JP6311918B2 - Network structure with excellent compression durability - Google Patents

Description

  The present invention is excellent in repeated compression durability, such as office chairs, furniture, sofas, beds, beddings such as beds, cushion materials used for vehicle seats such as trains, automobiles, motorcycles, child seats, strollers, floor mats, collisions and pinchings. The present invention relates to a net-like structure suitable for an impact absorbing mat such as an anti-skid member.

Currently, foam-crosslinked urethane is widely used as a cushioning material used in furniture, bedding such as beds, and seats for vehicles such as trains, automobiles, and motorcycles.
Foam-crosslinked urethane has good durability as a cushioning material, but is inferior in moisture permeability and breathability and has a problem of being easily steamed due to heat storage. Furthermore, since it is not thermoplastic, it is difficult to recycle. Therefore, when it is incinerated, damage to the incinerator becomes large, and there are problems such as high costs for removing toxic gases. Therefore, landfill is often disposed, but there is a problem that the landfill site is limited and the cost is increased because it is difficult to stabilize the ground. Further, various problems have been pointed out, such as pollution problems of chemicals used during production, residual chemicals after foaming, and odors associated therewith, although the processability is excellent.

  Patent Documents 1 and 2 disclose a network structure. This can solve various problems derived from the above-mentioned foam-crosslinked urethane, and is excellent in cushioning performance. However, the repeated compression endurance characteristics are only excellent in 50% constant displacement repeated compression residual strain, and the hardness retention at 50% compression after 50% repeated compression is about 83%. There was a problem that the hardness was lowered.

  Conventionally, it has been recognized that durability is sufficient if repeated compression residual strain is small. However, in recent years, there has been an increasing demand for repeated compression durability. Rather than the evaluation method of 50% constant displacement repeated compression durability, the hardness at 40% compression after 750 N constant load repeated compression corresponding to a human weight of about 76 kg. The retention rate has been emphasized, and there is an increasing demand for improving this constant load repeated compression durability. The conventional network structure has a hardness retention at 40% compression of only about 50% after 750 N constant load repeated compression, and this improvement has been desired. However, it has been difficult to obtain a network structure having a high hardness retention rate after constant load repeated compression with a conventionally known network structure.

  Patent Document 3 discloses a different fineness network structure and a manufacturing method thereof. This is because the surface layer and the basic layer define the fineness difference using the ratio of the moment of inertia of the round cross section, the soft layer with a thin fiber diameter on the surface, and the inner layer with a large fiber diameter that bears durability on the basic layer Cushioning and durability are improved by providing. In these manufacturing methods, the conventional 50% constant displacement repeated compressibility was excellent, but the stricter 750N constant load repeated compression durability targeted by this patent is not necessarily superior. It was difficult to achieve the scope of the patent.

JP 7-68061 A JP 2004-244740 A JP 7-189105 A

  The object of the present invention is to solve the above-mentioned conventional problems, wherein the 750N constant load repeated compression residual strain is 15% or less, and the 40% hardness retention after the 750N constant load repeated compression is 70% or more. It is an object of the present invention to provide a network structure having excellent repeated compression characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have invented a network structure excellent in repeated compression durability and excellent in hardness retention and thickness retention.

That is, the present invention is as follows.
(1) A network structure comprising a three-dimensional random loop joining structure in which a continuous linear body made of a polyolefin-based thermoplastic elastomer is twisted to form a random loop, and the respective loops are brought into contact with each other in a molten state, The fiber diameter of the continuous linear body is 0.1 mm or more and 3.0 mm or less, the fiber diameter of the surface layer portion of the network structure is 1.05 times or more of the internal fiber diameter, and the apparent density is 0.01 g / cm ³ or more. A network structure having 20 g / cm ³ or less, a 750N constant load cyclic compression residual strain of 15% or less, and a 40% compression hardness retention after 55% constant load cyclic compression is 55% or more.
(2) The network structure according to (1), wherein the hardness retention at 65% compression after repeated compression at a constant load of 750 N is 70% or more.
(3) The network structure according to (1) or (2), wherein the compression deflection coefficient is 2.5 or more.
(4) The network structure according to any one of (1) to (3), wherein the network structure has a thickness of 10 mm to 300 mm.

  The network structure according to the present invention has a small constant load repeated compression residual strain, an excellent hardness retention rate, hardly changes in sitting comfort even after repeated use, and has a characteristic of excellent repeated compression durability. Can provide. With this excellent repeated compression durability, it is possible to provide a reticulated structure cushion with excellent repeated compression durability used for bedding such as office chairs, furniture, sofas, beds, and vehicle seats such as trains and cars. .

Hereinafter, the present invention will be described in detail.
As the polyolefin-based thermoplastic elastomer in the present invention, the polymer constituting the network structure is preferably a low density polyethylene resin having a specific gravity of 0.94 g / cm ³ or less, particularly from ethylene and an α-olefin having 3 or more carbon atoms. It is preferably made of an ethylene / α-olefin copolymer resin. The ethylene / α-olefin copolymer of the present invention is preferably a copolymer described in JP-A-6-293813, and is obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms. It is. Here, examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene, heptene-1, octene-1, nonene-1, and decene. -1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1, etc., preferably butene -1, pentene-1, hexene-1, 4-methyl-1-pentene, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1 , Pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and eicosene-1. Two or more of these can also be used, and these α-olefins are usually copolymerized in an amount of 1 to 40% by weight. This copolymer can be obtained by copolymerizing ethylene and an α-olefin using a catalyst system having a specific metallocene compound and an organometallic compound as basic components.
If necessary, two or more kinds of polymers polymerized by the above method, and polymers such as hydrogenated polybutadiene and hydrogenated polyisoprene can be blended. As a modifier, an antioxidant, an antifungal agent, a flame retardant, and the like can be added as necessary.

When the specific gravity of the polyolefin-based thermoplastic elastomer in the present invention exceeds 0.94 g / cm ³ , the cushion material tends to be hard, which is not preferable. More preferably, it is 0.935 g / cm ³ or less, and further 0.93 g / cm ³ or less is preferable. Although a minimum is not specifically limited, 0.8 g / cm < ³ > or more is preferable from a viewpoint of intensity | strength maintenance, and 0.85 g / cm < ³ > or more is more preferable.

  The component comprising the polyolefin-based thermoplastic elastomer constituting the network structure excellent in repeated compression durability of the present invention preferably has an endothermic peak below the melting point in the melting curve measured with a differential scanning calorimeter. Those having an endothermic peak below the melting point are significantly improved in heat resistance and sag resistance than those having no endothermic peak. For example, as a preferable polyolefin-based thermoplastic elastomer of the present invention, hexane, hexene, and ethylene are polymerized by a known method using a metallocene compound as a catalyst. If the number is reduced, the crystallinity of the hard segment is improved, plastic deformation is difficult, and heat sag resistance is improved. However, after heat-bonding, annealing at a temperature at least 10 ° C. lower than the melting point results in higher heat resistance. Improves drooling. In the annealing treatment, it is sufficient that the sample can be heat-treated at a temperature lower by at least 10 ° C. than the melting point, but the heat distortion resistance is further improved by applying compressive strain. An endothermic peak is more clearly expressed in a melting curve measured with a differential scanning calorimeter at a temperature not lower than the room temperature and not higher than the melting point of the cushion layer subjected to such treatment. In the case where annealing is not performed, an endothermic peak is not clearly expressed in the melting curve from room temperature to the melting point. By analogy with this, it is considered that a metastable intermediate phase in which hard segments are rearranged by annealing is formed, and the heat sag resistance is improved. As a method for utilizing the effect of improving the sag resistance in the present invention, it is useful for improving durability in use applications such as cushions and mats that are relatively repeatedly compressed.

  If the fiber diameter of the continuous linear body constituting the network structure of the present invention is small, the required hardness when used as a cushioning material cannot be maintained, and conversely, if the fiber diameter is too large, the fiber diameter becomes too hard. Therefore, it is necessary to set within an appropriate range. The fiber diameter is 0.1 mm or more and 3.0 mm or less, preferably 0.2 mm or more and 2.5 mm or less. If the fiber diameter is less than 0.1 mm, the fiber will be too thin, and the denseness and soft feel will be good, but it may be difficult to ensure the necessary hardness for the network structure. When the fiber diameter exceeds 3.0 mm, the network structure can have a sufficient hardness, but the network structure becomes rough and other cushioning performance may be inferior.

  In the network structure of the present invention, the fiber diameter of the surface layer portion is 1.05 times or more, preferably 1.08 times or more, more preferably 1.10 times or more the fiber diameter of the inner layer portion. If the fiber diameter of the surface layer portion is less than 1.05 times the fiber diameter of the inner layer portion, the required surface rigidity and surface contact strength cannot be ensured, and the hardness retention required for cushion characteristics cannot be achieved stably. There is a case. The upper limit of the ratio of the fiber diameter of the surface layer portion to the fiber diameter of the inner layer portion is not particularly defined, but is 1.25 times or less in the present invention.

Apparent density of the network structure of the present invention ^{is 0.01g / cm 3 ~0.20g / cm 3} , preferably ^{0.02g / cm 3 ~0.15g / cm 3} , more preferably 0.025 g / cm ^{3 to} 0.12 g / cm ³ . If the apparent density is less than 0.01 g / cm ³ , the cushion will not be able to maintain the required hardness when used as a cushioning material. Conversely, if it exceeds 0.20 g / cm ³ , the cushion becomes too hard and a soft tactile sensation is obtained. It may be unsuitable as a material.

  The 750N constant load cyclic compressive residual strain of the network structure of the present invention is 15% or less, preferably 10% or less. When the 750N constant load repeated compressive residual strain exceeds 15%, the thickness of the network structure decreases when used for a long time, which is not preferable as a cushioning material. The lower limit of the 750N constant load repeated compression residual strain is not particularly defined, but is 0.1% or more in the network structure obtained in the present invention.

  The 40% compression hardness of the network structure of the present invention is preferably 40 N / φ200 to 1000 N / φ200. If the hardness at 40% compression is less than 40 N / φ200, a feeling of bottoming may be felt, and if it exceeds 1000 N / φ200, it may be too hard to impair cushioning properties.

  The network structure according to the present invention has a 40% compression hardness retention after repeated compression at 750 N constant load of 55% or more, preferably 60% or more, more preferably 65% or more, and even more preferably 70% or more. It is. If the 40% -compression hardness retention after 750 N constant load repeated compression is less than 55%, the cushion material may decrease in hardness over time and may feel that the hardness has changed significantly. The upper limit value of 40% hardness retention after 750 N constant load repeated compression is not particularly specified, but is 95% or less in the network structure obtained in the present invention.

  The hardness at the time of 65% compression of the network structure of the present invention is preferably 80 N / φ200 to 2000 N / φ200. If the hardness at 65% compression is less than 80 N / φ200, a feeling of bottoming may be felt, and if it exceeds 2000 N / φ200, it may be too hard to impair cushioning properties.

  The network structure according to the present invention has a 65% compression hardness retention after a constant load repeated compression of 750 N, which is 70% or more, preferably 73% or more, and more preferably 75% or more. If the 65% hardness retention after repeated compression at a constant load of 750 N is less than 70%, the cushion material may be reduced in hardness for a long time, and a feeling of bottoming may be felt. The upper limit value of the hardness retention at 65% compression after 750N constant load repeated compression is not particularly specified, but is 99% or less in the network structure obtained in the present invention.

  The compression deflection coefficient of the network structure of the present invention is preferably 2.5 or more, more preferably 2.8 or more, and further preferably 3.0 or more. If it is 2.5 or less, the sitting comfort and sleeping comfort as a cushioning material may be impaired. The upper limit value of the compression deflection coefficient is not particularly defined, but is 8.0 or less in the network structure obtained by the present invention.

  The thickness of the network structure of the present invention is preferably 10 mm or more, more preferably 20 mm or more. If the thickness is less than 10 mm, it may become too thin when used as a cushioning material, resulting in a feeling of bottoming. The upper limit of the thickness is preferably 300 mm or less, more preferably 200 mm or less, and still more preferably 120 mm or less, in view of the manufacturing apparatus.

  The network structure of the present invention preferably has a hardness at 25% compression of 10 N / φ200 to 600 N / φ200. If the hardness at 25% compression is less than 10 N / φ200, a feeling of bottoming may be felt, and if it exceeds 600 N / φ200, it may be too hard to impair cushioning properties.

  The network structure of the present invention has characteristics that the hardness retention at 40% compression after 750N constant load repeated compression is 55% or more, and the hardness retention at 65% compression after 750N constant load repeated compression is 70% or more. It is preferable. By setting the hardness retention rate within the above range, the net structure that can be used comfortably for a long period of time can be obtained for the first time because the change in hardness of the net structure after a long period of use is small, the change in sitting comfort and sleeping comfort is small. . The 750N constant load repeated compression test is a test for evaluating higher durability than the 50% constant displacement repeated compression test that has been focused on in the prior literature. In the 50% constant displacement repeated compression test, the amount of compression is fixed at 50% of the thickness from the start of processing to the end of processing, but in the case of the 750N constant load repeated compression durability test, for example, the load 750N is thick at the start of processing. Even if it corresponds to a displacement of 50%, the hardness decreases during the repeated compression process, so the compression amount exceeds 50% of the thickness at the end of the process, and the deformation amount that the sample undergoes during the test is 50%. This is because it becomes larger than the constant displacement repeated compression test.

  In order to obtain a network structure that retains hardness in the 750N constant load repeated compression test, the external load (750N) is received at the surface layer of the network structure, and the load is distributed on the surface layer to reduce the burden on the inner layer. The present inventors have found that it is necessary to maintain the load dispersion effect on the surface layer even during the constant load repeated compression test. The former can be solved for the first time by providing a structural difference between the surface layer portion and the inner layer portion, and the latter by strengthening the contact strength between the continuous linear bodies existing in the surface layer portion. That is, the difference between the network structure having a small 50% constant displacement cyclic compression strain known so far and the network structure of the present invention is that the network structure of the present invention has a continuous linear structure constituting the network structure. By further strengthening the fusion between each other, the contact strength between the continuous linear bodies is increased, and at the same time, the fiber diameter of the surface layer part of the network structure is made higher than the fiber diameter of the inner layer part, The difference in the inner layer structure is given, the contact area of the continuous line is increased, the contact strength of the surface layer of the network structure is higher than that of the inner layer part, and the destruction of the contacts that occur during repeated compression processing is further suppressed. This is the point that the effect of surface-dispersing the load (750 N) received during repeated compression at the surface layer portion is maintained. Since it is difficult to stably increase the 40% hardness retention rate after repeated compression at a constant load of 750 N to 55% or more simply by increasing the contact strength between the continuous linear members constituting the network structure, the fibers of the surface layer The surface rigidity was increased by selectively increasing the diameter, the contact strength between the surface layer lines was designed to be higher, and the structure difference between the inner layer and the surface layer could be achieved stably.

  In order to obtain the network structure of the present invention, as described above, it is necessary to provide a structural difference between the surface layer portion and the inner layer portion and to increase the contact strength between the continuous linear portions of the surface layer portion. , It can be obtained by making the fiber diameter of the surface layer portion 1.05 times or more the fiber diameter of the inner layer portion. When the fiber diameter of the surface layer portion is less than 1.05 times the fiber diameter of the inner layer portion, the structural difference between the surface layer portion and the inner layer portion is small, and the required surface rigidity cannot be obtained. For this reason, the effect of surface dispersion at the surface layer portion of the load received during repeated compression is reduced, and a sufficient hardness retention cannot be obtained. The network structure described in Patent Document 3 has improved cushioning and durability by providing a soft layer with a thin fiber diameter on the surface and an inner layer with a large fiber diameter responsible for durability on the basic layer. In the patent, the surface fiber diameter is increased by increasing the fiber diameter of the surface layer to improve the hardness retention, and the essential design concept is different. In addition, in the manufacturing method of Patent Document 3, the conventional 50% constant displacement repeated compressibility was excellent, but the stricter 750N constant load repeated compression durability targeted by this patent is not necessarily excellent. It was difficult to achieve the scope of this patent.

  The network structure of the present invention preferably has a characteristic that the compression deflection coefficient is 2.5 or more. By setting the compression deflection coefficient within the above range, a net-like structure with good sitting comfort and sleeping comfort can be obtained. In particular, it has been found that when the hardness is relatively high, the comfortable seating and sleeping are improved by setting the compression deflection coefficient within the above range. The compression deflection coefficient is expressed as a ratio of 25% compression hardness and 65% compression hardness, and the coefficient can be increased by either decreasing the 25% compression hardness or increasing the 65% compression hardness. In the scope of the present invention, the mechanism by which the compression deflection coefficient is improved has not been fully elucidated, but probably the fiber diameter of the surface layer part described above is large and the surface rigidity is high, and the hardness at the time of compression is 65%. It is presumed that this is because it is getting larger. It is considered that this effect can stably increase the compression deflection coefficient.

  The network structure of the present invention is obtained, for example, as follows. The network structure is obtained based on a known method described in JP-A-7-68061. For example, a polyolefin thermoplastic elastomer is distributed to a nozzle orifice from a multi-row nozzle having a plurality of orifices, and discharged downward from the nozzle at a spinning temperature that is 20 ° C. or more and less than 120 ° C. higher than the melting point of the polyolefin thermoplastic elastomer. In a molten state, the continuous linear bodies are brought into contact with each other and fused to form a three-dimensional structure, sandwiched by a take-up conveyor net, cooled with cooling water in a cooling tank, and then drawn, drained or dried. Thus, a network structure having both sides or one side smoothed is obtained. In the case of smoothing only one surface, it is preferable that cooling is performed while relaxing the shape of only the take-up net surface while discharging it onto an inclined take-up net and bringing it into contact with each other in a molten state to form a three-dimensional structure. The obtained network structure can be annealed. The drying process of the network structure may be an annealing process.

  In order to obtain the network structure of the present invention, it is necessary to strengthen the fusion between the continuous linear bodies of the obtained network structure and to increase the contact strength between the continuous linear bodies. By increasing the contact strength between the continuous linear bodies constituting the network structure, the repeated compression durability of the network structure can be improved as a result.

  As one means for obtaining a network structure with increased contact strength, for example, it is preferable to increase the spinning temperature of a polyolefin-based thermoplastic elastomer. The spinning temperature varies depending on the characteristics of the resin, but in the present invention, the melting point is preferably at least 30 ° C. and 150 ° C., more preferably 40 ° C. and 140 ° C., and even more preferably 50 ° C. and 130 ° C.

  In the network structure of the present invention, as a method for imparting a difference in fiber diameter between the surface layer portion and the inner layer portion, a method in which only the fibers on the surface of the network structure are cooled quickly to increase the fiber diameter only in the surface layer portion is preferable. One of the methods. In the method of giving a difference in fiber diameter by a nozzle configuration in which the hole diameter of the nozzle as described in Patent Document 3 is changed between the surface layer portion and the inner layer portion to increase the fiber diameter only in the surface layer portion, the loop shape of the surface layer portion is distorted. With the aim of this patent, the density difference becomes clear and the quality problem, the discharge balance of the surface layer part and the inner layer part is easily lost, the production stability and the production of uniform products are difficult It was difficult to obtain a certain 750 N constant load repeated compression durability.

  As a method for cooling only the fibers on the surface of the network structure, there are a method of setting the ambient temperature low and a method of selectively blowing cooling air to the surface. In this patent, the atmospheric temperature is the temperature measured by a thermometer located in the same space as the spinning machine, located at a distance of 1 m or more and less than 1.5 m from the spinning machine, and located at the height from the discharge surface to the water surface. Point to. When the surface layer fibers are cooled at this atmospheric temperature, the atmospheric temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 35 ° C. or lower. The atmospheric temperature is preferably −10 ° C. or higher from the viewpoint of preventing the contact strength from significantly decreasing. When cooling air is selectively blown onto the surface, the temperature of the cooling air is preferably equal to or lower than the melting point of the resin, and preferably equal to or higher than the ambient temperature. In addition, even if the cooling air is flowed downward by the entrained flow on the surface or penetrates to the inner layer, it is designed so that the wind whose temperature has been increased by exchanging the temperature with the surface fiber penetrates so as not to decrease the contact strength of the inner layer. It is preferable. From such a viewpoint, it is preferable not to actively cool the fiber direction. The cooling air velocity is preferably 0.3 m / second or less, and more preferably 0.2 m / second or less. By combining the above-described methods singly or in combination of two or more, the fiber diameter of the surface layer portion can be made larger than the fiber diameter of the inner layer portion.

  The apparatus for blowing cooling air preferably has a structure in which the entire width direction is covered in the thickness direction of the network structure and blown from both sides. An apparatus for blowing cooling air can be appropriately selected according to the network structure to be obtained. The installation location in the height direction of the device for blowing the cooling air may be any location between the nozzle surface and the cooling water, and the height may be changed as necessary. The heights need not all be the same in the width direction, and may vary depending on the part. You may spray only to the location which makes surface formation stronger, according to a use, you may spray only one side, or you may spray cooling air from the whole surface toward the thickness direction of a network structure. The cooling air preferably has at least one rectification unit such as a wire mesh in order to make the wind speed as uniform as possible. When raising the temperature of the cooling air, it is preferable to use a hot air generator, and exhaust heat around the nozzle can also be used.

  The continuous linear body constituting the network structure of the present invention may be a composite linear combination with another thermoplastic resin as long as the object of the present invention is not impaired. Examples of the composite form include composite linear bodies such as a sheath / core type, a side-by-side type, and an eccentric sheath / core type when the linear body itself is combined.

  The network structure of the present invention may have a multilayer structure as long as the object of the present invention is not impaired. Examples of the multi-layered structure include a method of stacking network structures and fixing them with a side ground, a method of melting and fixing by heating, a method of bonding with an adhesive, and a method of binding with sewing or a band.

  The cross-sectional shape of the continuous linear body constituting the network structure of the present invention is not particularly limited, but a preferable anti-compression property and touch can be imparted by using a hollow cross-section, an atypical cross section, and a hollow atypical cross-section.

  The network structure of the present invention is processed from a resin production process to a molded body within a range not deteriorating the performance, and at any stage of commercialization, deodorizing antibacterial, deodorizing, antifungal, coloring, aroma, flame retardant, moisture absorption and desorption The functional processing such as chemical addition can be performed.

  The network structure of the present invention thus obtained has excellent repeated compression durability with low repeated compression residual strain and high hardness retention.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measurement and evaluation of the characteristic value in an Example were performed as follows.

(1) Fiber diameter A sample is cut into a size of 20 cm × 20 cm, and a linear body is collected at a length of about 5 mm from each of 10 portions of the surface layer portion and the inner layer portion of the network structure. The surface layer fiber is collected from the outermost surface layer in the thickness direction of the mesh body, that is, from a position where no fiber is present outside the fiber, and the inner layer fiber is 30% of the thickness based on the center portion in the thickness direction of the mesh body. Collect from within range. The fiber diameters of the linear bodies collected from 10 places are measured by focusing an optical microscope at a fiber diameter measurement place at an appropriate magnification. The fiber diameter obtained from the surface layer fiber is the fiber diameter of the surface layer part, and the fiber diameter obtained from the inner layer fiber is the fiber diameter of the inner layer part (unit: mm).

(2) Sample thickness and apparent density After cutting the sample into a size of 40 cm x 40 cm and leaving it to stand for 24 hours with no load, the height of four locations was measured with a polymer instrument FD-80N thickness gauge. The average value is taken as the sample thickness. The sample weight is measured by placing the sample on an electronic balance. Further, the volume is obtained from the sample thickness, and is represented by a value obtained by dividing the weight of the sample by the volume. (Each average value of n = 4)

(3) Melting point (Tm)
An endothermic peak (melting peak) temperature was determined from an endothermic curve measured using a differential scanning calorimeter Q200 manufactured by TA Instruments Co., Ltd. at a heating rate of 20 ° C./min.

(4) 25%, 40%, 65% compression hardness Samples were cut to a size of 40 cm x 40 cm, left under no load in an environment of 23 ° C ± 2 ° C for 24 hours, and then at 23 ° C ± 2 ° C. Measurement is performed in accordance with ISO 2439 (2008) E method using an autograph AG-X plus manufactured by Shimadzu Corporation under the environment. A sample is placed so that a pressure plate of φ200 mm is at the center of the sample, and the thickness when the load is 5 N is measured to obtain the initial hardness meter thickness. With the position of the pressure plate at this time as the zero point, preliminary compression is performed once at a speed of 100 mm / min to 75% of the initial hardness meter thickness, and after returning the pressure plate to the zero point at the same speed, Immediately after elapse of a predetermined time, compression is performed to 25%, 40%, and 65% of the initial hardness meter thickness at a speed of 100 mm / min, and the load at that time is measured. % Compression hardness, 65% compression hardness: unit N / φ200 (average value of n = 3).

(5) Residual strain after repeated compression with 750 N load The sample is cut into a size of 40 cm × 40 cm, and the initial hardness meter thickness (a) is measured by the method described in (4). Thereafter, the sample whose thickness is measured is subjected to 750 N constant load repeated compression in accordance with JIS K6400-4 (2004) A method (constant load method) using ASKER STM-536. The pressurizer uses a circular shape with a radius of curvature of 25 ± 1 mm at the bottom edge, a diameter of 250 ± 1 mm and a flat bottom surface, a load of 750 N ± 20 N, a compression frequency of 70 ± 5 times per minute, and the number of compressions The time during which the pressure is applied to 80,000 times and the maximum of 750 ± 20 N is 25% or less of the time required for repeated compression. After repeated compression, leave the specimen for 10 ± 0.5 minutes without applying any force, and use a Shimadzu Autograph AG-X plus to place the sample so that the pressure plate of φ200mm is at the center of the sample. The thickness when the load reaches 5N is measured, and is set as the hardness meter thickness (b) after repeated compression. Using the initial hardness meter thickness (a) and repeated compression hardness meter thickness (b), it is calculated from the formula {(a)-(b)} / (a) × 100: unit% (average value of n = 3) ).

(6) Hardness retention at 40% compression after 750N constant load repeated compression)
A sample is cut into a size of 40 cm × 40 cm, and the initial hardness meter thickness and 40% compression hardness (c) are measured by the method described in (4). Thereafter, the measured sample is subjected to 750 N constant load repeated compression according to JIS K6400-4 (2004) A method (constant load method) using ASKER STM-536. The pressurizer uses a circular shape with a radius of curvature of 25 ± 1 mm at the bottom edge, a diameter of 250 ± 1 mm and a flat bottom surface, a load of 750 N ± 20 N, a compression frequency of 70 ± 5 times per minute, and the number of compressions The time during which the pressure is applied to 80,000 times and the maximum of 750 ± 20 N is 25% or less of the time required for repeated compression. After repeated compression, leave the specimen for 10 ± 0.5 minutes without applying any force, and use a Shimadzu Autograph AG-X plus to place the sample so that the pressure plate of φ200mm is at the center of the sample. The sample thickness is 750N, with the initial hardness meter thickness before constant load repeated compression as zero point, pre-compression is performed once to 75% of the initial hardness meter thickness at a speed of 100mm / min, and the pressure plate is returned to the zero point at the same speed. After that, the sample is left as it is for 4 minutes. Immediately after the elapse of a predetermined time, it is compressed to 40% of the initial hardness meter thickness at a speed of 100 mm / min, and the load at that time is 40% after repeated compression at a constant load of 750 N. Compressive hardness (d). The hardness retention at the time of 40% compression after 750 N constant load repeated compression is calculated from the formula (d) / (c) × 100: unit% (average value of n = 3).

(7) 65% hardness hardness retention after repeated compression at a constant load of 750 N A sample was cut into a size of 40 cm × 40 cm, and the initial hardness meter thickness and 65% compression hardness (e) by the method described in (4) Measure. Thereafter, the measured sample is subjected to 750 N constant load repeated compression according to JIS K6400-4 (2004) A method (constant load method) using ASKER STM-536. The pressurizer uses a circular shape with a radius of curvature of 25 ± 1 mm at the bottom edge, a diameter of 250 ± 1 mm and a flat bottom surface, a load of 750 N ± 20 N, a compression frequency of 70 ± 5 times per minute, and the number of compressions The time during which the pressure is applied to 80,000 times and the maximum of 750 ± 20 N is 25% or less of the time required for repeated compression. After repeated compression, leave the specimen for 10 ± 0.5 minutes without applying any force, and use a Shimadzu Autograph AG-X plus to place the sample so that the pressure plate of φ200mm is at the center of the sample. The sample thickness is 750N, and the initial hardness meter thickness before repeated compression at a constant load is zero, and the pre-compression is performed once at a speed of 100 mm / min to 75% of the initial hardness meter thickness, and the pressure plate is returned to the zero point at the same speed After that, the sample is left as it is for 4 minutes. Immediately after the lapse of a predetermined time, it is compressed to 40% of the initial hardness meter thickness at a speed of 100 mm / min, and the load at that time is 65% after repeated compression at a constant load of 750 N. Hardness at compression (f). The 65% compression hardness retention after compression at 750 N constant load is calculated from the formula (f) / (e) × 100: unit% (average value of n = 3).

(8) Compression deflection coefficient A sample is cut into a size of 40 cm × 40 cm, left in an environment of 23 ° C. ± 2 ° C. with no load for 24 hours, and then auto manufactured by Shimadzu Corporation in an environment of 23 ° C. ± 2 ° C. It measures based on ISO2439 (2008) E method using graph AG-X plus. A sample is placed so that a pressure plate of φ200 mm is at the center of the sample, and the thickness when the load is 5 N is measured to obtain the initial hardness meter thickness. With the position of the pressure plate at this time as the zero point, preliminary compression is performed once at a speed of 100 mm / min to 75% of the initial hardness meter thickness, and after returning the pressure plate to the zero point at the same speed, Immediately after elapse of a predetermined time, compression is performed at a speed of 100 mm / min to 25% to 65% of the thickness of the initial hardness meter, and the load at that time is measured. % Hardness at compression (h). The compression deflection coefficient is calculated from the formula (h) / (g) (average value of n = 3).

[Synthesis Example 1]
Ethylene and hexene-1 are polymerized by a known method using hexane as a solvent and a metallocene compound as a catalyst to form an ethylene / α-olefin copolymer, and then 2% antioxidant is added and kneaded and pelletized. To obtain a polyolefin-based thermoplastic elastomer (A-1). The obtained polyolefin-based thermoplastic elastomer (A-1) had a specific gravity of 0.919 g / cm ³ and a melting point of 110 ° C.

[Synthesis Example 2]
By using hexane as a solvent and using a metallocene compound as a catalyst, ethylene and propylene are polymerized by a known method to obtain an ethylene / α-olefin copolymer, and then 2% antioxidant is added and kneaded and pelletized. A polyolefin-based thermoplastic elastomer (A-2) was obtained. The obtained polyolefin-based thermoplastic elastomer (A-1) had a specific gravity of 0.887 g / cm ³ and a melting point of 155 ° C.

[Example 1]
The obtained polyolefin-based thermoplastic elastomer (A-1) was spun at a temperature of 200 mm in a nozzle having an orifice with a hole diameter of 0.8 mm and a staggered arrangement with a hole pitch of 5 mm on the nozzle effective surface having a width direction of 1050 mm and a thickness direction of 60 mm. At ℃, the nozzle is discharged at a rate of 1.0 g / min at a single hole discharge rate, passes through a cooling space with an ambient temperature of 20 ℃, and the cooling air is not blown, and cooling water is arranged under 22 cm of the nozzle surface, A stainless steel endless net with a width of 150 cm is arranged in parallel with an opening width of 45 mm so that a part of the pair of take-up conveyors comes out on the water surface, and the molten discharge line is bent to form a loop. Then, a three-dimensional network structure is formed while fusing the contact portions, and both sides of the molten network are sandwiched by a take-up conveyor and drawn into cooling water at a rate of 0.9 m / min. After the surface was flattened, and dried heat-treated for 15 minutes at 70 ° C. hot air and cut to a predetermined size to obtain a network structure. Table 1 shows the characteristics of the network structure composed of the obtained polyolefin-based thermoplastic elastomer (A-1).
The obtained net-like body is formed in a linear shape having a solid cross-sectional shape with a fiber diameter of the surface layer portion of 0.52 mm and a fiber diameter of the inner layer portion of 0.48 mm, and the apparent density is 0.061 g / cm ³ , The surface is flattened thickness 46 mm, 25% compression hardness 155 N / φ200 mm, 40% compression hardness 225 N / φ200 mm, 65% compression hardness 470 N / φ200 mm, 750 N repeated compression residual strain 8.0%, The network structure had a 40% hardness retention after repetitive compression of 750N of 61.2%, a 65% hardness retention after repetitive compression of 750N of 74.2%, and a compression deflection coefficient of 3.0. The obtained network structure satisfied the requirements of the present invention, and was a network structure excellent in repeated compression durability.

[Example 2]
On the nozzle effective surface of the nozzle of width direction 1050mm and thickness direction width 60mm, the shape of the orifice is 2mm outer diameter, 1.6mm inner diameter, and the orifice which made the triple bridge hollow formation cross section into the nozzle which made the staggered arrangement of the hole pitch 5mm, The polyolefin-based thermoplastic elastomer (A-1) is discharged below the nozzle at a spinning hole temperature of 210 ° C. at a single hole discharge rate of 1.5 g / min. After passing through a cooling space with an ambient temperature of 20 ° C., a cooling air temperature of 50 Cooling air is blown at a cooling air velocity of 0.2 m / sec at a temperature of 0 ° C., cooling water is arranged 30 cm below the nozzle surface, and a pair of take-up conveyors are placed on the water surface at intervals of opening width 45 mm in parallel with a 150 cm wide stainless steel endless net. A three-dimensional network structure is formed by arranging the loop so that a part of the discharge line in a molten state is twisted to form a loop to fuse the contact portion. The both sides of the molten network are sandwiched by a take-up conveyor and drawn into cooling water at a speed of 1.6 m per minute to solidify the surfaces, flatten both sides, cut into a predetermined size, and heated with 70 ° C hot air. A heat treatment was performed for 15 minutes to obtain a network structure. Table 1 shows the characteristics of the network structure composed of the obtained polyolefin-based thermoplastic elastomer (A-1).
The obtained network structure is formed of filaments having a hollow cross-sectional shape, a hollow ratio of 25%, a fiber diameter of the surface layer portion of 0.71 mm, and a fiber diameter of the inner layer portion of 0.65 mm. The density is 0.053 g / cm ³ , the flattened thickness is 46 mm, 25% compression hardness is 185 N / φ200 mm, 40% compression hardness is 242 N / φ200 mm, 65% compression hardness is 573 N / φ200 mm, 750 N Repetitive compression residual strain is 8.0%, 40% hardness retention after 750N repeated compression is 66.4%, 65% hardness retention after 750N repeated compression is 79.1%, and compression deflection coefficient is 3.1. It was a network structure. The obtained network structure satisfied the requirements of the present invention, and was a network structure excellent in repeated compression durability.

[Example 3]
A network structure was obtained in the same manner as in Example 2 except that the ambient temperature of the cooling space was 15 ° C. and the opening width of the endless net was 40 mm apart. Table 1 shows the characteristics of the network structure composed of the obtained polyolefin-based thermoplastic elastomer (A-1).
The obtained network structure is formed of filaments having a hollow cross-sectional shape, a hollowness ratio of 25%, a fiber diameter of the surface layer portion of 0.76 mm, and a fiber diameter of the inner layer portion of 0.68 mm. The density is 0.060 g / cm ³ , the flattened thickness is 41 mm, 25% compression hardness is 208 N / φ200 mm, 40% compression hardness is 279 N / φ200 mm, 65% compression hardness is 629 N / φ200 mm, 750 N Repeated compression residual strain is 7.9%, 40% hardness retention after 750N repeated compression is 70.2%, 65% hardness retention after 750N repeated compression is 80.1%, and compression deflection coefficient is 3.0. It was a network structure. The obtained network structure satisfied the requirements of the present invention, and was a network structure excellent in repeated compression durability.

[Example 4]
A network structure was obtained in the same manner as in Example 3 except that the polyolefin-based thermoplastic elastomer (A-2) was used and the spinning temperature was 230 ° C. Table 1 shows the characteristics of the network structure composed of the obtained polyolefin-based thermoplastic elastomer (A-2).
The obtained network structure has a hollow cross-sectional shape, a hollow ratio of 22%, a fiber diameter of the surface layer portion of 0.69 mm, and a fiber diameter of the inner layer portion of 0.60 mm. The density is 0.060 g / cm ³ , the flattened thickness is 41 mm, 25% compression hardness is 215 N / φ200 mm, 40% compression hardness is 281 N / φ200 mm, 65% compression hardness is 645 N / φ200 mm, 750 N Repeated compression residual strain is 8.1%, 40% hardness retention after 750N repeated compression is 72.1%, 65% hardness retention after 750N repeated compression is 81.4%, and compression deflection coefficient is 3.0. It was a network structure. The obtained network structure satisfied the requirements of the present invention, and was a network structure excellent in repeated compression durability.

[Comparative Example 1]
A network structure was obtained in the same manner as in Example 1 except that the spinning temperature was 190 ° C., no cooling space was provided, and the opening width of the stainless steel endless net was 50 mm. Table 1 shows the characteristics of the network structure made of the polyolefin-based thermoplastic elastomer.
The obtained network structure is formed of filaments having a solid cross-sectional shape with a fiber diameter of the surface layer portion of 0.51 mm and a fiber diameter of the inner layer portion of 0.49 mm, and an apparent density of 0.056 g / cm ³ , Surface flattened thickness is 50mm, 25% compression hardness is 162N / φ200mm, 40% compression hardness is 216N / φ200mm, 65% compression hardness is 469N / φ200mm, 750N repeated compression residual strain is 8.9% The network structure had a 40% hardness retention after repeated compression of 750N of 51.6%, a 65% hardness retention after repeated compression of 750N of 67.6%, and a compression deflection coefficient of 2.9. The obtained network structure did not satisfy the requirements of the present invention, and was a network structure slightly inferior in repeated compression durability.

[Comparative Example 2]
A network structure was obtained in the same manner as in Example 2 except that the spinning temperature was 190 ° C., no cooling space was provided, cooling air was not blown, and the opening width of the stainless steel endless net was 50 mm. Table 1 shows the characteristics of the network structure made of the polyolefin-based thermoplastic elastomer.
The obtained network structure is formed of filaments having a hollow cross-sectional shape, a hollowness ratio of 24%, a fiber diameter of the surface layer portion of 0.70 mm, and a fiber diameter of the inner layer portion of 0.68 mm. Density is 0.048 g / cm ³ , surface flattened thickness is 50 mm, 25% compression hardness is 152 N / φ200 mm, 40% compression hardness is 219 N / φ200 mm, 65% compression hardness is 490 N / φ200 mm, 750 N Repetitive compressive residual strain is 11.3%, 40% hardness retention after 750N repeated compression is 53.1%, 65% hardness retention after 750N repeated compression is 68.9%, and compression deflection coefficient is 2.4. Some inferior network structure. The obtained cushion did not satisfy the requirements of the present invention, and was a network structure slightly inferior in repeated compression durability.

[Comparative Example 3]
A network structure was obtained in the same manner as in Comparative Example 2 except that the polyolefin-based thermoplastic elastomer (A-2) was used. Table 1 shows the characteristics of the network structure composed of the obtained polyolefin-based thermoplastic elastomer (A-2).
The obtained network structure is formed of filaments having a hollow cross-sectional shape, a hollowness of 23%, a fiber diameter of the surface layer portion of 0.71 mm, and a fiber diameter of the inner layer portion of 0.70 mm. The density is 0.048 g / cm ³ , the flattened thickness is 50 mm, the hardness at 25% compression is 148 N / φ200 mm, the hardness at 40% compression is 213 N / φ200 mm, the hardness at 65% compression is 452 N / φ200 mm, 750 N Repeated compression residual strain was 12.1%, 40% hardness retention after 750N repeated compression was 52.3%, 65% hardness retention after 750N repeated compression was 68.2%, and compression deflection coefficient was 3.1. It was a network structure. The obtained network structure satisfied the requirements of the present invention, and was a network structure excellent in repeated compression durability.

  The network structure of the present invention is an improvement in the durability after repeated compression of 750 N constant load, which was a problem of the conventional product, without impairing the comfortable sitting comfort and air permeability that the network structure has conventionally had, Cushions and floor mats used for seats for office chairs, furniture, sofas, bedding such as beds, trains, cars, motorcycles, child seats, strollers, etc. In addition, it is possible to provide a net-like structure suitable for a shock absorbing mat such as a member for preventing collision and pinching, and thus greatly contributing to the industry.

Claims (4)

A network structure consisting of a three-dimensional random loop joining structure in which a continuous linear body made of a polyolefin-based thermoplastic elastomer is twisted to form a random loop, and each loop is brought into contact with each other in a molten state. The fiber diameter of the body is 0.1 mm or more and 3.0 mm or less, the fiber diameter of the surface layer portion of the network structure is 1.05 times or more of the internal fiber diameter, and the apparent density is 0.01 g / cm ³ or more and 0.20 g / cm ³ or less, 750N constant load repeated compression residual strain is 15% or less, and 750N constant load repeated compression 40% compression hardness retention is 55% or more.   2. The network structure according to claim 1, which has a 65% compression hardness retention after 70% constant load repeated compression is 70% or more.   The network structure according to claim 1 or 2, wherein the compression deflection coefficient is 2.5 or more.   The network structure according to any one of claims 1 to 3, wherein the network structure has a thickness of 10 mm to 300 mm.