risk of occurrence of nodes be able to.

  Furthermore, the monofilament has a feature that the free shrinkage of the innermost layer portion measured over 10 days from the next day after the product is wound is 0.3% or less. Here, the innermost layer portion refers to a portion within 500 m after starting winding of the monofilament wound up on a bobbin or the like. The monofilament with high modulus properties as in this study tends to cause panic sinks due to the strain of the fiber structure inside the yarn. In order to reduce this, it is important to take up the product in a state in which the distortion in the product is sufficiently relaxed. In the present invention, after stretching, 0.3-0.5% relaxation treatment is performed, and by setting the conditions so as to have a relaxation time of 0.05 seconds or more from the final roller to winding, the panic sink is suppressed. can do. Further, if the relaxation treatment is 0.3 to 0.5%, the structural strain inside the fiber can be alleviated without impairing 5% ASE.

  Even in this monofilament, it is possible to stabilize the process after drawing by adopting an oil agent that contains a specific phosphate ester of a specific alkylene oxide addition ester in the ester base and setting the static friction between fiber and metal and fiber and fiber within a specific range. It was found that the properties are excellent. The oil agent is applied at the time of spinning in order to obtain very good process passability with very little thread shaving in the weaving process.

  For each oil component, as in the first embodiment, the aliphatic ester compound (a) and alkylene that reduce the frictional resistance and adjust the friction coefficient within the above range and suppress the occurrence of fluff and thread shaving. This is a combination of oxide addition ester (b) components. This oil agent is based on the above components (a) and (b), but if necessary, other components such as esters, nonionic surfactants, anionic surfactants, oxidation agents Inhibitors, compatibilizers, stability improvers and the like may be added as long as the object of the present invention is not impaired. When attaching the oil agent demonstrated above to a monofilament, the emulsion emulsified in water may be used, a stock solution may be used as it is, and arbitrary methods are employable.

  Generally, any generally known means can be used for applying the oil agent to the monofilament, but among them, a method in which a measured amount is applied through an oiling nozzle that reduces resistance given to the yarn is more preferable. It is.

  The amount of the oil agent (non-aqueous component) attached to the monofilament needs to be 0.1 to 0.4% by weight as an active ingredient with respect to the fiber. When the adhesion amount is less than 0.1% by weight, the smoothness becomes insufficient and the yarn is scraped and causes troubles such as scum. On the other hand, even if it exceeds 0.4% by weight, the improvement of the yarn scraping suppression effect is small, and on the contrary, excessive oil generation of scum on the heel will contaminate the yarn guide and the like, causing a new problem. It is not industrially profitable. The monofilament obtained by using the above method has a low fiber-fiber static coefficient of friction and is reinforced with an oil film, and is good without repetitive rubbing such as wrinkles and without shaving or scum. Can pass through the weaving process.

<About the third embodiment>
The third embodiment of the present invention requires a monofilament that can be dyed in dark color in atmospheric boiling water, and more specifically, requires a high degree of precision such as the manufacture of mesh fabrics for screen printing, printed wiring boards, etc. The present invention relates to a monofilament suitable for obtaining a high-mesh, high-modulus screen wrinkle that can be dyed darkly in boiling water at normal pressure.

  Polyester fibers, especially polyethylene terephthalate fibers, have many excellent properties such as strength and dimensional stability, and are used in various applications. On the other hand, the polyethylene terephthalate fiber is inferior in dyeability, and it requires dyeing at a high temperature and high pressure around 130 ° C., so that a special device is required.

  Several attempts have been made to improve polyethylene terephthalate dyeability and normal pressure dyeing. For example, a method using a carrier at the time of dyeing has been known. There are drawbacks that make it difficult. In addition, polyethylene terephthalate with improved dyeability is known as a copolymer of a metal sulfonate group-containing compound or polyether, but these modified polyesters improve dyeability, but polymerization and spinning are difficult, Or there existed faults, such as reducing the original outstanding property of a polyethylene terephthalate, and also inferior fastness.

  In the third embodiment of the present invention, it is possible to dye a deep color by excellent dimensional stability, an effect of suppressing thread scraping, an effect of preventing punning, and atmospheric pressure dyeing, which were not obtained with a conventional monofilament, and further halation There is provided a monofilament having a fineness, high strength, and high modulus that has a preventive effect and can be made into a high mesh. The monofilament of the present invention comprises a polymer having an intrinsic viscosity of 0.70 dL / g or more as a core component and a polyester in which 0.5 to 2.5 mol% of a sulfonic acid phosphonium salt is copolymerized as a sheath component. By making it possible to dye monofilaments that conventionally require high-pressure dyeing at normal pressure, it has the advantage of being superior to the conventional monofilament and having excellent modulus properties of the screen after processing by reducing the processing damage that occurs during dyeing. .

（Ｃ）モノフィラメントの繊維長手方向１０万メートルで繊維直径に対し１．１倍以上の節糸が１個以下であること；
（Ｄ）繊度が１５ｄｔｅｘ以下のモノフィラメントにおいて伸度５％時のモジュラスが３．０ｃＮ／ｄｔｅｘ以上、破断伸度が４０％以下を満足すること；
（Ｅ）製品巻上げ翌日から１０日間かけて測定した最内層部分のフリー収縮率が０．３％以下であること；
（Ｆ）脂肪族エステル化合物が５０〜８０重量％と炭素数８〜１８のアルコールにエチレンオキサイド及び／又はプロピレンオキサイド０〜１０モル付加物の部分リン酸エステル塩が１〜１０重量％含有する油剤が繊維重量を基準として０．１〜０．４重量％付着することによってモノフィラメントの繊維−繊維動摩擦係数が０．２〜０．３５に調整されていること。 That is, this monofilament has an intrinsic viscosity of a polyester, which is a sheath component in which a fiber-forming polymer having an intrinsic viscosity of 0.70 dL / g or more as a core component and 0.5 to 2.5 mol% of a sulfonic acid phosphonium salt is copolymerized. The core-sheath type composite monofilament composed of a sheath component of polyester in the range of 0.45 to 0.65 dL / g satisfies the following A to F.
(A) The weight ratio of the core component is 50 to 90%;
(B) The sheath component is an aromatic polyester copolymerized with a sulfonic acid phosphonium salt represented by the following formula;

(C) The length of the monofilament fiber is 100,000 meters and the number of knots is 1.1 or more times the fiber diameter;
(D) A monofilament having a fineness of 15 dtex or less satisfies a modulus at an elongation of 5% of 3.0 cN / dtex or more and a breaking elongation of 40% or less;
(E) The free shrinkage rate of the innermost layer portion measured over 10 days from the next day after product winding is 0.3% or less;
(F) Oil containing 50 to 80 wt% of an aliphatic ester compound and 1 to 10 wt% of a partial phosphate ester salt of ethylene oxide and / or propylene oxide 0 to 10 mol adduct in an alcohol having 8 to 18 carbon atoms The fiber-fiber dynamic friction coefficient of the monofilament is adjusted to 0.2 to 0.35 by adhering 0.1 to 0.4% by weight based on the fiber weight.

  In the third embodiment of the present invention, excellent dimensional stability, yarn scraping suppression effect, pirn-reducing effect, normal pressure dyeing, which could not be obtained with a conventional monofilament, can be dyed darkly, and further halation There is provided a monofilament having a fineness, high strength, and high modulus that has a preventive effect and can be made into a high mesh. That is, the monofilament has conventionally been constituted by comprising a polymer having an intrinsic viscosity of 0.70 dL / g or more as a core component and a polyester in which 0.5 to 2.5 mol% of a sulfonic acid phosphonium salt is copolymerized as a sheath component. It is possible to dye monofilaments that require high-pressure dyeing at normal pressure and reduce the processing damage that occurs during dyeing, thereby obtaining monofilaments that are superior to the conventional monofilament in the modulus characteristics of screens after processing. .

  For high mesh screens (300 to 400 mesh) suitable for precision printing, fine filament monofilaments of 15 dtex or less, particularly 10 to 15 dtex, are used. The filament for woven fabric needs to have dimensional stability sufficient to suppress the occurrence of deterioration of weaving property and elongation of cocoon. As a substitute characteristic for obtaining the dimensional stability, it is often discussed in terms of the stress generated in the low elongation region. Generally, the performance is evaluated by the stress at 5% elongation (modulus, hereinafter 5% LASE). It is common to do. The screen filament monofilament of the present invention can be strengthened by using a polymer having a high intrinsic viscosity of 0.7 dL / g or more as a core component, and the modulus at 5% elongation is 3.0 cN / dtex or more. The elongation can satisfy 40% or less.

  The kind of the core side polymer constituting the monofilament of the third embodiment in the present invention includes polyester, polyethylene, polypropylene, polyamide, acrylic and the like, as in the second embodiment described above. If the allowable intrinsic viscosity is 0.7 dL / g or more, the type of polymer is not limited and can be arbitrarily used. Of these, polyester is particularly preferred because of its good affinity with the antistatic polyester used on the sheath side. Examples of the type of polyester used for the core include aromatic polyesters such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). . Among these, PET is optimal in terms of operability and cost when performing melt spinning.

で表わされるスルホン酸ホスホニウム塩が３〜１０モル％程度共重合されている芳香族ポリエステルが好ましい。 As a kind of the sheath component polyester used in the third embodiment of the present invention, among others,

An aromatic polyester in which about 3 to 10 mol% of a sulfonic acid phosphonium salt represented by the formula (1) is copolymerized is preferable.

  The intrinsic viscosity of the sheath component polyester needs to be 0.40 to 0.65 dL / g, and 0.50 to 0.60 is preferable. Usually, monofilaments having a high modulus property and a fineness of 15 dtex or less cause surface shaving. However, according to the study by the present inventors, it was found that thread shaving can be suppressed by setting the intrinsic viscosity of the sheath portion to 0.40 to 0.65 dL / g. On the other hand, when the intrinsic viscosity of the sheath component exceeds 0.65, the effect of the core-sheath structure cannot be obtained, and thread cutting occurs. On the other hand, if the intrinsic viscosity is less than 0.40 dL / g, the liquid feeding viscosity is too low and not only the discharge during melt spinning becomes unstable, but also the core sheath formation is adversely affected, and the core portion is exposed to the surface. There is.

  As for the cross-sectional shape of the filament, as in the first and second embodiments, it is easy to obtain stable yarn forming properties and high-order workability, and halation that occurs when the emulsion after weaving is applied and exposed to light. A round cross-section is preferable in terms of prevention, stability of the opening of the screen ridge, and the like.

  The monofilament also needs to have a weight ratio of the core component of 50 to 90%, preferably 60 to 70%. If it is less than 50% by weight, the influence of the sheath component becomes significant as the yarn physical properties, and it is difficult to achieve high strength and high modulus. On the other hand, when the weight ratio of the core component exceeds 90% by weight, the thickness on the sheath side becomes about 5% of the fiber diameter and becomes very thin. In some cases, there is a risk that the core component is exposed on the yarn surface.

  Furthermore, the number of nodes is 1.1 or more times the fiber diameter per 100,000 meters in the fiber longitudinal direction of the monofilament. As a cause of the generation of the node portion, there are unmelted foreign matters contained in the polymer and deterioration of the polymer itself. About the unmelted foreign material in a polymer, the discharge | emission can be suppressed or disperse | distributed by forming a filtration layer from a spinning pack inlet_port | entrance to a nozzle | cap | die discharge port. For this filtration layer, an opening of about 10-15% of the monofilament diameter is preferred. If the mesh opening is less than 10% of the monofilament diameter, abnormal pressure is applied in the pack, leading to damage to the pack components and the pack body. If it is larger than 15%, unfused foreign matters that are the main cause of knotting are contained in the yarn as coarse particles, and the risk of occurrence of knots increases. In addition, with regard to the deterioration of the polymer itself, with regard to polymer feeding, the bending of the pipe is reduced, the time from introduction of the pack to discharge is within 1 minute, and the amount of heat received by the polymer is reduced as much as possible to reduce the risk of occurrence of nodes be able to.

  And as for this monofilament, the free shrinkage | contraction rate of the innermost layer part measured over 10 days from the next day after product winding is 0.3% or less. Here, the innermost layer portion refers to a portion within 500 m after starting winding of the monofilament wound up on a bobbin or the like. A monofilament having a high modulus property such as that of the present invention tends to cause panic sinks due to the influence of the fiber structure distortion inside the yarn. In order to reduce this, it is important to take up the product in a state in which the distortion in the product is sufficiently relaxed. In the present invention, after stretching, 0.3-0.5% relaxation treatment is performed, and by setting the conditions so as to have a relaxation time of 0.05 seconds or more from the final roller to winding, the panic sink is suppressed. can do. Further, if the relaxation treatment is 0.3 to 0.5%, the structural strain inside the fiber can be alleviated without impairing 5% ASE.

  Even in the monofilament according to the third embodiment, the oil agent having the specific composition described above, that is, the use of an oil agent in which a specific alkylene oxide addition ester or a phosphate ester salt is blended in an ester base, fiber, metal, fiber and fiber. By setting the static friction to a specific range, the process passage stability after stretching is improved. The oil agent is applied at the time of spinning in order to obtain extremely good process passability with very little yarn shaving in the weaving process.

  Generally, any generally known means can be used to apply the oil agent to the monofilament, but among them, a method of applying a measured amount via an oiling nozzle that reduces resistance given to the yarn is a more preferable method. is there.

  The amount of the oil agent attached to the monofilament needs to be 0.1 to 0.4% by weight as an active ingredient with respect to the fiber. When the adhesion amount is less than 0.1% by weight, the smoothness becomes insufficient and the yarn is scraped and causes troubles such as scum. On the other hand, even if it exceeds 0.4% by weight, the improvement of the yarn scraping suppression effect is small, and on the contrary, excessive oil generation of scum on the heel will contaminate the yarn guide and the like, causing a new problem. It is not a good industrial solution. The monofilament obtained by using the above method has a reduced fiber-fiber static friction coefficient and reinforced oil film, so that thread scraping and scum do not occur even against repeated rubbing such as wrinkles, It can pass through the weaving process well.

<About the fourth embodiment>
The fourth embodiment of the present invention is an antistatic monofilament, in particular, a mesh mesh for screen printing, a high mesh and high modulus screen kite that requires a high degree of precision, such as for manufacturing printed wiring boards. The present invention relates to an antistatic composite monofilament suitable for the above.

  In recent printing in the electronic circuit field, the degree of integration is increasing, and there is a demand for improved printing density and printability as a screen for printing, that is, high strength, high modulus and high mesh. The demand is getting stronger. For this reason, the monofilament that is the constituent yarn of the printing screen reed is also required to have high strength, high modulus, and finer fineness.

  On the other hand, high-mesh, high-modulus screen wrinkles enable high-density printing with a small amount of wrinkle opening, and even the slightest print defects that have not been a problem until now have become noticeable. Therefore, there is a need for a means for improving these very few printing defects. Many of these printing defects are caused not only by thread scraping but also by the fact that the wrinkles used are charged. For example, if static electricity is charged to the cocoon due to friction on the cocoon in the processing process, printing defects may occur due to adhesion of dust or dust, or printing ink may be scattered during printing due to static electricity that is charged with static electricity. There was a problem that occurred. In order to eliminate these printing defects, JP-A-2-289119, JP-A-2001-262438, etc. propose a core-sheath type composite monofilament having a polyester containing a polyalkylene ether as a core component. However, since the antistatic agent is contained on the core side and is not exposed on the surface, good antistatic performance cannot be obtained.

  In addition, in order to cope with these kinds of problems, an industrial fabric is known in which a metal wire such as a copper wire is woven into a part of a polyester monofilament fabric. This is not practical because of problems such as generation and rubbing of the roller that comes into contact with the fabric.

  In addition, an industrial woven fabric in which a conductive core-sheathed nylon monofilament using a conductive nylon resin composition blended with a high concentration of highly conductive carbon black as a sheath component was woven into a polyester monofilament fabric was also used. , Polyester monofilaments and conductive core-sheath nylon monofilaments have different dimensional stability during moisture absorption, which not only causes undulations in the dryer, but also has poor flowability of nylon resin blended with carbon black at a high concentration. Therefore, there was a problem that a uniform conductive core-sheath nylon monofilament could not be obtained.

  Further, a core component comprising a composition of a polyester mixture of aromatic polyester / aliphatic polyester (mixing weight ratio 80/20 to 98/2) and conductive carbon black as described in JP-A-56-85423, A conductive composite fiber having a sheath component made of an aromatic polyester has also been proposed, but the conductivity is insufficient because there is no conductive carbon black in the sheath component, so that the carbon black is 20 to 30% by weight. Therefore, there is a problem that the spinneret surface is soiled and stable production for a long time is difficult.

  Japanese Patent Application Laid-Open No. 8-74125 includes a sheath component containing 4 to 15% by weight of highly conductive carbon black and 96 to 85% by weight of a copolyester composition and a core component composed of an aromatic polyester. Core-sheath composite type conductive polyester monofilament has been proposed, but because carbon black is exposed on the surface, there are problems such as wrinkle wear during weaving and rubbing the roller that the fabric contacts, and dyeing is possible. Therefore, it is impossible to dye the antihalation color that occurs when the emulsion is applied and exposed to light when making a screen wrinkle.

  According to the fourth embodiment of the present invention, it has excellent dimensional stability, yarn scraping suppression effect, and punning prevention effect that could not be realized by a conventional monofilament, and also has excellent antistatic properties, and halation. There is provided a monofilament having a fineness, high strength, and high modulus, which has a prevention effect and can be made into a high mesh.

  In this embodiment, the core component is made of a fiber moldable polymer having an intrinsic viscosity of 0.70 dL / g or more, the sheath component is an aromatic polyester having an intrinsic viscosity of 0.50 to 0.65 dL / g, and 100 parts by weight of the aromatic polyester. Comprising an antistatic polyester composition containing 0.2 to 30 parts by weight of a polyoxyalkylene polyether and 0.05 to 10 parts by weight of an organic ionic compound substantially non-reactive with the polyester, The core-sheath type composite monofilament having a weight ratio of 50 to 90%, the coefficient of dynamic friction between the fibers of the monofilament being 0.2 to 0.35, and 1.1 with respect to the average fiber diameter of the monofilament. Winding measured over 10 days from the next day after winding the product, where the number of knots having a diameter of 1 or more is 1 or less per 100,000 meters of fiber length Ri package core-sheath composite monofilament wherein that free shrinkage of the innermost layer part is 0.3% or less is provided.

  In the monofilament, 50 to 80% by weight of the above-described aliphatic ester compound (a) and a partial phosphate ester salt of an ethylene oxide and / or propylene oxide 0 to 10 mol adduct with an alcohol having 8 to 18 carbon atoms ( b) An oil containing 1 to 10% by weight, but 0.1 to 0.4% by weight based on the fiber weight is adhered.

  In such a monofilament, a high mesh screen yarn suitable for precision printing has a fineness of 15 dtex or less, a modulus at an elongation of 5% of 3.0 cN / dtex or more, and an elongation of 40%. The following is preferable. The fiber-forming polymer that forms the core component of the monofilament is preferably an aromatic polyester having an intrinsic viscosity of 0.70 dL / g or more.

  The monofilament according to the fourth embodiment of the present invention has excellent dimensional stability, an effect of suppressing thread scraping, and an effect of preventing punning that cannot be obtained by a conventional monofilament. In addition, by using antistatic polyester that can be dyed as a sheath component, monofilaments with high fineness, high strength, and high modulus that have excellent antistatic properties, have antihalation effects, and can be made into high meshes. It is. Therefore, it can be used effectively in fields that have not been used so far.

  In particular, for fine filament monofilaments having a fineness of 15 dtex or less, particularly 10 to 15 dtex, used for the production of high-mesh screens (300 to 400 mesh) suitable for precision printing, the weaving property is reduced and the wrinkle elongation is reduced. Dimensional stability that suppresses the occurrence of such is required. As a substitute characteristic for realizing the dimensional stability, the stress is often discussed in terms of the generated stress in the low elongation region. In general, the performance is evaluated by the stress at 5% elongation (5% ASE). It is common. In the monofilament of the present invention, the core component is composed of a polymer having a high intrinsic viscosity of 0.7 dL / g or more, so that the strength can be increased, and the modulus at an elongation of 5% is 3.0 cN / dtex or more. Satisfies the characteristics of 40% or less.

  The monofilament according to the fourth embodiment of the present invention is a core-sheath type composite monofilament in which the core component is a fiber-forming polymer and the sheath component is composed of a specific antistatic polyester composition. The components are each composed of the following polymers and polymer compositions.

  That is, examples of the polymer constituting the core component in the monofilament of the fourth embodiment of the present invention include polyester, polyethylene, polypropylene, polyamide, acrylic polymer, and the like, and the core sheath with the polyester composition serving as the sheath component There is no particular limitation as long as the composite spinning is possible and the intrinsic viscosity is 0.7 dL / g or more, and it can be arbitrarily used. Of these, polyester is particularly preferred because of its good affinity with the antistatic polyester composition used on the sheath side. Specific examples of the polyester suitable for the core component include aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). In particular, polyethylene terephthalate (PET) having an intrinsic viscosity of 0.70 to 0.85 is most suitable in terms of operability and cost when performing melt spinning. The core component may contain additives such as a stabilizer, a flame retardant, and a filler as necessary.

On the other hand, the sheath component in the monofilament of the present embodiment is composed of an aromatic polyester composition having antistatic properties including two specific types of compounds.
That is, the antistatic aromatic polyester composition serving as the sheath component is mainly composed of the normal aromatic polyester as described above, and the polyoxyalkylene polyether (A) and the polyester as an antistatic agent are used as the antistatic agent. In particular, it contains both non-reactive organic ionic compounds (B).

  The polyoxyalkylene polyether (A) may be a polyoxyalkylene glycol composed of a single oxyalkylene unit as long as it is substantially insoluble in the aromatic polyester as a base. It may be a copolymerized polyoxyalkylene glycol composed of oxyalkylene units, or may be a polyoxyethylene polyether represented by the following general formula (I).

  Specific examples of the polyoxyalkylene polyether (A) include polyoxyethylene glycol having a molecular weight of 4000 or more, polyoxypropylene glycol having a molecular weight of 1000 or more, polyoxytetramethylene glycol, ethylene oxide having a molecular weight of 2000 or more, Propylene oxide copolymer, trimethylolpropane ethylene oxide adduct having a molecular weight of 4000 or more, nonylphenol ethylene oxide adduct having a molecular weight of 3000 or more, and a compound in which a substituted ethylene oxide having 6 or more carbon atoms is added to the terminal OH group. Among them, polyoxyethylene glycol having a molecular weight of 10,000 to 100,000 and polyoxyethylene glycol having a molecular weight of 5,000 to 16000 have an alkyl group having 8 to 40 carbon atoms at both ends. Compounds le-substituted ethylene oxide added are preferred.

  The content (blending amount) of the polyoxyalkylene polyether compound (A) is in the range of 0.2 to 30 parts by weight, preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the aromatic polyester. is there. When the content is less than 0.2 parts by weight, the hydrophilicity is insufficient and sufficient antistatic property cannot be imparted to the sheath component. On the other hand, even if it exceeds 30 parts by weight, the antistatic effect is no longer recognized, and the mechanical properties of the resulting composition are impaired, and the polyether is more likely to bleed out. The spinning ability of the chip into the ruder during spinning is lowered, and the spinning stability is also deteriorated.

  In addition to the polyoxyalkylene polyether compound (a) as described above, the polyester composition serving as the sheath component of the monofilament of the present invention further improves the antistatic property, in addition to the polyoxyalkylene polyether (A). ) Contains a non-reactive organic ionic compound (B).

  Preferable examples of the organic ionic compound (B) include a sulfonic acid metal salt represented by the following general formula (II) and a sulfonic acid quaternary phosphonium salt represented by the following general formula (III).

  In the above formula (II), when R is an alkyl group, it may be linear or have a branched side chain. M is an alkali metal such as Na, K, Li or the like, or an alkaline earth metal such as Mg, Ca. Among them, Li, Na, K are preferable. Such sulfonic acid metal salts may be used alone or in combination of two or more. Specific examples of preferable metal salts of sulfonic acid include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, sodium alkyl sulfonate mixture having an average of 14 carbon atoms, sodium dodecyl benzene sulfonate mixture, dodecyl benzene Examples thereof include sodium sulfonate (hard type, soft type), lithium dodecylbenzenesulfonate (hard type, soft type), magnesium dodecylbenzenesulfonate (hard type, soft type), and the like.

  Only one kind of the sulfonic acid quaternary phosphonium salt may be used, or two or more kinds thereof may be mixed and used. Specific examples of the preferred quaternary phosphonium salt of sulfonic acid include tetrabutylphosphonium alkyl sulfonate having an average of 14 carbon atoms, tetraphenyl phosphonium alkyl sulfonate having an average of 14 carbon atoms, Average butyl triphenylphosphonium alkyl sulfonate, tetrabutyl phosphonium dodecyl benzene sulfonate (hard type, soft type), tetraphenyl phosphonium dodecyl benzene sulfonate (hard type, soft type), benzyl triphenyl dodecyl benzene sulfonate Examples include phosphonium (hard type, soft type).

  These organic ionic compounds (B) may be used alone or in combination of two or more, but in any case, the total compounding amount is 0.05 to 100 parts by weight with respect to 100 parts by weight of the aromatic polyester. The range is 10 parts by weight. If the amount of the organic ionic compound is less than 0.05 parts by weight, the effect of improving the antistatic property is small, and if it exceeds 10 parts by weight, the mechanical properties of the composition are impaired, and the ionic compound also bleeds out. As a result, it becomes easier to bite the chip into the ruder during melt spinning, and the spinning stability also deteriorates.

The intrinsic viscosity of the polyester composition of the sheath component needs to be 0.40 to 0.65 dL / g, and preferably 0.50 to 0.65. Usually, monofilaments having a high modulus property and a fineness of 15 dtex or less cause surface shaving. In order to suppress this, thread shaving can be suppressed by setting the intrinsic viscosity of the sheath portion to 0.40 to 0.65 dL / g. When the intrinsic viscosity is less than 0.40 dL / g, not only does the feeding viscosity of the sheath component become too low during spinning and the discharge becomes unstable, but it also adversely affects the formation of the core-sheath composite filament, and the core part is the surface. There is a risk of exposure. On the contrary, if the intrinsic viscosity exceeds 0.65, the effect of the core-sheath structure cannot be obtained, and thread cutting occurs.
The aromatic polyester composition of the sheath component may contain additives such as a stabilizer, a flame retardant, a colorant, a matting agent, and a filler in addition to the above-described components.

  Also in the fourth embodiment of the present invention, the number of knots of 1.1 times or more with respect to the fiber diameter in the monofilament fiber longitudinal direction is 100,000 meters or less, and the elongation of monofilaments having a fineness of 15 dtex or less. The modulus at 5% is 3.0 cN / dtex or more, the elongation at break is 40% or less, and the free shrinkage of the innermost layer portion measured over 10 days from the day after the product is wound is 0.3% or less. In addition, the aliphatic ester compound contains 50 to 80% by weight and 1 to 10% by weight of a partial phosphate ester salt of ethylene oxide and / or propylene oxide 0 to 10 mol adduct in an alcohol having 8 to 18 carbon atoms. The oil agent adheres in an amount of 0.1 to 0.4% by weight based on the fiber weight. .35 It is necessary is adjusted to is the same as the first to third embodiments already described.

  The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited thereto. In each case, intrinsic viscosity, strength, elongation, strength retention, free shrinkage, adhesion rate of oil to yarn, measurement of dynamic friction coefficient, evaluation of the number of joints, evaluation of thread scraping, etc. The following method was used. In addition, “parts” in the examples means parts by weight unless otherwise specified.

(A) Intrinsic viscosity of aromatic polyester or aromatic polyester composition:
Dilution solutions of each concentration (C) in which the sample was dissolved in orthochlorophenol at 35 ° C. were prepared, and C was brought close to 0 from the viscosity (ηr) of these solutions by the following formula.

  In addition, the intrinsic viscosity of each core-sheath component is the same as the spinneret used at the time of spinning, and the residence time in melting is equivalent, and a spinneret designed so that the polymer of the core component and the sheath component can be discharged separately is sufficient. After the discharge state was stabilized, the discharge polymer was collected and measured.

(A) Strength and elongation:
The strength and elongation of the fiber (monofilament) are measured in accordance with JIS-L1017 using a Tensilon manufactured by Orientec Co., Ltd. with a sample length of 25 cm and an elongation rate of 30 cm / min, and the strength and elongation when the sample breaks. It is. 5% ASE is a value obtained by measuring the stress (cN / dtex) when the sample at the time of the above measurement is stretched by 5%.

(C) Strength retention:
The yarn sample was treated at 135 ° C. × 60 hr under the conditions of wet pyrolysis, the strength was measured, and the strength retention was evaluated as a ratio to the strength of the raw yarn (yarn before wet pyrolysis).

(D) Free shrinkage rate:
A sample weighed 2.0 kg was collected from the innermost layer portion so as not to cause distortion to the innermost layer portion, and allowed to stand at room temperature under no load in a skeined state, and the yarn length was measured again after 10 days. The yarn length after 10 days was divided by the yarn length of 5000 m before standing to obtain the free shrinkage as a percentage display.

(E) Adhesion rate of oil to thread:
After 3 g of drawn yarn was dried at 105 ° C. for 2 hours, its weight (A) was immediately measured. Then, it was immersed in 300 cc of an aqueous cleaning solution mainly composed of sodium alkylbenzene sulfonate, and ultrasonic waves were applied at 40 ° C. for at least 10 minutes. The washing liquid was discarded, washed with running water at 40 ° C. for 30 minutes, and then air-dried at room temperature. Thereafter, the weight (B) was measured immediately after drying at 105 ° C. for 2 hours, and the oil agent adhesion rate (OPU) to the yarn was calculated by the following formula.

(F) Coefficient of dynamic friction:
Using a drawn yarn, a fiber-metal running friction measuring machine, using a satin chrome pin with a diameter of 60 mm as a friction body at a running speed of 300 m / min, a contact angle of 180 degrees, and a friction body entry side tension of 10 g (T1). The exit tension (T2) was measured. The dynamic friction coefficient (f) between the fibers is calculated based on these measured values (T1, T2) from the following well-known formula relating to the friction of the belt running on the cylinder.

(G) Evaluation of the number of nodes:
In front of the dropper installed at the creel outlet of the warping machine, 12 slit guides having a clearance of thread diameter × 1.1 times and a tolerance of ± 2 μm were installed. Threads were passed through the slit guide, and 12 yarns × 8 stages = 96 yarns were warped at a yarn speed of 500 m / min, and each yarn length was 200,000 m. At that time, the number of times the yarn was cut by the slit guide was regarded as the number of knots, and the number of times the yarn was cut during warping was measured. The evaluation was performed by converting the detected number of times of yarn breakage into a yarn length of 100,000 m.

(H) Evaluation of thread cutting:
A mesh fabric was woven using a warp loom with a weaving speed of 250 rpm and 300 warps per inch of weaving width, and the woven fabric was visually inspected with a inspection machine. At this time, the number of fabric defects in which the mesh pattern that normally appears black was whitened was counted and evaluated. Based on the result, less than 5 defects due to thread cutting per 1.5 m woven width × 30 m fabric length were evaluated as “◯”, 5 or more and less than 10 as “Δ”, and 10 or more as “×”.

(G) Antistatic performance evaluation:
The drawn yarn was scoured as a woven fabric or a tubular knitting, and the frictional voltage was measured in accordance with JIS-L-1094 method. Friction cloth shall be wool, measured at room temperature of 20 ° C. and humidity of 40%, evaluated with ○ when the charged voltage after 500 seconds of friction is 500V or less, Δ when 1000V or less, and × when 1000V or more. did.

(E) Printing performance evaluation:
The woven fabric obtained above was stretched, an ultraviolet curable photosensitive resin was applied, and a fine line pattern having a line width of 50 μm was exposed and baked with a high-pressure mercury lamp, thereby producing a screen plate. Printing was performed on the substrate using the screen plate, and 40 sheets of ink fading were determined using a microscope 300 times. When the number of abnormal substrates was 0, 5 points, 1-10 were 4 points, 11-20 were 3 points, 21-30 were 2 points, 31-40 were 1 point.

(Sa) Dyeing evaluation:
A woven or knitted fabric obtained by making the drawn yarn into a tubular knitted or woven fabric and dyed under normal pressure at 100 ° C. The dyeing evaluation was performed in five stages, with the dark dyeing level being five points and the light dyeing level being one point. .

[Example 1]
As a core component, a hydrolysis-resistant polyethylene terephthalate having an intrinsic viscosity of 0.86 dL / g and having a terminal carboxyl group concentration of less than 10 eq / 10 ⁶ g polymer and containing 10 ppm of phosphoric acid ester by weight of phosphorus atom is used. As the sheath portion, 0.60 dL / g hydrolysis-resistant polyethylene terephthalate having a terminal carboxyl group concentration of less than 10 eq · 106 g and containing 10 ppm of phosphoric acid ester in terms of the weight of phosphorus atom is used independently. The mixture was melted at a temperature of 295 ° C. and weighed so that the core-sheath ratio was 60:40. The intrinsic viscosity of the polymer sampled 2 hours after the start of discharge was 0.72 dL / g for the core component and 0.55 dL / g for the sheath component.

  While the above-mentioned polymers of the core-sheath component are melt-combined and wound into a concentric core-sheath type at a spinning temperature of 295 ° C. and a spinning speed of 1200 m / min, the above oil agent is measured on the basis of fiber weight with an oiling nozzle. The amount shown in Table 1 was attached to obtain an undrawn yarn. Thereafter, the unstretched yarn was preheated with a heated hot roller, then stretched by 3.8 times while being heated with a slit heater, subjected to a relaxation treatment of 0.3%, wound up, and 13 dtex-1 fil A drawn yarn was obtained.

  The obtained drawn yarn (core-sheath type composite monofilament raw yarn) has a strength of 6.0 cN / dtex, an elongation of 23%, a strength retention of 67%, a 5% ASE of 3.9 cN / dtex, and a free shrinkage of 0.23%. The oil adhesion rate (OPU) was 0.21% by weight, and the dynamic friction coefficient was 0.25. Further, the strength retention after wet heat treatment was 67%, and the number of knots generated in the raw yarn was 0 per 100,000 m of yarn length. When this raw yarn was woven with a slewer type loom, the number of fabric defects due to the occurrence of yarn shaving was 0 per 30 m.

[Example 2]
In Example 1, drawn yarn was produced under the same conditions and method as in Example 1 except that the intrinsic viscosity of the hydrolysis-resistant polyethylene terephthalate used for the core component was changed to a polymer (chip) of 0.9 dL / g. The intrinsic viscosity of the core component from which the discharge sample was collected in the same manner as in Example 1 was 0.8 dL / g. There was no difference in terms of other quality except that 5% LASE was slightly improved.

[Comparative Example 1]
In Example 1, the amount of the oil agent discharged from the oiling nozzle was used, and other than that, a drawn yarn was obtained by the same method as in Example 1. However, although the strength retention rate was kept at 65%, the oil agent adhesion rate (OPU) ) Was 0.05% by weight, and thread shaving during weaving occurred frequently.
As described above, the results of Examples 1 and 2 and Comparative Example 1 in which the intrinsic viscosity and oil agent adhesion rate of the core component or the sheath component are changed are shown in Table 1 below.

[Example 3]
Polyethylene terephthalate having an intrinsic viscosity of 0.86 dL / g as a core component, and “Tinuvin 400” (registered trademark, hydroxyphenyl triazine UV absorber manufactured by Ciba Specialty Chemicals Co., Ltd.) in a polyethylene terephthalate having an intrinsic viscosity of 0.60 dL / g as a sheath component ) Was absorbed at a temperature of 295 ° C., and the core-sheath ratio was measured to be 60:40. The intrinsic viscosity sampled 2 hours after the start of discharge was 0.72 dL / g for the core component and 0.55 dL / g for the sheath component.

  Both of these components were melt melt-spun into a sheath-core type at a spinning temperature of 295 ° C., wound at a spinning speed of 1200 m / min, and the same oil agent as in Example 1 was attached with an oiling nozzle, Obtained. Then, after preheating with a heated hot roller, the film was stretched by 3.8 times while being heated with a slit heater, subjected to a relaxation treatment of 0.3%, and wound to obtain a stretched yarn of 13 dtex-1 fil. .

  The obtained drawn yarn (core-sheath type composite monofilament yarn) has a strength of 6.0 cN / dtex, an elongation of 23%, a 5% ASE of 3.9 cN / dtex, a free shrinkage of 0.23%, and an oil agent adhesion rate of 0.21. %, And the coefficient of dynamic friction was 0.25. The number of node yarn generation of the raw yarn was zero. When this raw yarn was woven using a slewer-type loom, the number of fabric defects due to the occurrence of yarn shaving was 0 per 30 m, and the printing performance was good at 5 points.

[Example 4]
In Example 3, a drawn yarn was obtained in the same manner as in Example 1, except that the intrinsic viscosity of the ultraviolet absorbing polyethylene terephthalate used for the core component was changed to 0.9 dL / g. A discharge sample was collected in the same manner as in Example 1. The intrinsic viscosity of the core component was 0.8 dL / g. There was no difference in terms of other quality except that 5% LASE was slightly improved.

[Comparative Example 2]
In Example 3, the oil component was changed, and the dynamic friction coefficient was set to 0.5. Otherwise, a drawn yarn was obtained in the same manner as in Example 1. The oil adhesion rate (OPU) was 0.19% by weight and the printing performance was as good as 5 points, but the yarn was frequently scraped during weaving.
As described above, the results of Examples 3 to 4 and Comparative Example 2 in which the new component, the sheath component, and the oil agent adhesion rate are changed are shown in Table 2 below.

[Example 5]
Polyethylene terephthalate having an intrinsic viscosity of 0.86 dL / g as a core component, and sulfonic acid phosphonium salt copolymerizable polyethylene terephthalate having an intrinsic viscosity of 0.60 dL / g as a sheath part, independently melted at a temperature of 290 ° C., The measurement was performed so that the core-sheath ratio was 60:40. The intrinsic viscosity sampled 2 hours after the start of discharge was 0.72 dL / g for the core component and 0.54 dL / g for the sheath component.

  Both these components are compound-spun into a sheath-core type at a spinning temperature of 290 ° C., unwound yarn while winding at a spinning speed of 1200 m / min and adhering the same oil agent as in Example 1 with an oiling nozzle. Got. Then, after preheating with a heated hot roller, the film was stretched by 3.8 times while being heated with a slit heater, subjected to a relaxation treatment of 0.3%, and wound to obtain a stretched yarn of 13 dtex-1 fil. .

  The obtained drawn yarn (core-sheath type composite monofilament yarn) has a strength of 6.0 cN / dtex, an elongation of 23%, a 5% ASE of 3.9 cN / dtex, a free shrinkage of 0.23%, and an oil agent adhesion rate of 0.21. %, And the coefficient of dynamic friction was 0.25. The number of node yarn generation of the raw yarn was zero. When this raw yarn was woven with a slewer type loom, the number of fabric defects due to the occurrence of yarn shaving was 0 per 30 m. In addition, the dyeing evaluation was 5 points, and all were good.

[Example 6]
In Example 5, a drawn yarn was obtained in the same manner as in Example 5 except that the intrinsic viscosity of polyethylene terephthalate used for the core component was changed to 0.9 dL / g. A discharge sample was collected in the same manner as in Example 1. The intrinsic viscosity of the core component was 0.8 dL / g. There was no difference in terms of other quality except that 5% LASE was slightly improved.

[Comparative Example 3]
In Example 5, a 5% oil agent discharge amount was obtained, and other than that, a drawn yarn was obtained in the same manner as in Example 5, but the oil agent adhesion rate (OPU) was 0.05% by weight, and the yarn during weaving There was frequent scraping.
The results of Examples 5 to 6 and Comparative Example 3 in which the sheath component or the core component, the core-sheath ratio, the oil agent adhesion rate, and the like are changed as described above are collectively shown in Table 3 below.

[Example 7]
An antistatic polyethylene terephthalate composition containing polyethylene terephthalate having an intrinsic viscosity of 0.86 dL / g as the core component and polyethylene glycol having a specific viscosity of 0.63 dL / g and a sulfonic acid metal salt as the sheath portion is used independently. Was measured at a temperature of 294 ° C. so that the core-sheath ratio (weight ratio) was 60:40. The intrinsic viscosity sampled 2 hours after the start of discharge was 0.72 dL / g for the core component and 0.58 dL / g for the sheath component.

  Both of these components were combined at a spinning temperature of 294 ° C. using a spinning pack and a die for composite spinning, combined and discharged into a core-sheath type, and wound up at a spinning speed of 1200 m / min. At that time, an undrawn yarn of monofilament was obtained while attaching the same oil agent as in Example 1 in the amount shown in Table 1 using an oiling nozzle. Then, after preheating the unstretched yarn with a heated hot roller, it was stretched by 3.8 times while being heated with a slit heater, and further subjected to a relaxation treatment of 0.3%, and then wound on a pirn. A 13 dtex / 1 fil drawn yarn was obtained.

The obtained drawn yarn (core-sheath type composite monofilament raw yarn) has a strength of 6.0 cN / dtex, an elongation of 25%, a 5% LASE of 4.0 cN / dtex, a free shrinkage of 0.21%, and an oil agent adhesion rate of 0.19. The weight percent and the coefficient of dynamic friction were 0.25. In addition, the number of node yarns generated per 100,000 m of the monofilament yarn was 0.
When this raw yarn was woven with a slewer type loom, the number of fabric defects due to the occurrence of yarn shaving was 0 per 30 m. When the frictional voltage of the fabric obtained by weaving was measured, the voltage after 60 seconds was 225V.

[Example 8]
In Example 7, a drawn yarn was obtained in the same manner as in Example 1 except that the intrinsic viscosity of polyethylene terephthalate used for the core component was changed to 0.9 dL / g. A discharge sample was collected in the same manner as in Example 1. The intrinsic viscosity of the core component was 0.8 dL / g. There was no difference in terms of other quality except that 5% LASE was slightly improved.

[Comparative Example 4]
In Example 7, the oil agent discharge amount from the oiling nozzle was changed to 5%, and other than that, a drawn yarn was obtained in the same manner as in Example 7, but the oil agent adhesion rate was 0.01% by weight, and during weaving Threading frequently occurred.

[Comparative Example 5]
In Example 7, a drawn yarn was obtained in the same manner as in Example 7, except that the core-sheath ratio (weight ratio) was changed to 95: 5 for spinning. The obtained drawn yarn (monofilament raw yarn) had many fabric defects due to yarn shaving due to the influence of many portions where the core component was exposed on the yarn surface. In addition, the stay in the melted region became longer due to the decrease in the discharge amount of the sheath component, and some knots were generated.
The results of Examples 7 to 8 and Comparative Examples 4 to 5 in which the respective conditions are changed as described above are summarized in Table 4 below.

  The core-sheath type composite monofilament of the present invention is useful as a raw yarn for ropes, nets, tegus, tarpaulins, tents, screens, paragliders, sailcloths, etc., especially for the production of mesh fabrics for screen printing, printed wiring boards, etc. It is preferably used to obtain a high mesh and high modulus screen wrinkle that requires high precision.

Claims (11)

A core-sheath type in which the core component is made of a fiber-forming polymer having an intrinsic viscosity of 0.70 dL / g or more, and the sheath component is made of polyester having an intrinsic viscosity of 0.40 to 0.65 dL / g or a composition containing the same as a main component. It is a composite monofilament, and the following conditions (A) to (E):
(A) The weight ratio of the core component is 50 to 90%,
(B) The number of node yarn portions having a diameter of 1.1 times or more with respect to the average fiber diameter of the monofilament is 1 or less per 100,000 meters in the fiber longitudinal direction;
(C) the fineness is 15 dtex or less, the modulus at an elongation of 5% satisfies 3.0 cN / dtex or more, and the elongation at break satisfies 40% or less,
(D) The free shrinkage of the innermost layer portion measured over 10 days from the next day after product winding is 0.3% or less, and
(E) The adhesion amount of the oil agent (non-aqueous component) applied to the surface of the monofilament with respect to the fiber weight is 0.1 to 0.4% by weight, and the dynamic friction coefficient of the monofilament is 0.2 to 0 by the oil agent. .35 adjusted,
A core-sheath type composite monofilament characterized by satisfying   The oil agent applied to the surface of the monofilament is an aliphatic ester compound of 50 to 80% by weight and an alcohol having 8 to 18 carbon atoms and a partial phosphate ester salt of an ethylene oxide and / or propylene oxide 0 to 10 mol adduct. The core-sheath type composite monofilament according to claim 1, which is an oil containing 10% by weight.   The core-sheath composite monofilament according to claim 1 or 2, wherein both the core component and the sheath component are polyester, and the polyester is an aromatic polyester having a terminal carboxyl group concentration of 15 eq / 106 g or less. . The polyester constituting the core component and the sheath component is a hydrolysis-resistant aromatic polyester containing 3 to 50 ppm of a phosphoric acid ester represented by the following general formula in terms of phosphorus atom content. The core-sheath type composite monofilament according to claim 3.

  The core-sheath type composite according to claim 1 or 2, wherein the polyester of the sheath component is an ultraviolet-absorbing polyester containing 0.01 to 5.0% by weight of an organic ultraviolet absorber relative to the polymer. Monofilament.   The organic UV absorber is at least one UV absorber selected from the group consisting of a benzotriazole UV absorber, a benzophenone UV absorber, a triazine UV absorber, and a benzoxazine UV absorber. The core-sheath type composite monofilament according to claim 5.   The core-sheath type composite monofilament according to claim 1 or 2, wherein the polyester of the sheath component is an easily dyeable polyester obtained by copolymerizing 0.5 to 2.5 mol% of a sulfonic acid phosphonium salt. The core-sheath type composite monofilament according to claim 7, wherein the sulfonic acid phosphonium salt copolymerized with the polyester of the sheath component is a sulfonic acid phosphonium salt represented by the following formula.

  The sheath component contains 0.2 to 30 parts by weight of a polyoxyalkylene polyether per 100 parts by weight of the aromatic polyester and 0.05 to 10 parts by weight of an organic ionic compound substantially nonreactive with the polyester. The core-sheath type composite filament according to claim 1 or 2, comprising an electrically conductive polyester composition. 10. The core-sheath composite filament according to claim 9, wherein the organic ionic compound is a sulfonic acid metal salt represented by the following general formula.

  An aromatic polyester having a core component made of a fiber moldable polymer having an intrinsic viscosity of 0.70 dL / g or more and a sheath component having an intrinsic viscosity of 0.50 to 0.65 dL / g, and a polyoxyalkylene type per 100 parts by weight of the aromatic polyester 10. The polyester composition comprising 0.2 to 30 parts by weight of a polyether and 0.05 to 10 parts by weight of an organic ionic compound substantially nonreactive with the polyester. 10. The core-sheath type composite monofilament according to 10.