WO2013168699A1 - 静粛性と硬さに優れた弾性網状構造体 - Google Patents
静粛性と硬さに優れた弾性網状構造体 Download PDFInfo
- Publication number
- WO2013168699A1 WO2013168699A1 PCT/JP2013/062831 JP2013062831W WO2013168699A1 WO 2013168699 A1 WO2013168699 A1 WO 2013168699A1 JP 2013062831 W JP2013062831 W JP 2013062831W WO 2013168699 A1 WO2013168699 A1 WO 2013168699A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- network structure
- structure according
- thermoplastic elastomer
- polyester
- random
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B68—SADDLERY; UPHOLSTERY
- B68G—METHODS, EQUIPMENT, OR MACHINES FOR USE IN UPHOLSTERING; UPHOLSTERY NOT OTHERWISE PROVIDED FOR
- B68G1/00—Loose filling materials for upholstery
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B68—SADDLERY; UPHOLSTERY
- B68G—METHODS, EQUIPMENT, OR MACHINES FOR USE IN UPHOLSTERING; UPHOLSTERY NOT OTHERWISE PROVIDED FOR
- B68G11/00—Finished upholstery not provided for in other classes
- B68G11/02—Finished upholstery not provided for in other classes mainly composed of fibrous materials
- B68G11/03—Finished upholstery not provided for in other classes mainly composed of fibrous materials with stitched or bonded fibre webs
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/018—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the shape
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/601—Nonwoven fabric has an elastic quality
Definitions
- Examples of the ⁇ olefin having 3 or more carbon atoms include propylene, isoprene, 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 can be exemplified as preferred examples, and propylene and isoprene are exemplified. It can illustrate as a more preferable example. Two or more of these ⁇ -olefins can be used in combination.
- 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.
- the continuous filaments constituting the network structure of the present invention can be composed of a mixture of two or more different thermoplastic resins depending on the purpose.
- a mixture of two or more different thermoplastic resins at least one selected from the group consisting of soft polyolefin, polystyrene-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer. It is preferable to include 50% by weight or more of the selected thermoplastic resin, more preferably 60% by weight or more, and even more preferably 70% by weight or more.
- the continuous filaments constituting the network structure of the present invention preferably have an endothermic peak below the melting point in the melting curve measured with a differential scanning calorimeter (DSC). Those having an endothermic peak below the melting point have significantly improved heat and sag resistance than those having no endothermic peak.
- DSC differential scanning calorimeter
- the heat sag resistance is further improved.
- Heat annealing resistance is further improved by annealing after applying compressive strain.
- the filaments of the network structure subjected to such treatment more clearly express an endothermic peak at a temperature not lower than the melting point and not higher than the melting point in the melting curve measured by a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- this annealing treatment is sometimes referred to as “pseudo crystallization treatment.”
- This pseudo crystallization treatment effect is also effective for soft polyolefins, polystyrene-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers. It is.
- a preferred range of the average apparent density of the random loop bonded structure is a network structure of the present invention is 0.005g / cm 3 ⁇ 0.200g / cm 3. Expression of the function as a cushioning material can be expected within the above range. If it is less than 0.005 g / cm 3 , the repulsive force is lost, so it is unsuitable for a cushioning material. If it exceeds 0.200 g / cm 3 , the repulsive force is too high and the seating comfort is deteriorated.
- a more preferable apparent density of the present invention is 0.010 g / cm 3 to 0.150 g / cm 3. A more preferable range is 0.020 g / cm 3 to 0.100 g / cm 3 .
- the number of bonding points per unit weight of the random loop bonded structure which is the network structure of the present invention is preferably 500 to 1200 / g.
- the joint point refers to the fusion part between two filaments, and the number of joint points per unit weight (unit: pieces / g) is the size of the network structure in the longitudinal direction 5 cm ⁇ width direction 5 cm. Then, in the rectangular parallelepiped pieces that are cut into a rectangular parallelepiped shape so as not to include the sample ears, the number of junction points per unit volume in the individual pieces (unit: pieces / cm3) Is a value obtained by grading the apparent density of the individual pieces (unit: g / cm 3 ).
- the number of bonding points per unit weight of the conventional network structure is less than 500 / g, but in the present invention, the desired effect can be obtained by setting it to 500 / g or more.
- the number of bonding points per unit weight is larger than 1200 pieces / g, the air permeability deteriorates and the comfort is impaired, which is not preferable. More preferably, it is 550 to 1150 / g, still more preferably 600 to 1100 / g, still more preferably 650 to 1050 / g, and particularly preferably 700 to 1000 / g.
- the fineness of the filaments forming the network structure of the present invention is not particularly limited, but by reducing the fineness, it is possible to reduce the size of the repelling sound between the filaments, the effect of the number of joint points per unit weight described above In combination with this, the silence of the network structure can be further enhanced. However, if the fineness becomes too small, the hardness of the filaments becomes extremely small and an appropriate cushioning property cannot be maintained. In order to further improve the quietness while maintaining a moderate cushioning property, the fineness is preferably 200 to 10,000 dtex, more preferably 200 to 5000 dtex, and even more preferably 200 to 3000 dtex. . In the present invention, it is possible to use not only continuous filaments composed of filaments having a single fineness but also filaments having different finenesses, and an optimum configuration can be obtained by combining with the apparent density.
- the hardness at the time of 25% compression of the network structure of the present invention is not particularly limited, but is preferably 5 kg / ⁇ 200 mm or more.
- the 25% compression hardness is the stress at 25% compression of the stress-strain curve obtained by compressing the network structure to 75% with a circular compression plate having a diameter of 200 mm. If the hardness at 25% compression is less than 5 kg / ⁇ 200 mm, sufficient elasticity cannot be obtained, and comfortable cushioning properties are impaired. More preferably, it is 10 kg / ⁇ 200 mm or more, and particularly preferably 15 kg / ⁇ 200 mm or more.
- the upper limit is not particularly defined, but is preferably 50 kg / ⁇ 200 mm or less, more preferably 45 kg / ⁇ 200 mm or less, and particularly preferably 40 kg / ⁇ 200 mm or less. If it is 50 kg / ⁇ 200 mm or more, it becomes too hard, which is not preferable from the viewpoint of cushioning properties.
- the manufacturing method of the network structure which consists of a three-dimensional random loop junction structure of this invention is described below, the following method is an example and is not limited to this.
- the thermoplastic elastomer is heated to a temperature 10 to 120 ° C. higher than the melting point to be in a molten state, discharged downward from a nozzle having a plurality of orifices, and naturally lowered to form a loop. .
- the loop diameter, the fineness of the filaments, and the number of joints are determined by the distance between the nozzle surface and the take-up conveyor installed on the cooling medium for solidifying the resin, the melt viscosity of the resin, the hole diameter and discharge amount of the orifice, and the like.
- a pair of take-up conveyors that can be adjusted on the cooling medium can be adjusted so that a molten discharge wire is sandwiched and stopped, and a loop is generated.
- the generated loops are brought into contact with each other, and the contact portions are fused while the loops form a random three-dimensional form.
- the hole interval of the orifice affects the number of joint points.
- the continuous filaments in which the contact portions are fused while forming a random three-dimensional form are continuously drawn into the cooling medium and solidified to form a network structure.
- the pitch between the holes of the orifice needs to be a pitch at which the loop formed by the filament can sufficiently contact.
- the pitch between holes is shortened to obtain a dense structure, and the pitch between holes is increased to obtain a dense structure.
- the pitch between holes of the present invention is preferably 3 mm to 20 mm, more preferably 4 mm to 10 mm.
- different density and different fineness can be achieved as desired.
- the different density layer can be formed by a configuration in which the pitch between rows or the pitch between holes is changed, and a method in which both the pitch between rows and between holes are also changed.
- both outer surfaces of the melted three-dimensional structure are sandwiched by a take-off net, and the twisted discharge filaments on both surfaces are bent and deformed by 30 ° or more, and the surface is flattened and not bent at the same time.
- a structure is formed by adhering contact points with the discharge filaments.
- the network structure comprising the three-dimensional random loop joint structure of the present invention is continuously cooled rapidly with a cooling medium (usually room temperature water is preferable because the cooling rate can be increased and the cost is reduced). Get the body.
- a cooling medium usually room temperature water is preferable because the cooling rate can be increased and the cost is reduced. Get the body.
- draining and drying are performed. However, adding a surfactant or the like to the cooling medium is not preferable because draining or drying becomes difficult and the thermoplastic elastomer may swell.
- a pseudo crystallization treatment is performed after cooling.
- the pseudo-crystallization temperature is at least 10 ° C. lower than the melting point (Tm) and is equal to or higher than the Tan dispersion ⁇ dispersion rising temperature (T ⁇ cr).
- This treatment has an endothermic peak below the melting point, and the heat sag resistance is remarkably improved as compared with the case where the pseudo crystallization treatment is not performed (the case where no endothermic peak is provided).
- the preferred pseudocrystallization temperature of the present invention is (T ⁇ cr + 10 ° C.) to (Tm ⁇ 20 ° C.). When pseudo-crystallization is performed by simple heat treatment, heat sag resistance is improved.
- annealing with 10% or more of compressive deformation is more preferable because the heat sag resistance is remarkably improved.
- pseudo-crystallization treatment can be simultaneously performed by setting the drying temperature to the annealing temperature.
- a pseudo crystallization process can be performed separately.
- the volume (unit: cm 3 ) is obtained, and the apparent density (unit: g) is determined by gradually decreasing the weight (unit: g) of the sample by volume. / Cm 3 ) was calculated.
- the number of junction points of this piece is counted, and the number of junction points per unit volume (unit: pieces / cm 3 ) is calculated by dividing this number by the volume of the piece, and the number of junction points per unit volume
- the number of junctions per unit weight (unit: pieces / g) was calculated by dividing the apparent density by the apparent density.
- the joining point was a fusion part between two filaments, and the number of junctions was measured by pulling the two filaments and peeling the fusion part.
- Silencer 30 panelists (20-39-year-old males; 5 males) in a body weight range of 40 kg to 100 kg on a sample cut into a rectangular parallelepiped shape so as to include 2 sample surface layers with a size of 50 cm in the longitudinal direction and 50 cm in the width direction 20-39-year-old women: 5; 40-59-year-old men: 5; 40-59-year-old women: 5; 60- to 80-year-old men: 5; 60- to 80-year-old Women: 5) were seated and the sound generated from the network structure was qualitatively evaluated.
- 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), 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 the resin composition were obtained.
- ADEKA STAB AO330 a hindered phenol-based antioxidant
- ADEKA STAB PEP36 0.25 kg of phosphorus-based antioxidant
- the obtained resin composition was melted at a temperature of 240 ° C. from a nozzle in which circular hollow orifices having a hole diameter of 3.0 mm were arranged at an interval of 6 mm on a nozzle effective surface having a width of 66 cm and a length of 5 cm, and a single hole was discharged. Discharge at a rate of 2.4 g / min, dispose cooling water 35 cm below, and arrange a 70 cm wide stainless steel endless net in parallel at intervals of 4 cm so that a pair of take-up conveyors partially emerge on the water surface.
- Example 2 100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 0.25 kg of a hindered phenol antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 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 the resin composition were obtained.
- the obtained resin composition was melted at a temperature of 245 ° C. from a nozzle in which round solid-shaped orifices having a hole diameter of 1.0 mm were arranged at intervals of 4 mm on a nozzle effective surface having a width of 64 cm and a length of 3.5 cm, Single-hole discharge rate is 2.2 g / min, cooling water is placed 50 cm below the nozzle surface, and a pair of take-up conveyors are partially exposed on the water surface at intervals of 3 cm in parallel with a 70 cm wide stainless steel endless net. In this way, it is drawn into the cooling water at a speed of 2.6 m / min while sandwiching both surfaces while fusing the contact portion, and then solidified by pulling into the cooling water at 100 ° C. for 15 minutes in a hot air dryer at 100 ° C. After the treatment, it was cut into a predetermined size to obtain a network structure. Table 2 shows the characteristics of the obtained network structure.
- the obtained resin composition was melted at a temperature of 230 ° C. from a nozzle in which round hollow orifices having a hole diameter of 3.0 mm were arranged at an interval of 6 mm on a nozzle effective surface having a width of 66 cm and a length of 5 cm, and single-hole ejection was performed. Discharge at a rate of 2.4 g / min, dispose cooling water below the nozzle surface 37 cm, and arrange a 70 cm wide stainless steel endless net in parallel at intervals of 4 cm so that a pair of take-up conveyors partially emerge on the water surface.
- Example 4 100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 0.25 kg of a hindered phenol antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 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 the resin composition were obtained.
- the obtained resin composition was melted at a temperature of 230 ° C. from a nozzle in which round hollow orifices having a hole diameter of 3.0 mm were arranged at an interval of 6 mm on a nozzle effective surface having a width of 66 cm and a length of 5 cm, and single-hole ejection was performed. Discharge at a rate of 2.4 g / min, dispose cooling water below the nozzle surface 32 cm, and arrange a 70 cm wide stainless steel endless net in parallel at intervals of 4 cm so that a pair of take-up conveyors partially exits the water surface.
- Example 5 100 kg of the polyester-based thermoplastic elastomer (A-3) obtained in Synthesis Example 3, 0.25 kg of a hindered phenol-based antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 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 200 ° C and a screw rotation speed of 130 rpm, and extruded into a water bath in a strand shape. After cooling, pellets of the resin composition were obtained.
- ADEKA STAB AO330 a hindered phenol-based antioxidant
- ADEKA STAB PEP36 0.25 kg of phosphorus-based antioxidant
- the obtained resin composition was melted at a temperature of 220 ° C. from a nozzle in which circular hollow orifices having a hole diameter of 3.0 mm were arranged at an interval of 6 mm on a nozzle effective surface having a width of 66 cm and a length of 5 cm.
- Discharge at a rate of 2.4 g / min dispose cooling water below the nozzle surface 37 cm, and place a pair of take-up conveyors partially above the water surface at 4.5 cm intervals in parallel with a 70 cm wide stainless steel endless net
- the material is drawn on the surface, and the contact part is fused, while both sides are sandwiched, while being drawn into the cooling water at a speed of 1.8 m / min and solidified, and then pseudo-crystallizing in a hot air dryer at 100 ° C. for 15 minutes Then, it was cut into a predetermined size to obtain a network structure.
- Table 2 shows the characteristics of the obtained network structure.
- Example 6 From a nozzle in which 100 kg of low density polyethylene (“Nipolon Z 1P55A” manufactured by Tosoh Corporation) is arranged on a nozzle effective surface having a width of 66 cm and a length of 5 cm and circular hollow orifices having a hole diameter of 3.0 mm are arranged at intervals of 6 mm. And a single hole discharge rate of 2.0 g / min, cooling water is arranged under the nozzle surface 37 cm, and a pair of pulling stainless steel endless nets with a width of 70 cm in parallel at intervals of 4.5 cm. Taking up the take-out conveyor so that it comes out partly on the surface of the water, pulling it into the cooling water at a speed of 1.7 m / min. After pseudo-crystallization treatment in a dryer for 15 minutes, the product was 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), 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 the resin composition were obtained.
- the obtained resin composition was melted at a temperature of 245 ° C. from a nozzle in which round hollow orifices having a hole diameter of 5.0 mm were arranged at an interval of 8 mm on a nozzle effective surface having a width of 64 cm and a length of 4.8 cm.
- the hole discharge rate is 3.6 g / min
- cooling water is placed 35 cm below the nozzle surface, and a pair of take-up conveyors are partially exposed on the water surface at intervals of 4 cm in parallel with a 70 cm wide stainless steel endless net.
- the material is drawn on the surface, and the contact part is fused, while both sides are sandwiched, it is drawn into cooling water at a rate of 2.2 m / min and solidified, and then pseudo-crystallized in a hot air dryer at 100 ° C. for 15 minutes. Then, it was 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 and 0.25 kg of a hindered phenol antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 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 the resin composition were obtained.
- the obtained resin composition was melted at a temperature of 235 ° C. from a nozzle in which round solid orifices having a hole diameter of 1.0 mm were arranged at intervals of 6 mm on a nozzle effective surface having a width of 66 cm and a length of 3.5 cm, Single-hole discharge rate is 1.6 g / min, cooling water is arranged 30 cm below the nozzle surface, and a pair of take-up conveyors are partially exposed on the water surface at intervals of 3 cm in parallel with a 70 cm wide stainless steel endless net.
- ⁇ Comparative Example 3 100 kg of the polyester-based thermoplastic elastomer (A-2) obtained in Synthesis Example 2 and 0.25 kg of a hindered phenol antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 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 the resin composition were obtained.
- the obtained resin composition was melted at a temperature of 240 ° C. from a nozzle in which round hollow orifices having a hole diameter of 5.0 mm were arranged at intervals of 8 mm on a nozzle effective surface having a width of 64 cm and a length of 4.8 cm.
- Discharge at a hole discharge rate of 3.6 g / min arrange cooling water below the nozzle face 38 cm, and partially pull out a pair of take-up conveyors on the water surface at intervals of 4 cm in parallel with a 70 cm wide stainless steel endless net
- the material is drawn on the surface, and the contact part is fused, while both sides are sandwiched, while being drawn into the cooling water at a speed of 2.0 m / min and solidified, and then subjected to a pseudo crystallization treatment in a hot air dryer at 100 ° C. for 15 minutes. Then, it was cut into a predetermined size to obtain a network structure.
- Table 2 shows the characteristics of the obtained network structure.
- the obtained resin composition was melted at a temperature of 240 ° C. from a nozzle in which round hollow orifices having a hole diameter of 3.0 mm were arranged at intervals of 6 mm on a nozzle effective surface having a width of 64 cm and a length of 4.8 cm.
- the hole discharge rate is 1.6 g / min
- cooling water is placed 25 cm below the nozzle surface, and a pair of take-up conveyors are partially exposed on the water surface at intervals of 4 cm in parallel with a 70 cm wide stainless steel endless net.
- the material is taken up on the surface, and the contact part is fused, while both sides are sandwiched, it is drawn into cooling water at a speed of 1.4 m / min and solidified, and then pseudo-crystallization treatment is performed in a hot air dryer at 100 ° C. for 15 minutes. Then, it was cut into a predetermined size to obtain a network structure.
- Table 2 shows the characteristics of the obtained network structure.
- ⁇ Comparative Example 5 100 kg of the polyester-based thermoplastic elastomer (A-3) obtained in Synthesis Example 3, 0.25 kg of a hindered phenol-based antioxidant (“ADEKA STAB AO330” manufactured by ADEKA), 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 200 ° C and a screw rotation speed of 130 rpm, and extruded into a water bath in a strand shape. After cooling, pellets of the resin composition were obtained.
- the obtained resin composition was melted at a temperature of 230 ° C. from a nozzle in which round hollow orifices having a hole diameter of 5.0 mm were arranged at intervals of 8 mm on a nozzle effective surface having a width of 64 cm and a length of 4.8 cm.
- Discharge at a hole discharge rate of 3.6 g / min arrange cooling water below the nozzle face 38 cm, and partially pull out a pair of take-up conveyors on the water surface at intervals of 4 cm in parallel with a 70 cm wide stainless steel endless net
- the material is drawn on the surface, and the contact part is fused, while both sides are sandwiched, while being drawn into the cooling water at a speed of 2.0 m / min and solidified, and then subjected to a pseudo crystallization treatment in a hot air dryer at 100 ° C. for 15 minutes. Then, it was 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 that exhibits excellent quietness while maintaining cushioning properties, and can be used for vehicle seats, mattresses, and the like by taking advantage of the characteristics.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonwoven Fabrics (AREA)
- Laminated Bodies (AREA)
Abstract
Description
(項1)
熱可塑性樹脂のランダムル-プ接合構造体からなる網状構造体であって、(a)該ランダムル-プ接合構造体の見掛け密度が0.005~0.200g/cm3であり、(b)該ランダムル-プ接合構造体の単位重さあたりの接合点数が500~1200個/gであることを特徴とする網状構造体。
(項2)
該ランダムル-プ接合構造体の単位重さあたりの接合点数が550~1150個/gである、項1に記載の網状構造体。
(項3)
該ランダムル-プ接合構造体の単位重さあたりの接合点数が600~1100個/gである、項2に記載の網状構造体。
(項4)
該熱可塑性樹脂が、軟質ポリオレフィン、ポリスチレン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマー、及びポリアミド系熱可塑性エラストマーからなる群より少なくとも一つ選ばれる熱可塑性樹脂である、項1~3のいずれかに記載の網状構造体。
(項5)
該熱可塑性樹脂が軟質ポリオレフィン及びポリエステル系熱可塑性エラストマーからなる群より少なくとも一つ選ばれる熱可塑性樹脂である、項4に記載の網状構造体。
(項6)
該熱可塑性樹脂がポリエステル系熱可塑性エラストマーである、項5に記載の網状構造体。
(項7)
該連続線条体の繊度が200~10000デシテックスである、項1~6のいずれかに記載の網状構造体。
(項8)
該連続線条体の繊度が200~5000デシテックスである、項7に記載の網状構造体。
(項9)
該連続線条体の繊度が200~3000デシテックスである、項8に記載の網状構造体。
(項10)
該ランダムループ接合構造体の25%圧縮時硬さが5kg/Φ200mm以上、50kg/Φ200mm以下である、項1~9のいずれかに記載の網状構造体。
(項11)
該連続線条体が中空断面であることを特徴とする、項1~10のいずれかに記載の網状構造体。
(項12)
該連続線条体が中空断面であり、かつ該中空断面の中空率が10~50%である、項11に記載の網状構造体。
(項13)
該連続線条体が中空断面であり、かつ該中空断面の中空率が20~40%である、項12に記載の網状構造体。
(項14)
該連続線条体が異形断面であることを特徴とする、項1~13のいずれかに記載の網状構造体。
であり、更に好ましい範囲は0.020g/cm3 ~0.100g/cm3である。
まず、一般的な溶融押出機を用いて熱可塑性エラストマーを融点より10~120℃高い温度に加熱して溶融状態とし、複数のオリフィスを持つノズルより下向きに吐出させ、自然降下させループを形成させる。このときノズル面と樹脂を固化させる冷却媒体上に設置した引取りコンベアとの距離、樹脂の溶融粘度、オリフィスの孔径と吐出量などによりループ径と線条体の繊度および接合点数がきまる。冷却媒体上に設置した間隔が調整可能な一対の引取りコンベアで溶融状態の吐出線条体を挟み込み停留させることでループが発生し、オリフィスの孔間隔を発生ループが接触できる孔間隔にしておくことで発生したループを互いに接触させ、接触することでループがランダムな三次元形態を形成しつつ接触部は融着する。尚、オリフィスの孔間隔は接合点数に影響を与える。次いでランダムな三次元形態を形成しつつ接触部が融着した連続線条体を連続して冷却媒体中に引込み固化させ網状構造体を形成する。
なお、実施例中の評価は以下の方法で行った。
(1)融点(Tm)
島津製作所TA50、DSC50型示差走査型熱量計を使用し、10gの試料を昇温速度20℃/分で20℃から250℃まで測定した吸発熱曲線から吸熱ピーク(融解ピーク)温度を求めた。
(2)曲げ弾性率
射出成形機によって長さ125mm×幅12mm×厚み6mmの試験片を作成し、ASTM D790規格により測定した。
(1)見掛け密度
試料を長手方向15cm×幅方向15cmの大きさで試料表層面2面を含み、試料耳部を含まないように直方体形状に切断し、直方体の4角の高さを測定した後、体積(cm3)を求め、試料の重さ(g)を体積で徐することによって見掛け密度(g/cm3)を算出した。尚、見掛け密度はn=4の平均値とした。
(2)単位重さあたりの接合点数
まず最初に、試料を長手方向5cm×幅方向5cmの大きさで、試料表層面2面を含み、試料耳部を含まないように直方体形状に切断して個片を作成した。次に、この個片の4角の高さを測定した後、体積(単位:cm3)を求め、試料の重さ(単位:g)を体積で徐することによって見掛け密度を(単位:g/cm3)を算出した。次に、この個片の接合点の数を数え、この数を個片の体積で除することによって単位体積あたりの接合点数(単位:個/cm3)を算出し、単位体積あたりの接合点数を見掛け密度で除することによって単位重さあたりの接合点数(単位:個/g)を算出した。尚、接合点は2本の線条間の融着部分とし、2本の線条を引張って融着部分を剥離する方法で接合点数を計測した。また、単位重さあたりの接合点数はn=2の平均値とした。また、試料の長手方向あるいは幅方向に見掛け密度にして0.005g/cm3以上の帯状の疎密差のある試料の場合は、密の部分と疎の部分の境界線が個片の長手方向あるいは幅方向の中間線となるように試料を切断し、同様の方法で単位重さあたりの接合点数を計測した(n=2)。
(3)線条の繊度
まず最初に、試料を長手方向30cm×幅方向30cmの大きさで試料表層面2面を含み、試料耳部を含まないように直方体形状に切断し、均等な4マスに分割して各マス5か所、計20か所で採取した長さ1cmの線条体の40℃での比重を密度勾配管を用いて測定した。次に、上記20か所で採取した線条体の樹脂部分の断面積を顕微鏡で拡大した写真より求め、それより、線条体の長さ10000m分の体積を求めた後、得られた比重と体積を乗じた値を繊度(線条体10000m分のグラム重量:デシテックスdtex)とした。(n=20の平均値)。
(4)中空率
まず最初に、試料を長手方向30cm×幅方向30cmの大きさで試料表層面2面を含み、試料耳部を含まないように直方体形状に切断し、均等な4マスに分割して各マス5か所、計20か所で採取した長さ1cmの線条体を採取し、液体窒素で冷却した後に割断し、その断面を電子顕微鏡で倍率50倍にて観察し、得られた画像をCADシステムにて解析して樹脂部分の断面積(A)と中空部分の断面積(B)を測定し、{B/(A+B)}×100の式により中空率を算出した。(n=20の平均値)。
(5)25%圧縮硬さ
試料を長手方向30cm×幅方向30cmの大きさで試料表層面2面を含み、試料耳部を含まないように直方体形状に切断し、オリエンテック社製テンシロンにてφ200mm圧縮板にて75%まで圧縮して得た応力-歪み曲線の25%圧縮時の応力で示した。(n=3の平均値)
(6)床つき感
長手方向50cm×幅方向50cmの大きさで試料表層面2面を含むように直方体形状に切断した試料に体重40kg~100kgの範囲にあるパネラー30名(20歳~39歳の男性;5名、20歳~39歳の女性:5名、40歳~59歳の男性:5名、40歳~59歳の女性:5名、60歳~80歳の男性:5名、60歳~80歳の女性:5名)を座らせ、座ったときの「どすん」と床に当たった感じの程度を感覚的に定性評価した。感じない;◎、弱く感じる;○、中程度に感じる;△、強く感じる;×
(7)消音性
長手方向50cm×幅方向50cmの大きさで試料表層面2面を含むように直方体形状に切断した試料に体重40kg~100kgの範囲にあるパネラー30名(20歳~39歳の男性;5名、20歳~39歳の女性:5名、40歳~59歳の男性:5名、40歳~59歳の女性:5名、60歳~80歳の男性:5名、60歳~80歳の女性:5名)を座らせ、網状構造体から発生する音を感覚的に定性評価した。聞こえない;◎、弱く聞こえる;○、中程度に聞こえる;△、強く聞こえる;×
ジメチルテレフタレート(DMT)と1,4-ブタンジオール(1,4-BD)とポリテトラメチレングリコール(PTMG:平均分子量1000)を少量の触媒と仕込み、常法によりエステル交換後、昇温減圧しつつ重縮合せしめ、DMT/1,4-BD/PTMG=100/88/12mol%のポリエステルエーテルブロック共重合エラストマーを生成させ、次いで抗酸化剤1%を添加混合練込み後ペレット化し、50℃48時間真空乾燥してポリエステル系熱可塑性エラストマー原料(A-1)を得た。その特性を表1に示す。
ジメチルテレフタレート(DMT)と1,4-ブタンジオール(1,4-BD)とポリテトラメチレングリコール(PTMG:平均分子量1000)を少量の触媒と仕込み、常法によりエステル交換後、昇温減圧しつつ重縮合せしめ、DMT/1,4-BD/PTMG=100/84/16mol%のポリエステルエーテルブロック共重合エラストマーを生成させ、次いで抗酸化剤1%を添加混合練込み後ペレット化し、50℃48時間真空乾燥してポリエステル系熱可塑性エラストマー原料(A-2)を得た。その特性を表1に示す。
ジメチルテレフタレート(DMT)と1,4-ブタンジオール(1,4-BD)とポリテトラメチレングリコール(PTMG:平均分子量1000)を少量の触媒と仕込み、常法によりエステル交換後、昇温減圧しつつ重縮合せしめ、DMT/1,4-BD/PTMG=100/72/28mol%のポリエステルエーテルブロック共重合エラストマーを生成させ、次いで抗酸化剤1%を添加混合練込み後ペレット化し、50℃48時間真空乾燥してポリエステル系熱可塑性エラストマー原料(A-3)を得た。その特性を表1に示す。
100kgの合成例1で得られたポリエステル系熱可塑性エラストマー(A-1)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅66cm、長さ5cmのノズル有効面に孔径3.0mmの丸型中空形状オリフィスを6mmの間隔で配列したノズルより、240℃の温度で溶融して、単孔吐出量2.4g/分で吐出させ、35cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分2.2mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例2で得られたポリエステル系熱可塑性エラストマー(A-2)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅64cm、長さ3.5cmのノズル有効面に孔径1.0mmの丸型中実形状オリフィスを4mmの間隔で配列したノズルより、245℃の温度で溶融して、単孔吐出量を2.2g/分で吐出させ、ノズル面50cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に3cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分2.6mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例2で得られたポリエステル系熱可塑性エラストマー(A-2)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅66cm、長さ5cmのノズル有効面に孔径3.0mmの丸型中空形状オリフィスを6mmの間隔で配列したノズルより、230℃の温度で溶融して、単孔吐出量を2.4g/分で吐出させ、ノズル面37cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.9mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
<実施例4>
100kgの合成例2で得られたポリエステル系熱可塑性エラストマー(A-2)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅66cm、長さ5cmのノズル有効面に孔径3.0mmの丸型中空形状オリフィスを6mmの間隔で配列したノズルより、230℃の温度で溶融して、単孔吐出量を2.4g/分で吐出させ、ノズル面32cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.8mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
<実施例5>
100kgの合成例3で得られたポリエステル系熱可塑性エラストマー(A-3)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度200℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅66cm、長さ5cmのノズル有効面に孔径3.0mmの丸型中空形状オリフィスを6mmの間隔で配列したノズルより、220℃の温度で溶融して、単孔吐出量を2.4g/分で吐出させ、ノズル面37cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4.5cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.8mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
<実施例6>
100kgの低密度ポリエチレン(東ソー株式会社製「ニポロンZ 1P55A」)を幅66cm、長さ5cmのノズル有効面に孔径3.0mmの丸型中空形状オリフィスを6mmの間隔で配列したノズルより、200℃の温度で溶融して、単孔吐出量を2.0g/分で吐出させ、ノズル面37cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4.5cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.7mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例1で得られたポリエステル系熱可塑性エラストマー(A-1)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅64cm、長さ4.8cmのノズル有効面に孔径5.0mmの丸型中空形状オリフィスを8mmの間隔で配列したノズルより、245℃の温度で溶融して、単孔吐出量を3.6g/分で吐出させ、ノズル面35cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分2.2mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例2で得られたポリエステル系熱可塑性エラストマー(A-2)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅66cm、長さ3.5cmのノズル有効面に孔径1.0mmの丸型中実形状オリフィスを6mmの間隔で配列したノズルより、235℃の温度で溶融して、単孔吐出量を1.6g/分で吐出させ、ノズル面30cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に3cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.0mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例2で得られたポリエステル系熱可塑性エラストマー(A-2)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅64cm、長さ4.8cmのノズル有効面に孔径5.0mmの丸型中空形状オリフィスを8mmの間隔で配列したノズルより、240℃の温度で溶融して、単孔吐出量を3.6g/分で吐出させ、ノズル面38cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分2.0mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例2で得られたポリエステル系熱可塑性エラストマー(A-2)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度220℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅64cm、長さ4.8cmのノズル有効面に孔径3.0mmの丸型中空形状オリフィスを6mmの間隔で配列したノズルより、240℃の温度で溶融して、単孔吐出量を1.6g/分で吐出させ、ノズル面25cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.4mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの合成例3で得られたポリエステル系熱可塑性エラストマー(A-3)および0.25kgのヒンダードフェノール系酸化防止剤(ADEKA社製「アデカスタブAO330」)、0.25kgの燐系酸化防止剤(ADEKA社製「アデカスタブPEP36」)をタンブラーにて5分間混合した後、スクリュー径φ57mmの二軸押出機でシリンダー温度200℃、スクリュー回転数130rpmにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物を幅64cm、長さ4.8cmのノズル有効面に孔径5.0mmの丸型中空形状オリフィスを8mmの間隔で配列したノズルより、230℃の温度で溶融して、単孔吐出量を3.6g/分で吐出させ、ノズル面38cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分2.0mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
100kgの低密度ポリエチレン(東ソー株式会社製「ニポロンZ 1P55A」)を幅64cm、長さ4.8cmのノズル有効面に孔径5.0mmの丸型中空形状オリフィスを8mmの間隔で配列したノズルより、200℃の温度で溶融して、単孔吐出量を3.0g/分で吐出させ、ノズル面35cm下に冷却水を配し、幅70cmのステンレス製エンドレスネットを平行に4.0cm間隔で一対の引取りコンベアを水面上に一部出るように配した上に引取り、接触部分を融着させつつ、両面を挟み込みつつ毎分1.5mの速度で冷却水中へ引込み固化させ、次いで100℃の熱風乾燥機中で15分間疑似結晶化処理した後、所定の大きさに切断して網状構造体を得た。得られた網状構造体の特性を表2に示す。
Claims (14)
- 熱可塑性樹脂のランダムル-プ接合構造体からなる網状構造体であって、(a)該ランダムル-プ接合構造体の見掛け密度が0.005~0.200g/cm3であり、(b)該ランダムル-プ接合構造体の単位重さあたりの接合点数が500~1200個/gであることを特徴とする網状構造体。
- 該ランダムル-プ接合構造体の単位重さあたりの接合点数が550~1150個/gである、請求項1に記載の網状構造体。
- 該ランダムル-プ接合構造体の単位重さあたりの接合点数が600~1100個/gである、請求項2に記載の網状構造体。
- 該熱可塑性樹脂が、軟質ポリオレフィン、ポリスチレン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマー、及びポリアミド系熱可塑性エラストマーからなる群より少なくとも一つ選ばれる熱可塑性樹脂である、請求項1~3のいずれか一項に記載の網状構造体。
- 該熱可塑性樹脂が軟質ポリオレフィン及びポリエステル系熱可塑性エラストマーからなる群より少なくとも一つ選ばれる熱可塑性樹脂である、請求項4に記載の網状構造体。
- 該熱可塑性樹脂がポリエステル系熱可塑性エラストマーである、請求項5に記載の網状構造体。
- 該連続線条体の繊度が200~10000デシテックスである、請求項1~6のいずれか一項に記載の網状構造体。
-
該連続線条体の繊度が200~5000デシテックスである、請求項7に記載の網状構造体。 - 該連続線条体の繊度が200~3000デシテックスである、請求項8に記載の網状構造体。
- 該ランダムループ接合構造体の25%圧縮時硬さが5kg/Φ200mm以上、50kg/Φ200mm以下である、請求項1~9のいずれか一項に記載の網状構造体。
- 該連続線条体が中空断面であることを特徴とする、請求項1~10のいずれか一項に記載の網状構造体。
- 該連続線条体が中空断面であり、かつ該中空断面の中空率が10~50%である、請求項11に記載の網状構造体。
- 該連続線条体が中空断面であり、かつ該中空断面の中空率が20~40%である、請求項12に記載の網状構造体。
- 該連続線条体が異形断面であることを特徴とする、請求項1~13のいずれか一項に記載の網状構造体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013540131A JP5418741B1 (ja) | 2012-05-07 | 2013-05-07 | 静粛性と硬さに優れた弾性網状構造体 |
US14/399,244 US11168421B2 (en) | 2012-05-07 | 2013-05-07 | Elastic network structure with excellent quietness and hardness |
EP13788112.4A EP2848721B1 (en) | 2012-05-07 | 2013-05-07 | Elastic network structure with excellent quietness and hardness |
CN201380024126.6A CN104285003B (zh) | 2012-05-07 | 2013-05-07 | 安静性和硬度优异的弹性网状结构体 |
KR1020147030986A KR101961514B1 (ko) | 2012-05-07 | 2013-05-07 | 정숙성과 경도가 우수한 탄성 망상 구조체 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-105759 | 2012-05-07 | ||
JP2012105759 | 2012-05-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013168699A1 true WO2013168699A1 (ja) | 2013-11-14 |
Family
ID=49550734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/062831 WO2013168699A1 (ja) | 2012-05-07 | 2013-05-07 | 静粛性と硬さに優れた弾性網状構造体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11168421B2 (ja) |
EP (1) | EP2848721B1 (ja) |
JP (1) | JP5418741B1 (ja) |
KR (1) | KR101961514B1 (ja) |
CN (1) | CN104285003B (ja) |
TW (1) | TWI597232B (ja) |
WO (1) | WO2013168699A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5459436B1 (ja) * | 2013-04-26 | 2014-04-02 | 東洋紡株式会社 | 熱寸法安定性に優れた網状構造体 |
JP2016070194A (ja) * | 2014-09-30 | 2016-05-09 | 帝人株式会社 | 燃料電池の排気系統用吸音材および燃料電池の排気音低減方法および燃料電池の消音器 |
JP2016141915A (ja) * | 2015-02-04 | 2016-08-08 | 東洋紡株式会社 | 低反発性に優れた網状構造体 |
WO2023190527A1 (ja) * | 2022-03-31 | 2023-10-05 | 東洋紡エムシー株式会社 | 網状構造体およびその製造方法 |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI597232B (zh) | 2012-05-07 | 2017-09-01 | 東洋紡股份有限公司 | 消音性與硬度優異之彈性網狀構造體 |
JP6011204B2 (ja) * | 2012-09-26 | 2016-10-19 | 東洋紡株式会社 | 寝具 |
JP5339107B1 (ja) * | 2013-02-27 | 2013-11-13 | 東洋紡株式会社 | 圧縮耐久性に優れた網状構造体 |
JP5569641B1 (ja) | 2013-10-28 | 2014-08-13 | 東洋紡株式会社 | 静粛性と軽量性に優れた弾性網状構造体 |
CN107532356B (zh) * | 2015-04-28 | 2020-07-14 | 东洋纺株式会社 | 网状结构体 |
US10766761B2 (en) * | 2016-01-13 | 2020-09-08 | Airweave Inc. | Three-dimensional filaments-linked structure manufacturing apparatus, manufacturing method of three-dimensional filaments-linked structure, and mattress core material |
CN106120161B (zh) * | 2016-06-23 | 2019-06-07 | 江阴和创弹性体新材料科技有限公司 | 一种轻量化高弹性能的立体网状结构 |
KR102288664B1 (ko) * | 2016-07-13 | 2021-08-11 | 도요보 가부시키가이샤 | 망상 구조체 |
US11304536B2 (en) * | 2016-07-28 | 2022-04-19 | Airweave Inc. | Bedding and bedding cover sheet |
US10751164B2 (en) * | 2017-11-28 | 2020-08-25 | Biosense Webster (Israel) Ltd. | Inelastic noiseless air bag in a breast implant |
EP3802659A1 (en) * | 2018-05-29 | 2021-04-14 | Dow Global Technologies LLC | Composite structure |
NL2021753B1 (en) | 2018-10-03 | 2020-05-11 | Ubed B V | Body support assembly |
NL2021752B1 (en) | 2018-10-03 | 2020-05-11 | Ubed B V | Body support assembly |
CN113438913A (zh) * | 2018-10-03 | 2021-09-24 | 优百得私人有限责任公司 | 身体支撑组件 |
EP3889332B8 (en) * | 2018-11-29 | 2023-06-21 | TOYOBO MC Corporation | Net-shaped structure body |
EP4033941A1 (en) | 2019-09-27 | 2022-08-03 | Ubed B.V. | Body support assembly |
NL2023913B1 (en) | 2019-09-27 | 2021-05-27 | Ubed B V | Body support assembly |
CN111040464A (zh) * | 2019-12-31 | 2020-04-21 | 安吉万众化纤科技有限公司 | 一种高回弹环保垫、配方及使用 |
CN111041605A (zh) * | 2019-12-31 | 2020-04-21 | 安吉万众化纤科技有限公司 | 一种高回弹环保垫制造方法 |
CN111719247B (zh) * | 2020-07-17 | 2021-05-25 | 无锡科逸新材料有限公司 | 耐疲劳的层状弹性体 |
US20220314854A1 (en) * | 2021-03-31 | 2022-10-06 | Lear Corporation | Seat support |
NL2029887B1 (en) | 2021-11-24 | 2022-12-19 | Ubed B V | Modular body support assembly |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0768061A (ja) | 1993-02-26 | 1995-03-14 | Toyobo Co Ltd | クッション用網状構造体及び製法 |
JPH0813310A (ja) * | 1994-07-05 | 1996-01-16 | Toyobo Co Ltd | ポリエステル系ワディング材とその製法 |
JP2000073271A (ja) * | 1998-08-24 | 2000-03-07 | Toyobo Co Ltd | 抗菌性網状構造体及びその製法 |
JP2000328422A (ja) * | 1999-05-26 | 2000-11-28 | Toyobo Co Ltd | 抗菌防黴性ポリ乳酸構造体及びその製造方法 |
JP2010043376A (ja) | 2008-08-13 | 2010-02-25 | Toyobo Co Ltd | 静粛性に優れたポリエステル系弾性網状構造体およびその製造方法 |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1778026C3 (de) | 1968-03-21 | 1981-06-11 | Enka Ag, 5600 Wuppertal | Polstermaterial aus einer Vielzahl von in Schlaufen liegenden, sich überkreuzenden synthetischen Endlosfäden |
DE2431871C3 (de) | 1974-07-03 | 1978-10-12 | Akzo Gmbh, 5600 Wuppertal | Verfahren und Düsenplatte zur Herstellung einer elastischen Mattenbahn |
JPS5418741B2 (ja) | 1973-03-14 | 1979-07-10 | ||
US3936337A (en) | 1973-12-18 | 1976-02-03 | Akzona Incorporated | Apparatus and process for the manufacture of structural mats |
JPS5531222A (en) | 1978-08-23 | 1980-03-05 | Babcock Hitachi Kk | Method for incinerating oil residue |
JPH01207462A (ja) | 1988-02-09 | 1989-08-21 | Risuron:Kk | フィラメントループ集合体からなるマット及びその製造方法及び装置 |
KR0130813B1 (ko) * | 1993-02-26 | 1998-04-03 | 시바타 미노루 | 쿠션용 망상 구조체 및 제법 |
JP3518615B2 (ja) | 1993-08-24 | 2004-04-12 | 東洋紡績株式会社 | 立体網状構造体 |
JP3344511B2 (ja) | 1993-12-21 | 2002-11-11 | 東洋紡績株式会社 | 網状構造体及びその製造法 |
JPH08196755A (ja) * | 1995-01-30 | 1996-08-06 | Teijin Ltd | クッション構造物 |
EP1053127B1 (en) * | 1998-02-11 | 2003-08-06 | CASCADE ENGINEERING, Inc. | Sound absorber mat with integrally molded retainer |
JP3572406B2 (ja) * | 1999-03-05 | 2004-10-06 | 日産自動車株式会社 | 繊維集合体及びその製造方法 |
JP2001061605A (ja) * | 1999-08-27 | 2001-03-13 | Toyobo Co Ltd | 車両用座席 |
JP4053264B2 (ja) | 2000-08-30 | 2008-02-27 | 三菱化学株式会社 | 積層成形体 |
WO2005018386A1 (ja) * | 2003-08-26 | 2005-03-03 | Ein Co., Ltd. Technical Center | スプリング構造樹脂成形品から成るクッション材及びその製造方法並びに前記製造方法に用いる型 |
WO2006068120A1 (ja) * | 2004-12-21 | 2006-06-29 | Toyo Boseki Kabushiki Kaisha | 弾性網状構造体 |
JP2007175482A (ja) * | 2005-11-30 | 2007-07-12 | Honda Motor Co Ltd | 車両用シート及び船艇用シート |
JP2008013310A (ja) * | 2006-07-05 | 2008-01-24 | Sharp Corp | 画像形成装置 |
EP2184391B1 (en) * | 2007-08-31 | 2016-10-12 | Kuraray Co., Ltd. | Buffer substrate and use thereof |
JP5180020B2 (ja) * | 2008-09-30 | 2013-04-10 | 株式会社クラレ | 嵩高繊維構造体及びクッション材 |
JP2013090658A (ja) | 2011-10-24 | 2013-05-16 | Toyobo Co Ltd | クッション |
JP2013091862A (ja) | 2011-10-24 | 2013-05-16 | Toyobo Co Ltd | 網状構造体 |
TWI597232B (zh) | 2012-05-07 | 2017-09-01 | 東洋紡股份有限公司 | 消音性與硬度優異之彈性網狀構造體 |
CN105612279A (zh) | 2013-10-01 | 2016-05-25 | 东洋纺株式会社 | 压缩耐久性优异的网状结构体 |
JP5569641B1 (ja) | 2013-10-28 | 2014-08-13 | 東洋紡株式会社 | 静粛性と軽量性に優れた弾性網状構造体 |
TWI639549B (zh) | 2013-10-29 | 2018-11-01 | 東洋紡股份有限公司 | 壓縮耐久性優異之網狀構造物 |
-
2013
- 2013-05-03 TW TW102115858A patent/TWI597232B/zh active
- 2013-05-07 EP EP13788112.4A patent/EP2848721B1/en active Active
- 2013-05-07 US US14/399,244 patent/US11168421B2/en active Active
- 2013-05-07 WO PCT/JP2013/062831 patent/WO2013168699A1/ja active Application Filing
- 2013-05-07 CN CN201380024126.6A patent/CN104285003B/zh active Active
- 2013-05-07 KR KR1020147030986A patent/KR101961514B1/ko active IP Right Grant
- 2013-05-07 JP JP2013540131A patent/JP5418741B1/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0768061A (ja) | 1993-02-26 | 1995-03-14 | Toyobo Co Ltd | クッション用網状構造体及び製法 |
JPH0813310A (ja) * | 1994-07-05 | 1996-01-16 | Toyobo Co Ltd | ポリエステル系ワディング材とその製法 |
JP2000073271A (ja) * | 1998-08-24 | 2000-03-07 | Toyobo Co Ltd | 抗菌性網状構造体及びその製法 |
JP2000328422A (ja) * | 1999-05-26 | 2000-11-28 | Toyobo Co Ltd | 抗菌防黴性ポリ乳酸構造体及びその製造方法 |
JP2010043376A (ja) | 2008-08-13 | 2010-02-25 | Toyobo Co Ltd | 静粛性に優れたポリエステル系弾性網状構造体およびその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2848721A4 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5459436B1 (ja) * | 2013-04-26 | 2014-04-02 | 東洋紡株式会社 | 熱寸法安定性に優れた網状構造体 |
WO2014175247A1 (ja) * | 2013-04-26 | 2014-10-30 | 東洋紡株式会社 | 熱寸法安定性に優れた網状構造体 |
JP2016070194A (ja) * | 2014-09-30 | 2016-05-09 | 帝人株式会社 | 燃料電池の排気系統用吸音材および燃料電池の排気音低減方法および燃料電池の消音器 |
JP2016141915A (ja) * | 2015-02-04 | 2016-08-08 | 東洋紡株式会社 | 低反発性に優れた網状構造体 |
WO2023190527A1 (ja) * | 2022-03-31 | 2023-10-05 | 東洋紡エムシー株式会社 | 網状構造体およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2848721B1 (en) | 2018-01-03 |
CN104285003A (zh) | 2015-01-14 |
EP2848721A4 (en) | 2016-01-13 |
TW201350423A (zh) | 2013-12-16 |
US20150087196A1 (en) | 2015-03-26 |
KR101961514B1 (ko) | 2019-03-22 |
JPWO2013168699A1 (ja) | 2016-01-07 |
EP2848721A1 (en) | 2015-03-18 |
US11168421B2 (en) | 2021-11-09 |
KR20150003264A (ko) | 2015-01-08 |
JP5418741B1 (ja) | 2014-02-19 |
TWI597232B (zh) | 2017-09-01 |
CN104285003B (zh) | 2017-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5418741B1 (ja) | 静粛性と硬さに優れた弾性網状構造体 | |
JP5569641B1 (ja) | 静粛性と軽量性に優れた弾性網状構造体 | |
JP5966471B2 (ja) | 静粛性と硬さに優れた弾性網状構造体 | |
JP5978674B2 (ja) | 振動吸収性の高い弾性網状構造体 | |
JP5966472B2 (ja) | 振動吸収性の高い弾性網状構造体 | |
JP2013091862A (ja) | 網状構造体 | |
JP6011204B2 (ja) | 寝具 | |
WO2014192790A1 (ja) | 軽量性と硬さに優れた弾性網状構造体 | |
JP6115015B2 (ja) | 静粛性と硬さに優れた弾性網状構造体 | |
JP3430444B2 (ja) | クッション用網状構造体、その製造法およびクッション製品 | |
JP2014064767A (ja) | クッション | |
JPH07238456A (ja) | クッション用網状構造体、その製法およびクッション製品 | |
JP3346506B2 (ja) | 難燃性複合網状構造体と製法及びそれを用いた製品 | |
JP3698212B2 (ja) | 難燃性網状構造体と製法 | |
JPH07238462A (ja) | 不織布積層構造体と製法及びそれを用いた製品 | |
JPH07300762A (ja) | 不織布積層網状体と製法及びそれを用いた製品 | |
JPH07238461A (ja) | 積層構造体と製法及びそれを用いた製品 | |
JPH07300760A (ja) | 不織布積層網状体と製法及びそれを用いた製品 | |
JPH07252761A (ja) | 難燃性網状体と製法及びそれを用いた製品 | |
JPH07238460A (ja) | 積層弾性構造体と製法及びそれを用いた製品 | |
JPH07243163A (ja) | 不織布積層網状体と製法及びそれを用いた製品 | |
JPH07289756A (ja) | 不織布積層網状体と製法及びそれを用いた製品 | |
JPH07300761A (ja) | 不織布積層網状体と製法及びそれを用いた製品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013540131 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13788112 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147030986 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14399244 Country of ref document: US Ref document number: 2013788112 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |