JP2013076187A - Crimped yarn and fiber structure using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crimped yarn of a polymer alloy, which is superior in abrasion resistance and is suitably used as a carpet.SOLUTION: The crimped yarn of the present invention comprises the polymer alloy obtained by blending an aliphatic polyester resin (A), a thermoplastic polyamide resin (B), and a styrene/(meth)acrylate copolymer (C) having a glycidyl group. The crimped yarn is superior in abrasion resistance and is suitably used as the carpet.

Description

  The present invention relates to a crimped yarn composed of a polymer alloy synthetic fiber in which an aliphatic polyester resin and a thermoplastic polyamide resin are uniformly blended.

  In recent years, in order to prevent depletion of fossil fuel resources and to prevent global warming, development has been actively carried out to replace synthetic fibers made of conventional petroleum polymers with aliphatic polyester polymers made from plant resources. . Among them, attention is focused on plastics that are decomposed by microorganisms, that is, fibers using biodegradable plastics.

  Among them, polylactic acid fibers have been actively developed because there is a possibility that they can be used as practical products in terms of mechanical properties and thermal properties, and recently, polymer costs are becoming realistic prices. However, in spite of great expectations, there are few uses that can utilize the characteristics of polylactic acid fibers as they are, and although technical developments have been made to improve the defect characteristics of polylactic acid, the results are not sufficient. For this reason, the production and sales volume of polylactic acid fibers is still small, and early expansion is eagerly desired.

  In particular, the market for automobile carpets and interior carpets is large, and despite the expectation of early conversion to environmentally friendly materials such as polylactic acid, crimping is a drawback of polylactic acid crimped yarn. The reality is that the product has not yet been commercialized without clearing the carpet characteristics such as durability and wear resistance.

  Under such circumstances, apart from the technological development that makes the best use of the characteristics of polylactic acid or drastically improves the defect characteristics, a part of the synthetic fiber is replaced with polylactic acid fiber by mixing with the conventional synthetic fiber. Attempts have been made to do so. Specifically, it relates to a polymer blend or a core-sheath composite of polylactic acid and polyamide. Examples of techniques disclosed so far include Patent Document 1 and Patent Document 2.

  Patent Document 1 discloses a polymer alloy fiber in which an aliphatic polyester is uniformly finely dispersed in a polyamide, and durability such as wear resistance and settling resistance when a carpet is formed by adding various inorganic particles. A technique for improving the performance is disclosed. However, since the fiber described in Patent Document 1 is incompatible with polyamide and aliphatic polyester, the adhesiveness at the interface between these phases is inferior, and the wear resistance and the settling resistance are insufficient.

  In addition, by adding a compatibilizer containing two or more active hydrogen reactive groups in one molecule, the adhesion at the interface between the polyamide and the aliphatic polyester is strengthened, and the alloy that suppresses the separation of the interface due to external force is suppressed. Fibers are disclosed (Patent Document 2 and Patent Document 3).

JP 2008-81911 (Claims) JP 2006-233375 A (Claims) JP 2007-197886 A (Claims)

  However, even in the methods described in the above Patent Documents 1 to 3, peeling of the interface is not sufficiently suppressed, and it has been desired to provide even more excellent wear resistance. An object of the present invention is to solve the above-mentioned problems, and to provide a polymer alloy crimped yarn excellent in wear resistance and suitable as a carpet.

  The above-mentioned problem is a crimp made of a polymer alloy formed by blending an aliphatic polyester resin (A), a thermoplastic polyamide resin (B), and a styrene / (meth) acrylate ester copolymer (C) having a glycidyl group. Can be achieved with thread.

  According to the present invention, the wear resistance is remarkably improved, and a polymer alloy crimped yarn suitable as a carpet and a carpet using the same can be provided.

It is an example of the discharge hole sectional drawing of the nozzle | cap | die for 3 leaf cross sections (Y type) used for manufacture of the crimped yarn of this invention.

  The present invention is described in detail below.

  The aliphatic polyester resin (A) in the present invention (hereinafter sometimes referred to as “component A”) refers to a polymer in which aliphatic alkyl chains are linked by ester bonds. As aliphatic polyester resin (A) used by this invention, it is preferable that it is crystalline, and it is more preferable that melting | fusing point is 150-230 degreeC.

  Examples of the aliphatic polyester resin (A) used in the present invention include polylactic acid, polyhydroxybutyrate, polybutylene succinate, polyglycolic acid, and polycaprolactone. Of these, polylactic acid is most preferable from the viewpoint of easy melt molding.

The polylactic acid is a polymer having — (O—CHCH ₃ —CO) _n — as a repeating unit and is obtained by polymerizing oligomers of lactic acid such as lactic acid and lactide. Lactic acid has two optical isomers, D-form and L-form. In either L-form or D-form, higher optical purity is preferable because the melting point is higher, that is, the heat resistance is improved. Specifically, the L-form or D-form is preferably 90% or more, and more preferably 95% or more, based on the total of the L-form and D-form. Further, the melting point is preferably 150 ° C. or higher, more preferably 150 ° C. to 230 ° C., in order to maintain the heat resistance of the fiber. More preferably, it is 170 degreeC-230 degreeC. The melting point is a temperature that gives an extreme value of a melting endothermic curve obtained by a method described later using a differential scanning calorimeter DSC.

  However, apart from the system in which the polymers of the two optical isomers are simply mixed as described above, the two optical isomer polymers are blended and formed into a fiber, and then a high temperature of 140 ° C. or higher. A stereo complex in which racemic crystals are formed by heat treatment is preferable because the melting point can be increased to 220 to 230 ° C. In this case, “component A” refers to a mixture of poly (L lactic acid) and poly (D lactic acid). When the blend ratio is 40/60 to 60/40, the ratio of stereocomplex crystals can be increased. Is the best.

  Polylactic acid also contains residual lactide as a low molecular weight residue, and these low molecular weight residues can pass through the process of spinning, drawing and crimping processes due to contamination of the die, heating roller and crimp nozzle. Not only does it lead to defects, but it also causes abnormal dyeing such as dyed spots in the dyeing process. In addition, the hydrolysis of fibers and fiber molded products is promoted, and the durability is lowered. Therefore, the amount of residual lactide in polylactic acid is preferably 0.3% by weight or less, more preferably 0.1% by weight or less, and still more preferably 0.03% by weight or less. As a method for measuring the residual lactide, 1 g of a sample (polylactic acid) was dissolved in 20 ml of dichloromethane, 5 ml of acetone was added to this solution, and the solution was fixed with cyclohexane and precipitated, followed by liquid chromatography using GC17A manufactured by Shimadzu Corporation. And a method for obtaining a lactide amount by an absolute calibration curve.

  In addition, components other than lactic acid may be copolymerized within a range that does not impair the properties of polylactic acid. The components to be copolymerized include polyalkylene ether glycols such as polyethylene glycol, aliphatic polyesters such as polybutylene succinate and polyglycolic acid, aromatic polyesters such as polyethylene isophthalate, and hydroxycarboxylic acids, lactones, dicarboxylic acids, and diols. An ester bond-forming monomer such as Among these, a polyalkylene ether glycol having good compatibility with the thermoplastic polyamide resin (B) (hereinafter sometimes referred to as “component B”) is preferable. The copolymerization ratio of such copolymerization components may be in a range that does not impair the heat resistance reduction due to the melting point drop, but is preferably 0.1 to 10 mol% with respect to the lactic acid units constituting the polylactic acid.

  In addition, the molecular weight of the polylactic acid polymer is preferably high in order to increase the wear resistance, but if the molecular weight is too high, the stretchability tends to decrease, for example, yarn breakage or fluff frequently occurs in the spinning process. The weight average molecular weight is preferably 80,000 or more, more preferably 100,000 or more in order to maintain wear resistance. More preferably, it is 120,000 or more. On the other hand, when the molecular weight exceeds 350,000, the stretchability is lowered as described above. As a result, the molecular orientation is deteriorated and the fiber strength is lowered. Therefore, the weight average molecular weight is preferably 350,000 or less, and more preferably 300,000 or less. More preferably, it is 250,000 or less. The weight average molecular weight is a value determined by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

  The thermoplastic polyamide resin (B) used in the present invention is preferably a copolymer polymer with other polyamide components mainly composed of polycaproamide or caprolactam. Examples of preferable copolymer are caprolactam: 80 to 99 parts by weight, hexamethylene adipamide, trimethylene adipamide, hexamethylene sebacamide, based on 100 parts by weight of the whole monomer constituting the copolymer. It is a polyamide obtained by copolymerizing 1 to 20 parts by weight of one or more of the above. Polycaproamide has been a suitable material for crimped yarns for carpets. Copolyamides based on the polycaproamide component have a slightly lower crystallinity than polycaproamide, but have a melting point of polylactic acid. Therefore, in the melt spinning process, the thermal degradation of polylactic acid is reduced, the occurrence of yarn breakage and fluff is suppressed, and stable yarn production becomes possible. In the present invention, the presence or absence of crystallinity can be determined to be crystalline if the melting peak can be observed by differential scanning calorimetry (DSC) measurement.

  In general, when an aliphatic polyester has a melting point, the melting point is usually not higher than 200 ° C., and thus heat resistance is not high, and physical properties tend to deteriorate if the temperature during melt storage becomes too high. Therefore, the thermoplastic polyamide resin (B) to be blended preferably has a melting point of 150 to 250 ° C., and the upper limit of the melting point of the thermoplastic polyamide resin (B) is preferably 230 ° C. or less. On the other hand, considering the heat resistance of the fiber, the lower limit of the melting point of the polyamide is preferably 150 ° C. or higher.

  Further, if the viscosity of the thermoplastic polyamide resin (B) is too low, the degree of deformity cannot be kept high, the bulkiness and texture of the carpet will be lowered, and the durability may be deteriorated due to a decrease in wear resistance. is there. On the other hand, when the viscosity is too high, the fluidity of the polymer is deteriorated and the spinnability at the spinning portion is deteriorated. Therefore, the relative viscosity is preferably 1.8 to 3.0. More preferably, it is 2.5-2.8. The relative viscosity referred to here is a value obtained from the ratio of the number of seconds that the polymer solution and sulfuric acid dropped when 0.25 g of a sample was dissolved in 25 ml of 98% sulfuric acid and measured at 25 ° C. using an Ostwald viscometer. Say.

  The blend ratio of component A and component B of the present invention is not particularly limited, but in the present invention, it is preferable to use component A as an island component and component B as a sea component, as will be described later, and this can be achieved. A ratio is preferable. In order to obtain a polymer alloy having a sea-island structure in which component A is an island component and component B is a sea component, the blend ratio (weight ratio) of component A / component B should be in the range of 10/90 to 50/50. Is preferred. Moreover, since the blend ratio of the component A and the component B becomes easier as the ratio of the component B is increased, it is more preferably 20/80 to 40/60.

  The crimped yarn of the present invention and a carpet using the crimped yarn are composed of a polymer alloy containing an aliphatic polyester resin (A) and a thermoplastic polyamide resin (B). The crimped yarn of the present invention and the carpet using the crimped yarn preferably have a sea-island structure in which the aliphatic polyester resin (A) forms an island component and the thermoplastic polyamide resin (B) forms a sea component. Here, since the aliphatic polyester and the polyamide usually hardly react (ester-amide exchange hardly occurs), the interfacial adhesion of the two polymers is not so high as it is. Therefore, the crimped yarn of the present invention and the carpet using the crimped yarn are further added with a styrene / (meth) acrylate polymer (C) (hereinafter sometimes referred to as “component C”) having a glycidyl group. Thus, the wear resistance is improved by dramatically improving the interfacial adhesion.

  Component C used in the present invention is a styrene / (meth) acrylate copolymer having a glycidyl group. The “/” means copolymerization, and the same applies to the following description. By using a styrene / (meth) acrylate copolymer having a glycidyl group as component C, the interfacial adhesion between the aliphatic polyester resin (A) and the thermoplastic polyamide resin (B) is drastically improved. be able to.

  The styrene / (meth) acrylate copolymer (C) having a glycidyl group is usually a copolymerizable vinyl monomer (preferably a (meth) acrylate copolymer having a styrene, a (meth) acrylate ester and a glycidyl group. It can be obtained by copolymerizing comonomers such as) glycidyl acrylate).

  Here, (meth) acrylic acid ester means methacrylic acid ester and / or acrylic acid ester.

  Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic Lauryl acid, alkyl (meth) acrylate such as tridecyl (meth) acrylate and stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate, etc. (Meth) acrylic acid alicyclic alkyl, (meth) acrylic acid 2- And heteroatom-containing (meth) acrylic acid esters such as toxiethyl, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. . These monomers can be used alone or in combination of two or more.

  Examples of the copolymerizable vinyl monomer having a glycidyl group include glycidyl (meth) acrylate, epoxycyclohexyl (meth) acrylate, epoxycyclohexanemethyl (meth) acrylate, allyl glycidyl ether and Examples thereof include vinyl glycidyl ether. Among these, glycidyl methacrylate, which is easily available and easily improves the adhesive strength, is preferably used.

  Among them, as the component C, a copolymer of polystyrene / butyl (meth) acrylate / glycidyl methacrylate or polystyrene / butyl (meth) acrylate / methyl (meth) acrylate / glycidyl methacrylate is preferable.

  As such a product, “ARUFON” manufactured by Toagosei is commercially available.

  Styrene / (meth) acrylic acid ester copolymer (C) having glycidyl group is added to component A and / or component B, melt blended, and spinning is performed, so that the compound is composed of component A and component B. It is considered that interfacial delamination can be suppressed by reacting with any component to form a cross-linked structure or reacting with either component and existing at the interface between both component A and component B.

Glycidyl groups have reactivity with COOH end groups, OH end groups, and NH ₂ end groups present at the ends of polylactic acid resins and thermoplastic polyamide resins. In melt spinning, which is a method for producing crimped yarns of the present invention, Since molding is performed at a relatively low temperature of 250 ° C. or lower, a glycidyl group is preferable in terms of excellent low-temperature reactivity.

  When the amount of glycidyl group of the styrene / (meth) acrylic acid ester-based copolymer having a glycidyl group is 20 mgKOH / g or more, a preferable role as a compatibilizing agent can be satisfied. On the other hand, if there is a reactive group exceeding 200 mgKOH / g in one molecule, the viscosity tends to be excessively increased during spinning and the spinnability tends to decrease, so the amount of glycidyl group in one molecule is 20 mgKOH / g. As mentioned above, 200 mgKOH / g or less is preferable, More preferably, it is 100 mgKOH / g or less, More preferably, it is 40 mgKOH / g or less. The glycidyl group amount mentioned here is a theoretical value based on the polymerization raw material used.

  Further, the compound having 20 mgKOH / g or more of the glycidyl group described above preferably has a weight average molecular weight of 250 to 30,000 because of excellent heat resistance and dispersibility during melt molding, and more preferably 250-20,000.

The glycidyl group is known to be more reactive with the NH ₂ end group than the OH end group, and is excellent in reactivity with the thermoplastic polyamide resin (B). Furthermore, the acrylic polymer which is the main chain of the styrene / (meth) acrylic acid ester copolymer (C) of the polymer having these reactive groups is a phase with the aliphatic polyester (A), particularly polylactic acid. It has good solubility and is excellent in reactivity and dispersibility as a compatibilizer with both the thermoplastic polyamide resin (B) and polylactic acid.

  The reason why the styrene / (meth) acrylate copolymer (C) having a glycidyl group used in the present invention is effective is not clear, but this component (C) is a glycidyl group in the main chain of the polymer. It is a copolymer obtained by copolymerizing the containing comonomer, and it is considered that the main chain does not have a long branch and has no steric hindrance, and thus has high reactivity. In addition, since it is not necessary to use an auxiliary material such as a chain transfer agent at the time of polymerization of this component (C), it is considered that the heat resistance at high temperature is excellent, and compatibilization of a polymer alloy using polyamide that is spun at high temperature. It is preferably used as an agent.

  Moreover, since the styrene / (meth) acrylic acid ester-based copolymer (C) having a glycidyl group generally has a small molecular weight and composition distribution, it is considered to be rich in uniform reactivity at the time of melting.

  Also, by adding the styrene / (meth) acrylate copolymer (C) having a glycidyl group, the compatibility between the aliphatic polyester (A) and the thermoplastic polyamide resin (B) is improved, and spinning is performed. As a result, the high-viscosity thermoplastic polyamide (B), which has heretofore been very difficult to use due to the occurrence of the ballast, can be used. It has been found that by using this high-viscosity thermoplastic polyamide (B), a crimped yarn having a high degree of deformation can be obtained, and the abrasion resistance on the carpet can be improved.

  The addition method of the styrene / (meth) acrylic acid ester copolymer (C) having a glycidyl group is to melt these resins from the polymerization of the aliphatic polyester resin (A) and the thermoplastic polyamide resin (B). It may be added in the process until spinning, but it is preferably added at the melt spinning stage from the viewpoint of easy handling, and the addition method at that time is preferably a master batch method.

  In the case of using the master batch method, a master chip is prepared by kneading component C into a molten base polymer, and this is mixed with an aliphatic polyester resin (A) and a thermoplastic polyamide resin (B) and melt-spun. can do.

  The amount of component (C) added can be appropriately determined according to the equivalent weight per unit mass of the reactive group of the compound to be used, the dispersibility and reactivity during melting, and the blend ratio of component A and component B. In terms of suppressing interfacial peeling, it is preferable that the amount is 0.005% by mass or more with respect to the total amount (100% by mass) of Component A, Component B, and Component C. More preferably, it is 0.02 mass% or more, More preferably, it is 0.1 mass% or more. When the amount of component C added is too small, the diffusion and reaction amount at the interface between the two components is small, and the effect of improving the interfacial adhesion becomes limited. On the other hand, the amount of component C added is preferably 5% by mass or less in order for component C to exhibit performance without impairing the properties of component A and component B, which are the base material of the fiber, and the spinning property. % Or less is more preferable. More preferably, it is 1.5 mass% or less.

  Furthermore, for the purpose of accelerating the reaction of the compatibilizer, it is preferable to add a metal salt of carboxylic acid, particularly a catalyst in which the metal is an alkali metal or an alkaline earth metal because the reaction efficiency can be increased. Among these, it is preferable to use a catalyst based on lactic acid such as sodium lactate, calcium lactate and magnesium lactate. In addition, a catalyst having a relatively large molecular weight such as a metal stearate can be used alone or in combination for the purpose of preventing the heat resistance of the resin from being lowered due to the addition of the catalyst. The added amount of the catalyst is preferably 5 to 2000 ppm with respect to the synthetic fiber in order to control dispersibility and reactivity. More preferably, it is 10-1000 ppm, More preferably, it is 20-500 ppm.

  Moreover, although a dyeing process is generally applied as a method of coloring polylactic acid fibers, an original yarn that does not apply the dyeing process may be used.

  The colorant used in the crimped yarn of the present invention is a specific inorganic, organic pigment and dye suitable for polylactic acid crimped yarn. Specifically, oxide-based inorganic pigments excluding lead, chromium and cadmium, ferrocyanide inorganic pigments, silicate inorganic pigments, carbonate inorganic pigments, phosphate inorganic pigments, carbon black, aluminum powder, bronze powder and From inorganic pigments such as titanium powder-coated mica, organic pigments such as phthalocyanine organic pigments, perylene organic pigments, isointoserinone organic pigments, and heterocyclic dyes, helinone dyes, perylene dyes, and thioindio dyes It is a combination of two or more selected. For example, inorganic pigments include oxides such as titanium oxide, zinc white, titanium yellow, zinc-iron-based brown, titanium-cobalt green, cobalt green, cobalt blue, copper-iron black, and ferrocyans such as bitumen. , Silicates such as ultramarine, carbonates such as calcium carbonate, phosphates such as manganese violet, carbon black, aluminum powder and bronze powder, and titanium powder-coated mica are used. Lead, chromium, cadmium, etc. Inorganic pigments containing heavy metals are not used. As the organic pigment, phthalocyanine series such as copper phthalocyanine blue, copper phthalocyanine green and brominated copper phthalocyanine green, perylene series such as perylene scarlet, perylene la, perylene maroon, isoindolinone, etc. are used. As the dye, anthraquinone, heterocyclic, helinone, perylene, and thioindio are used.

  The colorant used for the crimped yarn of the present invention and the carpet using the crimped yarn is preferably used in combination of two or more selected from the above inorganic pigments, organic pigments and dyes. By adjusting using two or more of the above-mentioned colorants, it is possible to express a subtle color tone that can be compared to conventional dyed polylactic acid crimped yarns, and the design and aesthetics of carpets can be achieved. Can be satisfied.

  The concentration of the colorant varies depending on the type of the dye, but is preferably 0.01 to 3.0 parts by mass, more preferably 0.5 to 1.0, as the total amount of the colorant per 100 parts by mass of the polymer. Used by mass parts. The colorant can also be used in combination with a commonly used dispersant.

  As a method for adding the colorant, in the same manner as the method for adding the component C, it is added in the process from the polymerization of the aliphatic polyester resin (A) and the thermoplastic polyamide resin (B) to the melt spinning of these resins. However, it is preferable to add at the melt spinning stage because of easy handling. In this case, the addition method includes a master batch method and a liquid color method, and the master batch method is preferable from the viewpoint of productivity, color tone stability, and the like.

  Further, the crimped yarn of the present invention and the carpet using the same are, in addition to the colorant, a light resistance agent, a weather resistance agent, an ultraviolet absorber, a heat resistance agent, a thermal degradation inhibitor, an antioxidant, a lubricant, a plasticizer, and a dispersant. Conventionally known additives such as stabilizers, flame retardants, antibacterial agents, and antifouling agents can be appropriately used.

  The total fineness of the crimped yarn of the present invention is preferably 500 dtex or more, so that when tufted as it is as a carpet pile, it is not necessary to raise stitches to obtain a practical weight, and tufting properties are preferable. More preferably, it is 1000 dtex or more. Also, when twisted yarns are used as cut piles of various twisted yarns, it is preferable because it is not necessary to raise the gauge or stitches more than necessary. On the other hand, the upper limit is 3000 dtex or less because, in the spinning process, in order to perform stable spinning without reducing the drawability, it is necessary to make cooling and solidification uniform and to sufficiently transfer heat. Is more preferable, and 2000 dtex or less is more preferable.

  The single yarn fineness of the crimped yarn of the present invention is preferably 5 to 50 dtex. If it is less than 5 dtex, it is lacking in wear resistance, sag resistance and treadiness for carpets. If it exceeds 50 dtex, the texture becomes coarse and not preferred for carpets.

  Furthermore, the crimped yarn in the present invention maintains the bulkiness and texture of the carpet and suppresses durability failure due to a decrease in wear resistance. The cross section is preferable, more preferably 2.5 or more, and still more preferably 4.0 or more. Moreover, since it is technically difficult to produce a cross-sectional shape having a degree of irregularity exceeding 6.0 by a normal production method, the upper limit of the degree of irregularity is preferably 6.0 or less. Examples of the multilobe cross section include 2 leaves (flat cross section, saddle cross section), 3 lobes, 4 lobes, 5 lobes, 6 lobes, etc., but 3 lobes are preferable because gaps between single yarns are more easily formed. The degree of deformation referred to here is represented by the ratio (D / d) of the diameter D of the circumscribed circle of the single yarn cross section and the diameter d of the inscribed circle of the single yarn cross section.

  Moreover, a hollow cross section is mentioned as cross-sectional shape other than the above for providing bulkiness to a carpet. In the case of a hollow cross section, the hollowness is preferably 5 to 25%. When the hollow ratio is less than 5%, the bulkiness and texture of the carpet are lowered, and durability may be deteriorated due to a decrease in wear resistance. On the other hand, if the hollowness exceeds 25%, the rigidity of the single yarn tends to be lowered, the carpet tends to fall down, and the quality of the carpet is remarkably lowered. One or a plurality of hollow portions (such as a rice field cross section) may be used. In the case of a plurality of hollow portions, the total hollow ratio of these hollow portions may be 5 to 25%.

  The crimped yarn of the present invention can be suitably used for carpet applications. As a carpet, it can be used in a wide range of fields such as a car mat, a tile carpet, a roll carpet, a rug mat, and a dascon mat. In particular, it can be suitably used in a field where importance is placed on the cost and environment suitable for the gist of the present invention. The form of the carpet can be appropriately selected so as to obtain a desired carpet product, such as a cut pile, a loop pile, or a combination thereof.

  The strength is preferably 1 cN / dtex to 5 cN / dtex or more, more preferably 2 cN / dtex to 5 cN / dtex or more in order to keep the process passability and the mechanical strength of the product high. A crimped yarn having such strength can be produced by a melt spinning method and a drawing method described later. Further, it is preferable that the elongation is 15 to 70% because the process passability when the fiber product is made is good. A crimped yarn having such an elongation can be produced by a melt spinning method and a drawing method described later.

  The crimped yarn and the carpet using the same in the present invention preferably have a crimp elongation of 5 to 25%, more preferably 15 to 25%. Compared with conventional polylactic acid crimped yarns, it has excellent crimp characteristics, has a high crimp rate and feels volume, and also has good resistance to wear and wear when made into a carpet. Although not as good as nylon crimped yarns, its crimping properties are far superior to conventional polylactic acid crimped yarns and polyethylene terephthalate crimped yarns, and are sufficiently practical. When the crimp elongation is less than 5%, the bulkiness and texture of the carpet are lowered, and the durability may be deteriorated due to a decrease in wear resistance. Further, in order to produce a crimped yarn having a crimp elongation of over 25% by a normal production method, it is necessary to set the heat treatment temperature in the drawing step to 200 ° C. or higher, and the aliphatic polyester having a melting point of 200 ° C. or lower. Since the resin melts, it is technically difficult.

  The method for producing a crimped yarn in the present invention is produced by a crimped yarn production process comprising melt spinning, cooling, oiling, drawing, and crimping. The melt spinning apparatus used in the present invention can be an extruder-type spinning machine or a pressure melter-type spinning machine, but an extruder-type spinning machine is preferred in terms of product uniformity, yarn production yield, and the like.

  When adding a colorant, a master chip to which a colorant is added at a high concentration is used as an aliphatic polyester resin (A), a thermoplastic polyamide resin (B), a styrene / (meth) acrylate ester copolymer having a glycidyl group. Chips blended with the union (C) may be charged into the spinning machine, or each chip may be charged while being measured directly above the spinning machine. In addition, the colorant may be directly put into the spinning machine in a powder or liquid state.

  In order to bring the specific total fineness, single yarn fineness, cross-sectional shape, and the like of the crimped yarn into a preferable range, the viscosity, spinning temperature, spinneret hole shape of the aliphatic polyester resin (A) and the thermoplastic polyamide resin (B), Melt spinning is performed by appropriately setting spinning conditions such as discharge amount and cooling.

  The melt-spun yarn is cooled and solidified by cold air, and after an oil agent is applied, the yarn is wound around a take-up roller that rotates at a predetermined take-up speed. The take-up speed is preferably 300 to 1000 m / min. The drawn yarn is usually continuously stretched and crimped continuously. As another method, a method of once winding with undrawn yarn and then drawing and crimping in another step, or a method of once winding drawn yarn and then crimping in another step is also possible. .

  The crimped yarn according to the present invention preferably has a crimp elongation of 5 to 25%, but for that purpose, it is preferable to sufficiently crimp the molecular chain in the drawing step before crimping. The stretching ratio is preferably in the range of 2.0 to 4.0 times, and is preferably stretched so that the elongation is 15 to 70%. Next, the drawn yarn is subjected to a crimping process through a crimping device. Crimping is performed by heated fluid processing such as saturated steam, superheated steam or heated air. As the crimping apparatus, for example, a crimping nozzle apparatus disclosed in Japanese Patent Application Laid-Open No. 2004-84080 can be used. Normally, crimping is performed by a jet nozzle method having the crimping nozzle, and a high-temperature high-temperature fluid such as superheated steam or heated air is brought into contact with the yarn passing through the needle from the surroundings and released into the atmosphere for cooling. To give crimp. Furthermore, for the purpose of fixing crimps, it is possible to employ a method in which cold air is blown to the crimped yarn that has passed through the crimp nozzle, or the crimped yarn is deposited on the surface of the rotary filter that is sucked inside and cooled. it can.

  The crimped yarn that has been crimped is imparted with an appropriate stretch to make a part of the crimp latent, and then wound by a winder. The crimped yarn may be subjected to an entanglement process to give convergence before winding.

In the subsequent step, the obtained crimped yarn may be entangled and mixed with a plurality of multifilaments, or may be subjected to yarn processing such as a twisting and setting step. Thus, the aliphatic polyester resin (A) in the present invention A crimped yarn excellent in abrasion resistance and a carpet using the crimped yarn are obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited at all by these Examples. In addition, the measuring method of each measured value in an Example is as follows.

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

(2) Relative viscosity of thermoplastic polyamide 0.25 g of a sample was dissolved in 25 ml of 98% sulfuric acid and measured at 25 ° C. using an Ostwald viscometer. The relative viscosity was determined from the ratio of the number of seconds that the polymer solution and sulfuric acid dropped.

(3) Melting point (Tm)
The measurement was performed using a DSC-7 differential scanning calorimeter manufactured by Perkin-Elmer. Using a sample amount of 20 mg, as 1st RUN, the temperature was increased from 20 ° C. to a temperature about 30 ° C. higher than the end of the melting peak at a temperature increase rate of 10 ° C./minute, held at this temperature for 10 minutes, and then the temperature decrease rate −10 ° C. / When the temperature is lowered to 20 ° C. for 1 minute and held at the temperature of 20 ° C. for 1 minute, the temperature is further increased from 20 ° C. to about 30 ° C. higher than the end of the melting peak at 20 ° C./min. The peak temperature of the observed melting endotherm curve was taken as the melting point.

(4) Slit ratio In the Y-type cross-sectional yarn cap, it was calculated by the following formula.
Slit ratio = slit length / slit width

  Here, the slit length and the slit width are as shown in FIG. That is, FIG. 1 is an example of a discharge hole cross-sectional view of a three-leaf cross-section (Y-type) die used for manufacturing the crimped yarn of the present invention, where 1 is the slit length of the discharge hole and 2 is the discharge hole. The slit width.

(5) Deformation The ends of the crimped yarn wrapped with rayon staples are passed through a hole (hole diameter: 1.0 mm) provided in a stainless steel preparation with a thickness of 0.5 mm, and along both sides of the preparation with a safety razor. A sample cut in parallel was used as a sample for cross-sectional observation. This sample was observed with a digital microscope “VHX-500” manufactured by KEYENCE Corporation at a magnification of 500 times. From the diameter D of the circumscribed circle of the single yarn cross section and the diameter d of the inscribed circle of the single yarn cross section, Asked. It calculated | required from the average value of 10 samples.
Degree of deformation = D / d

(6) Hollow rate The end of the crimped yarn wrapped with rayon staples is passed through a hole (hole diameter: 1.0 mm) in a stainless steel preparation with a thickness of 0.5 mm, and along both sides of the preparation with a safety razor. A sample cut in parallel was used as a sample for cross-sectional observation. This sample was observed at 500 times using a digital microscope “VHX-500” manufactured by KEYENCE, and was obtained from the cross-sectional area S of the fiber including the hollow part and the area s of the hollow part by the following equation using the area measurement function. It calculated | required from the average value of 10 samples.
Hollow ratio = (s / S) × 100 (%)

(7) Total fineness JIS L 1013 (2010) 8.3.1 Positive fineness b) According to the B method, the initial load is 0.882 mN / dtex, the official moisture content is 0.5% for polylactic acid, and 4.% for polyamide. Using 5%, it was measured using the case of calculating from JIS L 0105 (2006) 3.1 (1) absolute dry mixing rate.

(8) Single yarn fineness This was determined by dividing the total fineness by the number of filaments.

(9) Strength and Elongation The sample was measured with “TENSILON” UCT-100 manufactured by Orientec Co., Ltd. under the constant speed elongation conditions shown in the JIS L1013 (2010) 8.5.1 standard time test. At this time, the grip interval was 25 cm, the pulling speed was 30 cm / min, and the number of tests was 10 times. The elongation at break was determined from the elongation at the point showing the maximum strength in the SS curve.

(10) Boiling water shrinkage rate Using a yarn obtained by cutting one end of a yarn bundle wound with a measuring machine having a frame circumference of 1.125 m as a sample, a load of 0.882 mN / dtex was applied to the sample before boiling water treatment. The sample length (L1) when applied, and the sample when immersed in 98 ° C. boiling water for 30 minutes in an unloaded state and then dried to obtain an equilibrium moisture content, a load of 0.882 mN / dtex was applied. The sample length (L2) was calculated by the following formula, and the average value of 10 samples was defined as the boiling yield.
Boiling yield (%) = [(L1-L2) / L1] × 100

(11) Crimp elongation after treatment with boiling water After winding the crimped yarn, it is allowed to stand for 20 hours in a cheese-shaped atmosphere at 20 ° C. and a relative humidity of 65%. The crimp elongation rate when immersed in water is shown, specifically the value measured by the following method.

That is, the crimped yarn to be measured is immersed in 98 ° C. boiling water for 20 minutes in an unloaded state and then dried to obtain an equilibrium moisture content. An initial load of 0.0176 mN / dtex is applied to this sample. A sample length of 50 cm (L3) measured after 30 seconds was marked, then a constant load of 0.882 mN / dtex was applied to the sample, and the elongation (L4) after 30 seconds was measured. ) And (L4) were calculated according to the following formula, and the average value of 10 samples was used as the crimp elongation after boiling water treatment.
Crimp elongation after treatment with boiling water (%) = [(L4-L3) / L3] × 100

(12) Abrasion resistance of carpet A carpet processed to have a basis weight of 1100 g / m ² was cut into a circular shape having a diameter of 120 mm, and a 6 mm hole was formed in the center to obtain a test piece. This test piece is attached to a Taber abrasion tester (Rotary Abaster) stipulated in ASTM D 1175 (1994) with a pile surface facing upward, an H # 18 wear wheel, a compression load of 1 kgf (9.8 N), and a sample holder rotation. A wear test was performed under the conditions of a speed of 70 rpm and a wear frequency of 5500, and the wear loss rate was calculated using the following formula.
Wear loss rate (%) = (W0−W1) × 100 / (W2 × T)
W0: Weight of circular carpet before measurement (g)
W1: Weight of the circular carpet after measurement (g)
W2: Carpet weight (g / m ² )
T: The total area (m ² ) of the portion where the wear wheel contacts.

[Example 1]
Polylactic acid (weight average molecular weight: 200,000, melting point: 177 ° C., L-form ratio in L-form / D-form: 98%) as component A, nylon 6 (relative viscosity: 2.63, melting point: 225 ° C.) as component B 20 parts by weight of styrene / (meth) acrylic acid ester copolymer having a glycidyl group as component C (Toagosei Co., Ltd .: ARUFON UG-4070, glycidyl group amount: 39 mmg KOH / g, weight average molecular weight: 9700) % Of nylon 6 (relative viscosity: 2.15, melting point: 225 ° C.) while continuously measuring with a measuring instrument so that the weight ratio is 30: 65: 5. Charged and melt spun. Spinning temperature 250 ° C. Using a die having a hole specification (slit length / slit width = 10.8) for a three-leaf section (Y type), the total fineness of the crimped yarn is 1450 dtex, the number of filaments is 54, and the single yarn The yarn was produced so that the fineness was 26.9 dtex.

  The drawing speed was 770 m / min, the draw ratio was 2.8 times, the draw temperature was 110 ° C, and the set temperature was 150 ° C. Next, the drawn yarn is continuously crimped with 0.9 MPa heated air with a crimped nozzle at a crimped nozzle temperature of 220 ° C., cooled with a cooling roll, and then stretched over 0.12 cN / dtex. Then, after making the crimps latent, through the entanglement nozzle, about 10 pieces / m was entangled and wound at 1800 m / min.

The crimped yarn obtained was tufted according to the following tuft standard to obtain a cut pile carpet. A spunbond nonwoven fabric made of polyethylene terephthalate having a basis weight of 120 g / m ² was used as the base fabric.
Weight per unit: 1100 g / m ² , gauge: 1/10 gauge, pile height: 10 mm, stitch: 12 pieces / inch, pile: cut pile

On the other hand, a water-based resin emulsion mainly composed of SBR (styrene / butadiene / latex) is applied to one side of a polyethylene terephthalate spunbond nonwoven fabric having a basis weight of 300 g / m ² and heated at 120 ° C. for 3 minutes to form a backing layer. Got ready.

Next, while transporting the cut pile carpet with the pile surface facing downward, polyethylene powder was applied onto the cut pile carpet at a spread rate of 250 g / m ² , and then the powder was heated to 150 ° C. The prepared backing layers were superposed and then pressure bonded with a pressure nip roll (25 ° C., linear pressure 10 kg / cm) to obtain a carpet.
Table 1 shows the properties of the obtained crimped yarn and carpet.

[Example 2]
The same procedure as in Example 1 was conducted except that the weight ratio of the component A: component B: component C master chip was weighed so as to be 20: 79.5: 0.5 and the extruder was introduced into the extruder type extrusion spinning machine. Thus, crimped yarn and carpet were obtained. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Example 3]
While weighing so that the weight ratio of component A: component B: component C master chip is 40:50:10, it is put into an extruder type extrusion spinning machine, and the total fineness of the resulting crimped yarn is 2430 dtex, single yarn A crimped yarn and a carpet were obtained in the same manner as in Example 1 except that the fineness was changed to 45 dtex. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Example 4]
Nylon 6 containing 20% by weight of carbon black (relative viscosity: 2.15, melting point: 225 ° C.), master component is component D, component A: component B: master chip of component C: weight ratio of component D is 35: A crimped yarn and a carpet were obtained in the same manner as in Example 1 except that it was put into an extruder type extrusion spinning machine while weighing to 50: 5: 10. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Example 5]
A crimped yarn and a carpet are obtained in the same manner as in Example 1 except that it is changed to a die for a Y-shaped hollow cross section, and the resulting crimped yarn has a total fineness of 810 dtex and a single yarn fineness of 15 dtex. Got. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Example 6]
A crimped yarn and a carpet were obtained in the same manner as in Example 1 except that nylon 6 (melting point: 225 ° C.) having a relative viscosity of 2.72 was used as Component B. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Example 7]
A crimped yarn and a carpet were obtained in the same manner as in Example 1 except that nylon 6 having a relative viscosity of 2.15 (melting point: 225 ° C.) was used as Component B. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that component C was not added, and that the mixture was weighed so that the weight ratio of component A: component B was 30:70, and was then fed into an extruder-type extruder. The spinnability at the exit portion was poor and the yarn could not be produced, and the crimped yarn could not be collected.

[Comparative Example 2]
A crimped yarn and a carpet were obtained in the same manner as in Comparative Example 1 except that nylon 6 having a relative viscosity of 2.15 (melting point: 225 ° C.) was used as Component B. Table 1 shows the properties of the obtained crimped yarn and carpet.

[Comparative Example 3]
A crimped yarn and a carpet were obtained in the same manner as in Example 1, except that Component C was monoallyldiglycidyl isocyanuric acid (manufactured by Shikoku Kasei Co., Ltd.). Table 1 shows the properties of the obtained crimped yarn and carpet.

[Comparative Example 4]
A crimped yarn and a carpet were obtained in the same manner as in Example 1 except that Component C was changed to methyl methacrylate / glycidyl methacrylate copolymer (graft polymer, glycidyl group amount: 34 mg KOH / g). Table 1 shows the properties of the obtained crimped yarn and carpet.

  The polymer alloy crimped yarn of the present invention has significantly improved wear resistance, which was a drawback of the polymer alloy yarn, and is suitably used mainly for carpet applications such as car mats, tile carpets, roll carpets, rug mats and dascon mats. is there. Moreover, since it is excellent in wear resistance, it is also suitable for use in high-grade carpet applications that require high wear resistance.

1: Slit length of discharge hole 2: Slit width of discharge hole

Claims (6)

A crimped yarn composed of a polymer alloy obtained by blending an aliphatic polyester resin (A), a thermoplastic polyamide resin (B), and a styrene / (meth) acrylic acid ester copolymer (C) having a glycidyl group.   Styrene / (meth) acrylic acid having glycidyl group with respect to the total amount of aliphatic polyester resin (A), thermoplastic polyamide resin (B) and styrene / (meth) acrylic ester copolymer having glycidyl group (C) The crimped yarn according to claim 1, comprising 0.005 to 5 mass% of the ester copolymer (C).   The crimped yarn according to claim 1 or 2, wherein the total fineness is 500 to 3000 dtex, and the single yarn fineness is 5 to 50 dtex.   The crimped yarn according to any one of claims 1 to 3, wherein the cross-sectional shape of the single yarn is a multi-leaf cross-section having an irregularity of 4.0 or more. The crimped yarn according to any one of claims 1 to 3, wherein the cross-sectional shape of the single yarn is a hollow cross section having a hollowness ratio of 5 to 25%. A carpet using the crimped yarn according to any one of claims 1 to 5.

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