JP2013091862A - Net-like structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a net-like structure with excellent cushioning property, capable of reducing a sound generated by compression and recovery from a compressed state.SOLUTION: A net-like structure comprises a three-dimensional random loop joint structure, which is made by winding a continuous filaments with 100 to 100000 dtex to form a random loop, and contacting each loop together in a melted state, and fusing a large portion of a contacted part. The continuous filament is composed of a composition including a polyester-based thermoplastic elastomer and substituted amides with a structure of R-CONH-Ror R-CONH-(CH)-NHCO-R. The weight ratio of the polyester-based thermoplastic elastomer and the substituted amides is from 100:0.01 to 100:20.

Description

  The present invention relates to a network structure having a continuous linear three-dimensional random loop junction structure.

  For cushions of furniture, beds, trains, cars, etc., continuous linear bodies of 300 denier or more are twisted to form random loops, and the loops are brought into contact with each other in a molten state, and most of the contact portions are melted. A network structure for cushions, which is a three-dimensional random loop joint structure that is worn, has been proposed (see, for example, Japanese Patent Laid-Open No. 7-68061 (Patent Document 1)). As the continuous linear body of the network structure, for example, a polyester elastomer, a polyurethane elastomer, or a polyamide elastomer is preferably used.

  However, since the net-like structure disclosed in Patent Document 1 has a sound that the random loops are rubbed or the random loops are repelled at the time of compression and recovery from the compressed state, When used, it has been pointed out that it is noisy and difficult to sleep.

  For example, Japanese Patent Application Laid-Open No. 2010-43376 (Patent Document 2) addresses such a problem, in which a fineness made of a polyester copolymer having a flexural modulus of 15 to 70 MPa and a surface hardness of 30 to 45 D is 300 dtex or more. A random loop is formed by winding a linear body, the respective loops are brought into contact with each other in a molten state, and a large portion of the contact portion is fused, and the surface of the random loop of the three-dimensional random loop joint structure is silicone. A polyester-based elastic network structure in which 0.4 to 4% by weight of a resin containing a resin is attached is disclosed.

  However, in the network structure disclosed in Patent Document 2, the sound that the random loops are rubbed at the time of compression and recovery from the compressed state is reduced, but the sound that the random loops are repelled is still There was still room for improvement in terms of quietness. In addition, the process of attaching a resin containing a silicone-based resin to the random loop surface is a separate process from the three-dimensional random loop bonded structure and is a batch formulation, which has a problem in manufacturing.

JP 7-68061 A JP 2010-43376 A

  The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a network structure that is excellent in cushioning properties and has reduced sound during compression and recovery from a compressed state. It is to be.

  As a result of intensive studies by the present inventors, a continuous linear body forming a three-dimensional random loop joint structure is composed of a specific composition containing a polyester-based thermoplastic elastomer, so as to ensure cushioning and at the time of compression. The inventors have found that a network structure with reduced sound generated upon recovery from a compressed state can be provided, and the present invention has been achieved. That is, the present invention is as follows.

The network structure of the present invention is formed by winding a continuous linear body of 100 to 100,000 decitex to form a random loop, bringing the respective loops into contact with each other in a molten state, and fusing most of the contact portion. A network structure having a three-dimensional random loop bonding structure, wherein the continuous linear body includes a polyester-based thermoplastic elastomer and R ₁ —CONH—R ₂ or R ₁ —CONH— (CH ₂ ) _n —NHCO—. Substituted amides having a structure consisting of R ₁ (R ₁ and R ₂ are each independently an alicyclic group, aromatic group, saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group having 6 or more carbon atoms. Wherein n is an integer of 1 to 20.), and the weight ratio of the polyester-based thermoplastic elastomer to the substituted amide is 100. : 0.01-20.

  In the network structure of the present invention, the continuous linear body preferably has a hollow cross section or an irregular cross section.

  According to the present invention, the elasticity at the time of compression can be reduced while greatly reducing the generation of a sound that rubs between random loops and a sound that repels random loops even during compression and recovery from a compressed state. A network structure that can be held at the same level as the network structure can be provided.

FIG. 1A is a schematic perspective view of an example of a network structure 1 as a preferred example of the present invention. FIG. 1B is an enlarged view of a part of the network structure 1 shown in FIG. FIG. It is a figure which shows typically the example of the cross section of the continuous linear body 2, FIG. 2 (a) has shown the case of a solid circular cross section, and FIG.2 (b) has shown the case of the hollow circular cross section. It is a figure which shows typically the example of the irregular cross section of the continuous linear body. FIG. 3 is a diagram schematically showing a part of an example of manufacturing the network structure 1. FIG. 3 is a diagram schematically showing a part of an example of manufacturing the network structure 1.

  FIG. 1A is a schematic perspective view of an example of a network structure 1 as a preferred example of the present invention. FIG. 1B is an enlarged view of a part of the network structure 1 shown in FIG. FIG. The network-like structure 1 of the present invention comprises a continuous loop (continuous linear body 2) having a fineness of 100 to 100,000 dtex, and randomly forms a loop (random loop 3), and the loops are brought into contact with each other. A three-dimensional random loop joining structure in which the contacted part (contact part) is fused is provided. By providing such a structure, even when the network structure 1 is deformed with a very large stress, the entire network structure 1 is deformed to absorb the stress, and when the stress is released, a continuous linear shape is obtained. The rubber elasticity of the thermoplastic elastomer forming the body 2 is developed and can be restored to its original form.

The fineness of the continuous linear body 2 forming the network structure of the present invention is in the range of 100 to 100,000 dtex, preferably in the range of 300 to 50000 dtex, and more preferably in the range of 500 to 30000 dtex. . When the fineness of the continuous linear body 2 is less than 100 dtex, the compressive strength is lowered and the repulsive force is lowered. Moreover, when the fineness of the linear body 2 exceeds 100,000 decitex, the individual linear compressing properties of the continuous linear body 2 are large, but the number of components is reduced, so that the dispersion of force is deteriorated, and 100 kg / cm. ^When a remarkably large compressive force of ² or more is applied, a sag due to stress concentration occurs, and the use portion may be limited.

  In the present invention, as the continuous linear body 2, not only a continuous linear body composed of a single fineness filament but also a continuous linear body 2 composed of a filament having different fineness is used, and the apparent density is It is also possible to obtain an optimum configuration by combination.

  The network structure 1 of the present invention is characterized in that the continuous linear body 2 is composed of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides. Note that the continuous linear body 2 in the network structure 1 of the present invention is composed of such a composition, for example, the nuclear magnetic resonance (NMR) spectrum or infrared absorption (IR) of the continuous linear body 2. This can be confirmed by analyzing the spectrum.

  Examples of the polyester-based thermoplastic elastomer include a polyester ether block copolymer having a thermoplastic polyester as a hard segment and a polyalkylene diol as a soft segment, or a polyester ester block copolymer having an aliphatic polyester as a soft segment.

  More specific configurations of the polyester ether block copolymer include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and the like. Dicarboxylic acids selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid dimer acid, or ester-forming derivatives thereof. And at least one of 1,4-butanediol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and other aliphatic diols, 1,1-cyclohexanedimethanol, 1,4-cyclohexane Dimethanol Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or ethylene oxide-propylene oxide having at least one diol component selected from any alicyclic diol, or an ester-forming derivative thereof, and an average molecular weight of about 300 to 5000 A ternary block copolymer composed of at least one of polyalkylenediols selected from copolymers and the like can be used.

  Examples of the polyester ester block copolymer include at least one of the above dicarboxylic acids, at least one of the above diol components, and at least one of polyester diols such as polylactone having an average molecular weight of about 300 to 5,000. The ternary block copolymer comprised from this is illustrated.

  Considering thermal adhesiveness, hydrolysis resistance, stretchability, heat resistance, etc., polyester-based thermoplastic elastomers are: (1) terephthalic acid and / or isophthalic acid as dicarboxylic acid, 1,4-butanediol as diol component , A ternary block copolymer comprising polytetramethylene glycol as a polyalkylene diol, or (2) terephthalic acid and / or naphthalene-2,6-dicarboxylic acid as a dicarboxylic acid, 1,4-butanediol as a diol component, polyester It is preferable to use a ternary block copolymer composed of polylactone as the diol. (1) From a dicarboxylic acid composed of terephthalic acid and / or isophthalic acid, a diol component composed of 1,4-butanediol, and polytetramethylene glycol Become It is particularly preferred to use a triblock copolymer composed of a alkylene diol. Moreover, what introduce | transduced the polysiloxane type soft segment as a polyester-type thermoplastic elastomer can also be used.

In the present invention, the substituted amides improve the slipperiness of the surface of the continuous linear body 2 and reduce the frictional noise between the continuous linear bodies 2 so that the network structure 1 is recovered from the compressed state when compressed. It is added for the purpose of reducing the sound of time. The substituted amides used in the present invention have a structure consisting of R ₁ —CONH—R ₂ or R ₁ —CONH— (CH ₂ ) _n —NHCO—R ₁ , of which R ₁ and R ₂ are independent of each other. And an alicyclic group having 6 or more carbon atoms, an aromatic group, a saturated aliphatic hydrocarbon group, or an unsaturated aliphatic hydrocarbon group. Examples of the alicyclic group having 6 or more carbon atoms include cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, tricyclo [3.3.1.1 ^3.7 ] decyl group and the like, and as an aromatic group having 6 or more carbon atoms. Examples thereof include a phenyl group, a phenylmethyl group, a toluyl group, and a xylyl group. Examples of the saturated aliphatic hydrocarbon group having 6 or more carbon atoms include hexyl group, heptyl group, capryl group, lauryl group, myristyl group, cetyl group, palmityl group, stearyl group, isostearyl group, and behelyl group. Examples of the unsaturated aliphatic hydrocarbon group having 6 or more carbon atoms include oleyl group, erucalyl group, linoleyl group, and linolenyl group. Moreover, said n is an integer of 1-20, Preferably it is an integer of 1-10. When n exceeds 20, the compatibility with the polyester-based thermoplastic elastomer is deteriorated, resulting in excessive blooming.

  As the substituted amides used in the present invention, oleyl oleic acid amide, stearyl oleic acid amide, oleyl stearic acid amide, and ethylene bis-oleic acid amide are particularly preferable examples because they exhibit a high effect of improving slipperiness.

  One of the characteristics of the composition constituting the continuous linear body 2 in the present invention is that the weight ratio of the thermoplastic elastomer and the substituted amide described above is 100: 0.01-20. When the weight ratio of the substituted amides is less than 0.01 when the thermoplastic elastomer is 100, the sound when the network structure 1 is compressed and recovered from the compressed state can be sufficiently reduced. This is because if the weight ratio of the substituted amides exceeds 20 when the thermoplastic elastomer is 100, the impact becomes too small to maintain an appropriate cushioning property. is there. In order to achieve both reduction of sound and retention of cushioning suitably, the weight ratio of the thermoplastic elastomer to the substituted amide is preferably 100: 0.05 to 15, and 100: 0.1 to 10 It is more preferable that

  Various additives can be blended in the composition constituting the continuous linear body 2 in the present invention depending on the purpose. Additives include phthalate ester, trimellitic acid ester, fatty acid, epoxy, adipic acid ester, polyester plasticizer, known hindered phenol, sulfur, phosphorus and amine oxidation Light stabilizers such as inhibitors, hindered amines, triazoles, benzophenones, benzoates, nickels, salicyls, antistatic agents, molecular modifiers such as peroxides, epoxy compounds, isocyanate compounds, carbodiimide compounds Compounds having reactive groups such as, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent whitening agents, fillers, flame retardants, flame retardant aids, organic And inorganic pigments.

  The continuous linear body 2 constituting the network structure 1 of the present invention preferably has an endothermic peak below the melting point in the melting curve measured with a differential scanning calorimeter. The network structure 1 composed of the continuous linear body 2 having an endothermic peak below the melting point is significantly improved in heat resistance and sag resistance than the network structure composed of a continuous linear body having no endothermic peak. . For example, as a polyester-based thermoplastic elastomer, terephthalic acid, naphthalene-2,6-dicarboxylic acid and the like having rigidity in the acid component of the hard segment is 90 mol% or more (more preferably 95 mol% or more, particularly preferably 100 mol). %) And the glycol component to be polymerized to a required degree of polymerization after transesterification, and then polytetramethylene glycol having an average molecular weight of preferably 500 to 5000 (more preferably 1000 to 3000) as polyalkylene diol. When copolymerized at 10 to 70% by weight (more preferably 20 to 60% by weight), if the acid component of the hard segment has a high content of terephthalic acid or naphthalene-2,6-dicarboxylic acid that is rigid, Improved crystallinity of the segment, resistance to plastic deformation, and heat resistance And sag resistance is improved. In addition, if the annealing treatment is performed at a temperature lower than the melting point by at least 10 ° C. after the fusion heat bonding, the heat resistance and the sag resistance are further improved. When annealing is performed after compressive strain is applied, heat resistance and sag resistance are further improved. The continuous linear body 2 of the network structure 1 subjected to such treatment expresses an endothermic peak more clearly in a melting curve measured by a differential scanning calorimeter (DSC) at a temperature of room temperature to a melting point. When annealing is not performed, an endothermic peak does not appear in the melting curve at room temperature or higher and below the melting point. By analogy with this, it is considered that the hard segments are rearranged by annealing, pseudo-crystallization-like cross-linking points are formed, and the heat resistance and sag resistance are improved (hereinafter referred to as this). The annealing process is sometimes referred to as “pseudo crystallization process”.)

  The cross-sectional shape of the continuous linear body 2 constituting the network structure 1 of the present invention is not particularly limited, but a solid circular cross section (FIG. 2 (a)) and a hollow circular cross section having holes 4 (FIG. 2 ( b)) and may be different from a circular cross section such as a triangular shape (FIG. 3 (a)), a Y-shape (FIG. 3 (b)) or a star shape (FIG. 3 (c)). It may have an irregular cross section. Especially, when the cross-sectional shape of the continuous linear body 2 is made into a hollow cross-section and / or an irregular cross-section, it is particularly preferable when it is possible to impart anti-compression property and bulkiness and to reduce the fineness. In addition to the hollow circular cross section shown in FIG. 2B, the hollow cross section includes a hollow triangular cross section, a hollow shape with protrusions, and the like.

  The anti-compressibility of the network structure 1 is adjusted by the modulus of the material to be used, and in the soft material, the hollowness (ratio of the hollow portion in the cross section) and / or the irregularity (cross sectional secondary moment ratio with respect to the circular shape) is increased. The slope of the initial compressive stress can be adjusted, and a material having a slightly high modulus lowers the hollowness and / or the degree of deformity, thereby imparting an anti-compression property so that the sitting comfort of the network structure is improved. As another effect of making the continuous linear body have a hollow cross section and / or a deformed cross section, by increasing the hollow ratio and / or the deformity, it is possible to further reduce the weight when the same anti-compression property is imparted. .

  As shown in FIG. 1, the continuous linear body 2 includes a random loop 3 having a curved shape that is not a complete ring or a complete ring due to the bending of the continuous linear body 2. The network structure 1 having a three-dimensional random loop joint structure has a joint where the random loop 3 of the continuous linear body 2 is joined to the random loop 3 of another continuous linear body 2. Here, the joint part of the random loop 3 is formed by bringing the random loops 3 of the continuous linear body 2 into contact with each other in a molten state and fusing most of the contact parts.

  The network structure 1 of the present invention preferably has a hardness at 25% compression of 10 kg / φ200 or more. Here, the hardness at the time of 25% compression is a stress at the time of 25% compression of a stress-strain curve obtained by compressing the network structure 1 to 75% with a circular compression plate having a diameter of 200 mm. When the hardness at 25% compression is less than 10 kg / φ200, the cushioning property is impaired. The 25% compression hardness of the network structure 1 of the present invention is preferably 15 kg / φ200 or more, and more preferably 20 kg / φ200 or more.

  The upper limit of the 25% compression hardness of the network structure 1 of the present invention is not particularly limited, but is preferably 50 kg / φ200 or less, more preferably 45 kg / φ200 or less, and 40 kg / φ200 or less. It is particularly preferred. When the 25% compression hardness of the network structure exceeds 50 kg / φ200, the network structure becomes too hard and the cushioning property may be deteriorated.

The network structure 1 of the present invention preferably has an average apparent density in the range of 0.005 to 0.20 g / cm ³ from the viewpoint that the function as a cushioning material can be expressed. more preferably in the range of 10 g / cm ^3, and particularly preferably in the range of 0.03~0.06g / cm ^3. This is because when the average apparent density of the network structure 1 is less than 0.005 g / cm ³ , the repulsive force is lost and the mesh structure may be inappropriate for the cushion material. This is because when the apparent density exceeds 0.20 g / cm ³ , the repulsive force is too high and the sitting comfort may be deteriorated.

  The network structure of the present invention may have a multi-layer structure formed by laminating a plurality of layers of a network structure using continuous linear bodies having different finenesses, for example. In this case, preferable characteristics can be imparted by changing the apparent density of each layer. For example, when a net-like structure is constituted by a layer (first layer) made of a continuous fine line with a fineness and a layer (second layer) made of a continuous line with a fine fineness, arranged on the surface side The first layer has a slightly higher density to increase the number of constituents, reduce the stress received by one of the continuous linear bodies, improve the stress distribution, and improve the cushioning ability to support the buttocks Comfort can be improved. Since the second layer is thickened by increasing the fineness and is a finer layer as a layer responsible for vibration absorption and body shape retention, it can be a continuous linear body with a slightly finer fineness and a higher density. As a result, in the case of a seat using such a net-like structure, vibrations and repulsive stress received from the frame surface of the seat are uniformly transmitted to the second layer, so that the whole can be deformed and the seating comfort is improved. The durability of the cushion can also be improved. Furthermore, in order to give the seat side thickness and tension, the fineness can be partially reduced to increase the density.

  Thus, when the network structure 1 is composed of a plurality of layers, the preferred apparent density and fineness of each layer constituting the network structure 1 can be arbitrarily selected according to the purpose.

  The thickness of each layer when the network structure 1 is composed of a plurality of layers is not particularly limited, but is preferably 3 mm or more, and more preferably 5 mm or more, because the function as a cushion body is easily expressed. .

  The network structure of the present invention is a surface layer in which a continuous linear body that is twisted and bent is formed to be substantially flat by being bent at 30 ° or more, preferably 45 ° or more in the middle, and most of the contact portion is fused. It is preferable to have a part. This significantly increases the number of fused contact areas, so that the local external force of the heel when sitting on the net-like structure can be received by the structural surface without giving a sense of foreign matter to the heel. The entire internal structure is deformed to absorb the stress, and when the stress is released, the elasticity of the polyester-based thermoplastic elastomer is developed, and the network structure can be restored to its original form. . When the surface layer part of the network structure is not formed substantially flat, it gives a foreign object feeling to the collar part, and a local external force is applied to the surface, until the continuous linear body of the surface layer part and the fused contact part In some cases, stress concentration occurs selectively, and fatigue due to stress concentration occurs, resulting in a decrease in sag resistance.

  When the net-like structure has a surface layer formed substantially flat, a seat for automobiles, railroads, etc., without using a padding layer or by laminating a very thin padding layer and covering the surface with the side ground And cushion mats for chairs or beds, sofas, and futons.

  When the network structure does not have a surface layer portion formed substantially flat, a relatively thick (preferably 10 mm or more) wadding layer is laminated on the surface of the network structure and the surface is covered with a side surface. It is necessary to form a seat and a cushion mat. Adhesion with the wadding layer or side surface as required is easy when the network structure has a substantially flat surface layer portion, but when the network structure does not have a substantially flat surface layer portion. Will be incompletely bonded due to unevenness.

  Next, with reference to FIG. 4 and FIG. 5, the manufacturing method of the network structure 1 of the present invention having a three-dimensional random loop junction structure will be described, but the following method is an example and the present invention is not limited to this. Absent. The network structure 1 of the present invention is produced by, for example, melt spinning.

  First, as shown in FIG. 4, a composition 11 containing a polyester-based thermoplastic elastomer and specific substituted amides is put into a general melt extruder 12 and heated to a temperature 10 to 80 ° C. higher than the melting point. In a molten state, the liquid is discharged downward from a discharge device 13 having a plurality of orifices 14.

  The shape of the orifice 14 is not particularly limited, but the orifice 14 may have a modified cross-section (for example, a triangle, Y-type, star-shaped or the like having a high cross-sectional secondary moment) or a hollow cross-section (for example, a triangular hollow, a round hollow, a protrusion). It is preferable to have a shape having a shape such as an attached hollow. In this case, the continuous linear body precursor 2a in the molten state is difficult to relax, and the continuous linear body precursor 2a is maintained by maintaining a long flow time at the contact point of the continuous linear body precursor 2a. The adhesion point of can be strengthened. In this case, the apparent bulk of the network structure 1 can be increased, the weight can be reduced, the anti-compression property can be improved, and the resilience can be improved. It is possible to make the formed network structure 1 difficult to sag.

  Further, when the orifice 14 has a hollow cross section, when the hollow ratio exceeds 80%, the hollow portion of the cross section of the continuous linear body precursor 2a is easily crushed. The hollowness of is preferably 10 to 70%, more preferably 20 to 60%, at which the effect of weight reduction can be exhibited.

  Moreover, it is preferable that the pitch between the orifices 14 is 3-20 mm, and it is more preferable that it is 5-10 mm or less. When the pitch between the orifices 14 is 3 to 20 mm, particularly 5 to 10 mm, the random loops formed by the continuous linear body precursor 2a can be sufficiently brought into contact with each other. In order to make the network structure 1 a dense structure, a shorter pitch between the orifices 14 is preferable, and in order to make a rough structure, a longer pitch between the orifices 14 is preferable.

  Note that the apparent density of the network structure 1 varies depending on the configuration in which the pitch between the rows of the orifices 14 or the pitch between the holes is changed, or the pitch between the rows and the pitch between the holes is changed. Can also be provided.

  Moreover, when the pressure loss at the time of discharge of the continuous linear body precursor 2a is provided by changing the cross-sectional area of the orifice 14, the composition containing the polyester-based thermoplastic elastomer in a molten state and specific substituted amides When an object is discharged from the nozzle at a constant pressure, the discharge amount of the continuous linear body precursor 2a decreases as the orifice 14 has a larger pressure loss. Using this principle, it is possible to make the continuous linear body 2 formed by the continuous linear body precursor 2a discharged from each orifice 14 different in fineness.

  And as shown in FIG. 5, the continuous linear body precursor 2a is discharged from the some orifice 14 to the atmosphere of temperature higher than the melting | fusing point, and forms a random loop in a molten state by making it twist. At this time, the distance between the nozzle surface, the take-up conveyor installed on the cooling medium for solidifying the composition containing the polyester-based thermoplastic elastomer and the specific substituted amides, the polyester-based thermoplastic elastomer and the specific substituted amides The loop diameter and the fineness of the linear body are determined by the melt viscosity of the composition containing, the pore diameter of the orifice and the discharge amount. The continuous linear body precursor 2a is sandwiched between the endless nets 55 of a pair of opposing take-up conveyors 51 and 52 provided in the cooling tank 54 in which the cooling medium 53 is accommodated, and the loop is generated. The generated loops are brought into contact with each other by setting the hole intervals so that the loops can contact each other. By bringing the loops into contact with each other in this manner, the loops are in contact with each other (contact part) while forming a three-dimensional form of random loops. Subsequently, the continuous linear body in which the contact portions are fused while forming a random three-dimensional form is continuously drawn into the cooling medium 53 and solidified to form the network structure 1.

  Here, in the take-up conveyors 51 and 52, the continuous linear body precursor 2a having a twisted outer surface on both sides of the network structure 1 having a molten three-dimensional random loop structure is preferably 30 ° or more, more preferably The network structure 1 is formed so that the outer surface of the network structure 1 is substantially flattened while being bent at 45 ° or more, and at the same time, the adhesion is made at the contact point with the unbent continuous linear body precursor 2a. It is preferable to do. Thereafter, the network structure 1 of the present invention is obtained by quenching continuously with the cooling medium 53 (usually using room temperature water is preferable because the cooling rate can be increased and the cost is also reduced). Next, draining and drying are not preferable, but adding a surfactant or the like to the cooling medium 53 is not preferable because draining or drying may be difficult or the polyester-based thermoplastic elastomer may swell.

  Moreover, it is preferable to perform a pseudo crystallization process by annealing the network structure 1 after cooling once. The annealing temperature of the network structure 1 for the pseudo-crystallization treatment is preferably at least 10 ° C. lower than the melting point (Tm) of the polyester-based thermoplastic elastomer, and is preferably equal to or higher than the α dispersion rising temperature (Tαcr) of Tanδ. By this treatment, the heat resistance and sag resistance of the network structure 1 are remarkably improved as compared with those having an endothermic peak below the melting point and not having a pseudo-crystallization treatment temperature (no endothermic peak). A preferable pseudo-crystallization treatment temperature is (Tαcr + 10 ° C.) to (Tm−20 ° C.). When pseudo-crystallization is performed by simple heat treatment, heat resistance and sag resistance are improved. Furthermore, it is more preferable that the heat treatment and the sag resistance are remarkably improved by applying a compression deformation of 10% or more after annealing and then performing an annealing treatment. Moreover, when it passes through a drying process after once cooling, a pseudo crystallization process can be performed simultaneously by making drying temperature into annealing temperature. Moreover, you may perform an annealing process separately from a drying process.

  Next, it is cut into a desired length or shape and used as a cushioning material. When the network structure of the present invention is used for a cushioning material, it is necessary to select a resin, a fineness, a loop diameter, and a bulk density to be used depending on the purpose of use and a use site. For example, when used for wading on the surface layer, it is preferable to have a low density, fine fineness, and a fine loop diameter in order to give a soft touch, moderate subsidence, and a tight bulge. In order to lower the resonance frequency, linearly change the appropriate hardness and hysteresis at the time of compression, improve the body shape retention, and maintain durability, medium density, thick fineness, slightly larger loop diameter Is preferred. Of course, it can be used in combination with other materials, for example, a hard cotton cushion material made of short fiber aggregates, non-woven fabric, etc., in order to meet the required performance in relation to the application. In addition, it can be processed into a molded product from the manufacturing process within a range that does not degrade the performance, and functions such as flame retardant, antibacterial and antibacterial, heat resistance, water and oil repellency, coloring, and fragrance can be given at any stage Processing such as addition can be performed.

The present invention is described in detail below with reference to examples. In addition, evaluation in an Example was performed with the following method.
<Resin characteristics>
(1) Melting point (Tm)
Using a Shimadzu TA50, DSC50 differential thermal analyzer, an endothermic peak (melting peak) temperature was determined from an endothermic curve obtained by measuring a 10 g sample from 20 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min.

(2) Flexural modulus A test piece having a length of 125 mm, a width of 12 mm, and a thickness of 6 mm was prepared by an injection molding machine and measured in accordance with ASTM D790.

<Characteristics of network structure>
(1) 25% compression hardness The sample was cut into a size of 30 cm × 30 cm and compressed to 75% with a φ200 mm compression plate using Tensilon manufactured by Orientec Co., Ltd. Indicated by stress (average value of n = 3).

(2) Apparent density A sample was cut into a size of 15 cm × 15 cm, the height of four locations was measured, the volume was determined, and the weight of the sample was shown as a value that was gradually reduced by volume (average value of n = 4) ).

(3) Fineness of linear body The network structure is cut into a size of 20 cm x 20 cm, and the linear body is collected from 10 locations. The specific gravity at 40 ° C. of the linear bodies collected at 10 locations is measured using a density gradient tube. Furthermore, the cross-sectional area of the linear body sampled at the 10 locations is determined from a photograph enlarged with a microscope, and the volume of the linear body for a length of 10,000 m is determined therefrom. The value obtained by multiplying the obtained specific gravity and volume is defined as the fineness (weight of linear body 10,000 m) (average value of n = 10).

(4) Hollow ratio A linear body is collected from a network structure, and after cooling with liquid nitrogen, it is cleaved. The cross section is observed with an electron microscope at a magnification of 50 times, and the obtained image is analyzed with a CAD system. Then, the cross-sectional area (A) of the resin part and the cross-sectional area (B) of the hollow part were measured, and the hollow ratio was calculated by the formula {B / (A + B)} × 100.

(5) Feeling with a floor 30 panelists in a weight range of 40 to 100 kg (male between 20 and 40 years old: males with a weight of 40 to 100 kg in a network structure of 50 cm square, thickness 5 cm, bulk density 0.040 to 0.050 g / cm ³ : 5 females, 20 to 40 years old: 5 males, 40 to 60 years old: 5 females, 40 to 60 years old: 5 males, 60 to 80 years old: 5 , 60 to 80 years old women: 5) sat down, and evaluated the qualitative evaluation according to the following classifications and scored the level of the feeling of hitting the floor when sitting. .

I don't feel: 2 points
I hardly feel it: 1 point
I feel a little: -1 point,
Feel: -2 points.

Next, the score results of 30 persons obtained were averaged and classified as follows.
2-1 points: ◎,
1 to 0 points: ○,
0-1 points: △,
−1 to −2 points: x.

(6) Silencer 30 panelists in a weight range of 40 to 100 kg in a network structure of 50 cm square, thickness 5 cm, bulk density 0.040 to 0.050 g / cm ³ (male between 20 and 40 years old: 5 Names: Women 20 to 40 years old: 5 Men 40 to 60 years old: 5 Women 40 to 60 years old: 5 Men 60 to 80 years old: 5 people Women aged between 60 and 80 years old: 5) were seated, and the compression sound when sitting was qualitatively evaluated according to the following classification and scored.

I don't feel: 2 points
I hardly feel it: 1 point
I feel a little: -1 point,
Feel: -2 points.

Next, the score results of 30 persons obtained were averaged and classified as follows.
2-1 points: ◎,
1 to 0 points: ○,
0-1 points: △,
−1 to −2 points: x.

<Synthesis Example 1>
Dimethyl terephthalate (DMT), 1,4-butanediol (1,4-BD), and polytetramethylene glycol (PTMG: average molecular weight 1000) are charged together with a small amount of catalyst. The polyester ether block copolymer elastomer having DMT / 1,4-BD / PTMG = 100/84/16 mol% was produced, and then 1% antioxidant was added and kneaded and pelletized. The polyester thermoplastic elastomer raw material (A-1) was obtained by vacuum drying for a period of time. The characteristics are shown in Table 1.

<Synthesis Example 2>
Dimethyl terephthalate (DMT), 1,4-butanediol (1,4-BD), and polytetramethylene glycol (PTMG: average molecular weight 1000) are charged together with a small amount of catalyst. Polyester ether block copolymer elastomer of DMT / 1,4-BD / PTMG = 100/72/28 mol% was formed, and then 1% of antioxidant was added and kneaded, pelletized, and then mixed at 50 ° C. 48 The polyester thermoplastic elastomer raw material (A-2) was obtained by vacuum drying for a period of time. The characteristics are shown in Table 1.

<Example 1>
100 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1, 0.5 kg of ethylenebisoleic acid amide (“Sripacks-O” manufactured by Nippon Kasei Co., Ltd.), 0.25 kg of hindered phenol Antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg phosphorous antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed for 5 minutes with a tumbler, and then mixed with a twin screw extruder having a screw diameter of φ57 mm. The mixture was melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand shape, cooled, and then pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle in which a round solid-shaped orifice having a hole diameter of 1.0 mm was arranged at an interval of 5.2 mm in the width direction and 6.0 mm in the length direction on an effective surface of the nozzle having a width of 65 cm and a length of 5 cm. Melting at a temperature of ° C., discharging a single hole at a discharge rate of 2.0 g / min, disposing cooling water below the nozzle surface 30 cm, and taking a pair of stainless endless nets 70 cm wide in parallel at intervals of 5 cm The conveyor is placed on the water surface so that it is partly pulled out, and the contact part is melted, the both sides are sandwiched and drawn into the cooling water at a speed of 0.5 m / min, and then dried at 100 ° C. After quasi-crystallization treatment for 15 minutes in the machine, quasi-crystallization treatment was performed and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Example 2>
100 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1, 0.5 kg of ethylenebisoleic acid amide (“Sripacks-O” manufactured by Nippon Kasei Co., Ltd.), 0.25 kg of hindered phenol Antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg phosphorous antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed for 5 minutes with a tumbler, and then mixed with a twin screw extruder having a screw diameter of φ57 mm. The mixture was melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand shape, cooled, and then pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle in which a round hollow orifice having a hole diameter of 1.0 mm was arranged at an interval of a width of 5.2 mm and a length of 6.0 mm on an effective surface of the nozzle having a width of 65 cm and a length of 5 cm. A single hole is discharged at a rate of 2.0 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the water surface so that it comes out partly, and the contact part is fused, while both sides are sandwiched, it is drawn into the cooling water at a rate of 1.18 m / min and solidified, and then a hot air dryer at 100 ° C. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Example 3>
100 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1, 0.5 kg of N-oleyl stearamide (“Nikka Amide-OS” manufactured by Nippon Kasei Co., Ltd.), 0.25 kg of hindered A phenolic antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg of a phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed for 5 minutes in a tumbler, and then twin screw extrusion with a screw diameter of φ57 mm The mixture was melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand form, cooled, and then pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, the obtained composition was 240 ° C. A single hole is discharged at a rate of 2.5 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the water surface so that it comes out partly, and the contact part is fused, while both sides are sandwiched, it is drawn into cooling water at a rate of 1.15 m / min and solidified, and then a hot air dryer at 100 ° C. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Example 4>
100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2, 1.0 kg of ethylenebisoleic acid amide (“Nikka Amide-OS” manufactured by Nippon Kasei Co., Ltd.), 0.25 kg of hindered phenol System antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg phosphorous antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then a twin screw extruder having a screw diameter of 57 mm Were melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in the form of a strand, cooled, and then pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, the obtained composition was 240 ° C. A single hole is discharged at a rate of 2.5 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the water surface so that it comes out partly, and the contact part is fused, while both sides are sandwiched, it is drawn into cooling water at a rate of 0.77 m / min and solidified, and then a hot air dryer at 100 ° C. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Example 5>
100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2, 2.0 kg of N-oleyl stearamide (“Nikka Amide-OS” manufactured by Nippon Kasei Co., Ltd.), 0.25 kg of hindered A phenolic antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg of a phosphorus antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed for 5 minutes in a tumbler, and then twin screw extrusion with a screw diameter of φ57 mm The mixture was melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in a strand form, cooled, and then pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, the obtained composition was 240 ° C. A single hole is discharged at a rate of 2.5 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the surface of the water so that it comes out partly, and the contact part is fused, while both sides are sandwiched, it is drawn into the cooling water at a rate of 1.20 m / min and solidified, and then a hot air dryer at 100 ° C. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Example 6>
100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2, 5.0 kg of ethylenebisoleic acid amide (“Nikka Amide-OS” manufactured by Nippon Kasei Co., Ltd.), 0.25 kg of hindered phenol System antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg phosphorous antioxidant (“ADEKA STAB PEP36” manufactured by ADEKA) were mixed in a tumbler for 5 minutes, and then a twin screw extruder having a screw diameter of 57 mm Were melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 130 rpm, extruded into a water bath in the form of a strand, cooled, and then pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle obtained by arranging a round hollow orifice having a hole diameter of 3.0 mm on the effective surface of the nozzle having a width of 65 cm and a length of 5 cm at intervals of 5.2 mm in the width direction and 6.0 mm in the length direction, the obtained composition was 240 ° C. A single hole is discharged at a rate of 2.5 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the surface of the water so that it comes out partly, and the contact part is fused, while both sides are sandwiched, it is drawn into the cooling water at a rate of 1.20 m / min and solidified, and then a hot air dryer at 100 ° C. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Comparative Example 1>
100 kg of the polyester-based thermoplastic elastomer (A-1) obtained in Synthesis Example 1, 0.25 kg of a hindered phenol-based antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg of a phosphorus-based antioxidant ("ADEKA STAB PEP36" manufactured by ADEKA) was mixed for 5 minutes with a tumbler, melted and kneaded with a twin screw extruder with a screw diameter of 57 mm at a cylinder temperature of 220 ° C and a screw rotation speed of 130 rpm, and extruded into a strand in a water bath. After cooling, pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle in which a round hollow orifice having a hole diameter of 1.0 mm was arranged at an interval of a width of 5.2 mm and a length of 6.0 mm on an effective surface of the nozzle having a width of 65 cm and a length of 5 cm. A single hole is discharged at a rate of 2.5 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the surface of the water so that it comes out partly, and the contact part is fused, while both sides are sandwiched, it is drawn into the cooling water at a rate of 1.20 m / min and solidified, and then a hot air dryer at 100 ° C. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

<Comparative example 2>
100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2, 0.25 kg of a hindered phenol-based antioxidant (“ADEKA STAB AO330” manufactured by ADEKA) and 0.25 kg of a phosphorus-based antioxidant ("ADEKA STAB PEP36" manufactured by ADEKA) was mixed for 5 minutes with a tumbler, melted and kneaded with a twin screw extruder with a screw diameter of 57 mm at a cylinder temperature of 220 ° C and a screw rotation speed of 130 rpm, and extruded into a strand in a water bath. After cooling, pellets of a composition containing a polyester-based thermoplastic elastomer and specific substituted amides were obtained. From the nozzle in which a round hollow orifice having a hole diameter of 1.0 mm was arranged at an interval of a width of 5.2 mm and a length of 6.0 mm on an effective surface of the nozzle having a width of 65 cm and a length of 5 cm. A single hole is discharged at a rate of 2.5 g / min, cooling water is disposed 30 cm below the nozzle surface, and a stainless steel endless net with a width of 70 cm is paired in parallel at intervals of 5 cm. Is placed on the surface of the water so that it comes out partly, and the contact part is fused, and the both sides are sandwiched and drawn into the cooling water at a rate of 1.22 m / min. After the crystallization treatment for 15 minutes, the crystallization treatment was performed, and then cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.

  The present invention relates to a network structure having high vibration absorption, and can be used for a vehicle seat, bedding, and the like by taking advantage of its characteristics.

  DESCRIPTION OF SYMBOLS 1 Network structure 2 Continuous linear body 3 Random loop 4 Hole 11 Composition 12 Melt extruder 13 Discharge device 14 Orifice 51,52 Take-up conveyor 53 Cooling medium 54 Cooling tank 55 Endless Net.

Claims (3)

It has a three-dimensional random loop bonding structure in which a continuous linear body of 100 to 100,000 decitex is twisted to form a random loop, and the respective loops are brought into contact with each other in a molten state, and most of the contact portions are fused. A reticulated structure,
The continuous linear body is a polyester-based thermoplastic elastomer and a substituted amide (R ₁ , R having a structure consisting of R ₁ —CONH—R ₂ or R ₁ —CONH— (CH ₂ ) _n —NHCO—R _{1. 2} is each independently any group of an alicyclic group having 6 or more carbon atoms, an aromatic group, a saturated aliphatic hydrocarbon group, or an unsaturated aliphatic hydrocarbon group, and n is an integer of 1 to 20 And a weight ratio of the polyester-based thermoplastic elastomer to the substituted amide is 100: 0.01-20.   The network structure according to claim 1, wherein the continuous linear body has a hollow cross section.   The network structure according to claim 1, wherein the continuous linear body has an irregular cross section.

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