JP3346506B2 - Flame-retardant composite network structure, manufacturing method and product using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant composite net structure having flame retardancy, generating little toxic gas during combustion, and having excellent cushioning properties, a method for producing the same, and a flame retardant composite net structure. Related to products using

[0002]

2. Description of the Related Art At present, urethane foam, non-elastic crimped fiber-filled cotton, and resin cotton and hard cotton to which non-elastic crimped fibers are bonded are used as cushioning materials for futons, furniture, beds, railways, automobiles, and the like. Have been.

[0003] However, foamed-crosslinked urethane has good durability as a cushioning material, but is inferior in moisture permeation and water permeability and has heat storage properties, so that it is easy to humid. In addition, the damage to the incinerator is large, and the cost for removing toxic gas is high.
For this reason, landfills have been increased, but there is a problem in that it is difficult to stabilize the ground, so that landfill locations are limited and costs increase. Further, although the processability is excellent, there is a problem of pollution of chemicals used during the production. In addition, since the fiber between the thermoplastic polyester cotton is not fixed,
When used, the form is collapsed, the fibers are moved, and the crimp is set, so that the bulkiness and the elastic force are reduced.

Japanese Patent Application Laid-Open Publication No. Sho 6 (1994) discloses a resin cotton in which polyester fibers are bonded with an adhesive, for example, a rubber using an adhesive as a rubber.
Nos. 0-11352, JP-A-61-141388 and JP-A-61-141392. Also,
JP-A-61-1377 discloses a method using a crosslinked urethane.
No. 32 publication. These cushioning materials are inferior in durability, are not thermoplastic, cannot be recycled because they are not a single composition, and have problems such as complicated workability and pollution of chemicals used during production. .

[0005] Polyester hard cotton, for example, JP-A-58-3
JP-A No. 1150, JP-A-2-154050, JP-A-3-220354, etc., are disclosed in Japanese Patent Application Laid-Open No. Sho 58-58, since the adhesive component of the heat-bonding fiber used is a brittle amorphous polymer. 136828, JP-A-3-
There is a problem in that the adhesive portion is brittle, and the adhesive portion is easily broken during use, and the durability and the like are deteriorated, for example, the form and elasticity are reduced. As an improved method, a method of performing confounding treatment is proposed in Japanese Patent Application Laid-Open No. 4-245965 or the like, but there is a problem that the brittleness of the bonded portion is not solved and the elasticity is greatly reduced. is there. Further, there is a problem that the bonded portion is not easily deformed and it is difficult to provide a soft cushioning property. For this reason, a heat-bonding fiber using a polyester elastomer which is soft and recovers even if deformed to some extent and uses an inelastic polyester as a core component is disclosed in Japanese Patent Application Laid-Open No. Hei 4-240219. Have been proposed in WO-91 / 19032, JP-A-5-156561, JP-A-5-163654 and the like. When the adhesive component used in the fiber structure is a soft segment of a polyester elastomer, the content of polyalkylene glycol is 30 to 5%.
0% by weight, 50-80 mol% of terephthalic acid in the acid component of the hard segment, and isophthalic acid as the other acid component composition to increase the amorphousness, and the melting point is 18
It has a low melt viscosity of 0 ° C or less and improves the formation of the heat-bonded part to form an amoeboid-shaped bonded part. However, since plastic deformation is easy and the core component is inelastic polyester, plasticity under heating is particularly high. There is a problem that the deformation becomes remarkable and the heat resistance and the compression resistance are reduced. In addition, this fiber is
The prior art is not improved because it is the same as the fiber described in JP-A-14-4.

A thermoplastic olefin network used for civil engineering is disclosed in Japanese Patent Application Laid-Open No. 47-44839. However, unlike a cushion material composed of fine fibers, the surface is uneven and the touch is poor. Since the material is an olefin, it has extremely poor heat resistance and cannot be used as a cushion material. Further, Japanese Patent Publication No. 3-17666 discloses a method in which discharge yarns having different finenesses are fused to each other to form a molding, but a net-like structure not suitable for a cushion material. Japanese Patent Publication No. 3-55583 discloses a method in which only a very small surface is thinned by a thinning device such as a rotating body before cooling. In this method, the surface cannot be flattened, and a thick and thin linear layer cannot be formed. Therefore, it does not become a cushion material with good sitting comfort. JP 1
JP207462 discloses a floor mat made of vinyl chloride, but has poor compression recovery at room temperature, and
Although it is a material that is difficult to burn, once it burns out, it has a problem of generating toxic gas at the time of burning, and is not preferable as a cushioning material because of its poor heat resistance.

[0007]

SUMMARY OF THE INVENTION In order to solve the above problems,
Flame-retardant composite reticulated structure with flame-retardant properties that generate less toxic gas during combustion, is recyclable, and has excellent shape retention and cushioning properties, and is suitable for non-steaming cushioning materials. An object is to provide a product using the composite network structure.

[0008]

Means for solving the above-mentioned problem, ie, the present invention is directed to a method for producing a thermoplastic resin having a fineness of 1%.
A flame-retardant polyester comprising 100 to 100,000 denier composite filaments, at least one of which is a thermoplastic elastic resin, and at least one of which is a copolymer of a phosphorus-containing ester-forming compound or contains a phosphorus-containing flame retardant; The composite structured continuous filaments are meandered and brought into contact with each other to form a three-dimensional network structure by fusing most of the contact portions, and have an apparent density of 0.005 g / cm ³ or more. Flame-retardant composite network structure of 20 g / cm ³ or less, distributed before each nozzle orifice so that thermoplastic elastic resin and flame-retardant polyester can be composited, at least 10 ° C. higher than the melting point of the high melting point component of the thermoplastic resin The nozzles are ejected downward at a melting temperature in a temperature range not higher than 125 ° C. higher than the melting point of the low melting point component and brought into contact with each other in a molten state to be fused. While forming a dimensional structures, a product using the method and the flame retardant network structure of the flame retardant composite network structure and forming a network structure allowed to cool in a cooling bath sandwiched between withdrawal device.

The thermoplastic elastic resin in the present invention includes polyester elastomers, polyamide elastomers obtained by block copolymerization of polyether glycol, polyester glycol, polycarbonate glycol or the like having a molecular weight of 300 to 5000 as a soft segment.
Polyurethane elastomers and the like can be mentioned. By using a thermoplastic elastic resin, regeneration becomes possible by re-melting, so that recycling becomes easy. For example, as the polyester-based elastomer, a thermoplastic polyester as a hard segment, a polyetherester block copolymer having a polyalkylenediol as a soft segment, or a polyester ester block copolymer having an aliphatic polyester as a soft segment is used. Can be illustrated. More specific examples of the polyester ether block copolymer include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene 2.6 dicarboxylic acid, naphthalene 2.7 dicarboxylic acid, and diphenyl 4.4 4 'dicarboxylic acid. Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid,
Aliphatic dicarboxylic acids such as dimer acid or at least one dicarboxylic acid selected from ester-forming derivatives thereof and the like, and 1,4-butanediol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, At least one diol component selected from aliphatic diols such as hexamethylene glycol, alicyclic diols such as 1.1 cyclohexane dimethanol, 1.4 cyclohexane dimethanol, and ester-forming derivatives thereof; A ternary polymer composed of at least one of polyalkylene diols having a molecular weight of about 300 to 5000, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide-propylene oxide copolymer. It is a lock copolymer. The polyester ester block copolymer is a ternary block copolymer composed of at least one of the above dicarboxylic acids and diols and at least one of polyester diols such as polylactone having an average molecular weight of about 300 to 5,000. Considering thermal adhesion, hydrolysis resistance, elasticity, heat resistance, etc.,
Terephthalic acid or naphthalene 2.6 dicarboxylic acid as a dicarboxylic acid, and 1.
4-butanediol, a polyalkylene diol as a polytetramethylene glycol ternary block copolymer,
Or 3 of polylactone as a polyester diol
Original block copolymers are particularly preferred. In a special case, a material into which a soft segment based on polysiloxane is introduced can also be used. The thermoplastic elastomer resin of the present invention also includes those obtained by blending a non-elastomeric component with the above-mentioned elastomer and copolymerized. Nylon 6 in the hard segment as a polyamide elastomer,
Nylon 66, Nylon 610, Nylon 612, Nylon 11, Nylon 12, etc. and their copolymerized nylon have a skeleton, and the soft segment has an average molecular weight of about 3
A block copolymer composed of at least one of polyalkylene diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer of 00 to 5000 is used alone or in combination of two or more. You may. Further, those obtained by blending or copolymerizing non-elastomeric components can be used in the present invention. As the polyurethane elastomer, (A) a number average molecular weight of 1,000 to 6,000 in the presence or absence of a usual solvent (dimethylformamide, dimethylacetamide, etc.)
Is reacted with a polyether and / or polyester having a hydroxyl group at a terminal thereof and (B) a polyisocyanate having an organic diisocyanate as a main component. A chain-extended polyurethane elastomer can be exemplified as a typical example. (A) polyester,
As polyethers, the average molecular weight is about 1000-6.
000, preferably 1300 to 5000 polybutylene adipate copolymerized polyester or polyalkylene diol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer is preferable, and as the polyisocyanate (B), Conventionally known polyisocyanates can be used, but diphenylmethane 4.
It is possible to use an isocyanate mainly composed of 4 ′ diisocyanate and to add a conventionally known triisocyanate or the like in a small amount, if necessary. As the polyamine (C), known diamines such as ethylenediamine and 1.2-propylenediamine are mainly used, and trace amounts of triamine and tetraamine may be used in combination as needed. These polyurethane elastomers may be used alone or in combination of two or more. In addition, the melting point of the thermoplastic elastic resin of the present invention is preferably 140 ° C. or higher, which can maintain the heat resistance, and the use of 160 ° C. or higher is more preferable because the heat resistance is improved. In addition, the durability can be improved by adding an antioxidant, a light stabilizer, or the like, if necessary.

[0010] It is preferable that the portion of the filaments constituting the structure of the present invention, which is formed of the thermoplastic elastic resin, has an endothermic peak below the melting point in a melting curve measured by a differential scanning calorimeter. Those having an endothermic peak below the melting point have remarkably improved heat resistance and sag resistance than those having no endothermic peak. For example, preferred polyester-based thermoplastic resins of the present invention include those containing 90 mol% or more of rigid terephthalic acid or naphthalene 2,6-dicarboxylic acid in the acid component of the hard segment, more preferably terephthalic acid or naphthalene 2 The content of 6 dicarboxylic acids is 95
After transesterification of the glycol component with a component containing at least 100 mol%, particularly preferably 100 mol%, the polymerization is carried out to the required degree of polymerization, and then the polyalkylene diol preferably has an average molecular weight of 500 to 5,000, more preferably 1,000 to 5,000. When 3,000 polytetramethylene glycol is copolymerized by 10 to 70% by weight, more preferably 20 to 60% by weight, the content of terephthalic acid or naphthalene 2.6 dicarboxylic acid having rigidity in the acid component of the hard segment is reduced. Because there are many, the crystallinity of the hard segment is improved, plastic deformation is difficult, and heat resistance resistance is improved,
If the annealing treatment is performed at a temperature lower by at least 10 ° C. than the melting point after the fusion heat bonding, the heat resistance and set resistance are further improved. Further, when an annealing treatment is performed after imparting a compressive strain, heat resistance and sag resistance are further improved. The line of the net-like structure treated in this way is identified by a differential scanning calorimeter (DS).
The melting curve measured in C) more clearly shows an endothermic peak at a temperature from room temperature to the melting point. When annealing is not performed, an endothermic peak at room temperature or higher and a melting point or lower is not exhibited in the melting curve. By analogy with this, it is considered that the hard segments are rearranged by annealing, pseudo-crystallization-like cross-linking points are formed, and heat resistance is improved. (This process is defined as a pseudo-crystallization process.) This pseudo-crystallization effect is also effective for polyamide-based elastic resins and polyurethane-based elastic resins.

The flame-retardant polyester (hereinafter abbreviated as flame-retardant polyester) obtained by copolymerizing a phosphorus-containing ester-forming compound or containing a phosphorus-containing flame retardant in the present invention includes polyethylene terephthalate (PET) and poly (ethylene terephthalate). Butylene terephthalate (abbreviated as PBT), polycyclohexylene dimethylene terephthalate (abbreviated as PCHDT), polyethylene naphthalate (abbreviated as PEN), polybutylene naphthalate (abbreviated as PBN), and a copolymerized polyester thereof such as polyethylene isophthalate ( A polyester obtained by introducing or imparting a phosphorus-containing flame retardant to a polyester having a main repeating unit of PEI or the like and PET or the like by polycondensation or mixture molding. Thus, those obtained by copolymerizing a phosphorus-containing ester-forming compound are preferable.
No. 92, JP-A-55-7888, JP-B-55
No. 41610 and the like.
However, a polyester obtained by copolymerizing a carboxylic acid represented by the following formula 1 as a part of the acid component is particularly preferable.

[0012]

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In the chemical formula 1, R ¹ and R ² are the same or different and each is a hydrogen atom (optionally a halogen atom) or a hydrocarbon group having 6 or less carbon atoms, and R ³ and R ⁴ are the same. Kamata hydrogen atom at different group, having 7 or less of the hydrocarbon group or a carbon - shows the (R ⁵ O) groups represented by r H.
R ⁵ represents an ethylene, propylene or butylene group;
Is an integer of 1 to 10, l and m are 0 or an integer of 1 to 4, n
Is 0, 1 or 2. In addition, examples of the phosphorus-containing flame retardant used in the production of polyester to modify the flame retardancy include various phosphoric esters, phosphites, and phosphonates (the above phosphoric esters having a halogen element as necessary). Or a polymer derived from these phosphorus compounds, or a polyarylphosphonate having a degree of polymerization of 6 or more, in which the compound shown in the following Chemical Formula 2 is entirely or partially contained in the diol component. here,
R ⁶ and R ⁷ are hydrogen or a lower alkyl group;
4 is an integer.

[0014]

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[0015] The content of phosphorus atoms in the flame-retardant polyester of the present invention is at least 500 ppm, at which the effect of flame retardancy is remarkable.
It is preferably 10,000 ppm or less, and more preferably 1,000 to 5,000 ppm, which causes little deterioration in physical properties. In addition,
Various modifiers, additives, coloring agents and the like can be added as needed. The flame-retardant composite network structure of the present invention uses a flame-retardant polyester containing phosphorus as a component. The reason for this is, from the viewpoint of safety, cyan gas generated during a fire,
It is an object of the present invention to minimize the amount of toxic gas having a small lethal amount such as halogen gas. For this reason, the toxicity index of the combustion gas of the flame-retardant composite network structure of the present invention is preferably 6 or less,
More preferably, it is 5 or less. In addition, when polyester fiber is used for the side layer and wadding layer, it can be recycled and recycled without separation, and when used in combination with other materials, it is easy to incinerate at the time of disposal. It is.

The reticulated structure of the present invention has a fineness of 10 in which a thermoplastic elastic resin and a flame-retardant polyester are formed into a composite structure.
A continuous filament of 0 to 100,000 denier is meandered, the filaments are brought into contact with each other, and the contact portion is fused to form a three-dimensional network structure. Due to this, even if a deformation is given by a large stress, the flame-retardant polyester undergoes deformation not exceeding the elastic limit while exhibiting compression resistance, and the thermoplastic elastic resin is subjected to a stress at which the flame-retardant polyester does not exceed the elastic recovery limit. The entire three-dimensional network structure in which continuous filaments are fused and integrated while undergoing large deformation partially deforms to absorb the stress, and when the stress is released, the flame-retardant polyester recovers elasticity and thermoplastic elasticity The resin also exhibits rubber elasticity, and the structure can be restored to its original form. As a result, the stress-strain curve (SS curve) at the time of compression changes the deformation strain with respect to the stress linearly, the sinking when sitting is moderate, and the stress due to the vertical movement when receiving vibration. Preferred characteristics can be imparted as a cushioning material capable of exhibiting the function of a preferred shock absorber that sinks the change moderately without feeling flat and supports the buttocks with low repulsion. Further, good sag resistance can be maintained. The present invention solves the disadvantage that the net-like structure made of only the thermoplastic elastic resin is soft and easily sinks when sitting down and in vertical movement due to vibration, and the body shape retention can be improved. A known cushion material made of a filament made of only an inelastic resin exhibits a remarkable repulsive force, increases the feeling of flooring, and causes plastic deformation due to compression deformation, resulting in insufficient recovery and poor heat resistance and durability. In the case where the filaments are not continuous, remarkable stress concentration occurs at the bonding point because the bonding point becomes a stress transmission point, causing structural destruction, and Japanese Unexamined Patent Publication No. 60-11352, which is also exemplified in the prior art, JP-A-61-137732, WO91-19
No. 032, the heat resistance and durability are inferior. If not fused, the shape cannot be maintained, and the structure does not deform integrally, so that fatigue phenomena occur due to stress concentration and the durability is deteriorated, and the shape is undesirably deformed. A more preferable degree of fusion according to the present invention is a state where most of the portions where the filaments are in contact are fused, and particularly preferably a state where all the contact portions are fused. In addition, when the fineness of the filament forming the structure of the present invention is 100 denier or less, the anti-compression strength is reduced and the repulsion is reduced, which is not preferable. If the denier is 100,000 denier or more, the individual compressive properties of the net are large, but the number of constituents is reduced, the dispersion of the force is deteriorated, and when a remarkably large compressive force of 100 kg / cm ² or more is applied, settling due to stress concentration occurs. Parts may be restricted. Preferably 300-5000
It is 0 denier, more preferably 500 to 30,000 denier. In addition, in the present invention, a method of obtaining an optimal configuration by combining the filaments having different fineness with the apparent density can also be selected as a preferable configuration. The structure comprising the thermoplastic elastic resin and the flame-retardant polyester of the present invention can exhibit cushioning performance by imparting the above-mentioned performance by forming a composite filament, and can impart flame retardancy.

Preferred forms of compounding of the filaments constituting the network structure of the present invention include a sheath core structure or a side-by-side structure, and a combination thereof. However, in order to obtain a three-dimensional structure that can recover even if the heat-bonded portion is greatly deformed, a sheath-core structure or a side-by-side structure occupying 50% or more of the surface of the filament with a thermoplastic elastic resin, and a combination structure thereof. Is mentioned. That is, in the sheath-core structure, the sheath component is a thermoplastic elastic resin, and in the side-by-side structure, the melt viscosity of the thermoplastic elastic resin is lower than the melt viscosity of the flame-retardant polyester, so that the thermoplastic elastic resin occupying the surface of the filaments is Structure with a high ratio (metamorphically, a structure with an eccentric sheath / core structure and a thermoplastic elastic resin placed on the sheath)
Assuming that the ratio of the thermoplastic elastic resin occupying the surface of the filament is 8
Those having 0% or more are preferable. More preferably, it has a sheath-core structure in which the proportion of the thermoplastic elastic resin occupying the surface of the filament is 100%. The cross-sectional shape is not particularly limited, but a hollow cross-section or a modified cross-section can impart compression resistance and bulkiness, and is particularly preferable when it is desired to reduce the fineness. The compression resistance is adjusted by the modulus of the material used, and the gradient of the initial compressive stress can be adjusted by increasing the hollow ratio and irregularity for soft materials, and the hollow ratio and irregularity can be decreased for materials with slightly higher modulus. Provides good anti-compression properties. As another effect of the hollow cross section and the irregular cross section, by increasing the hollow ratio and the degree of irregularity, when the same anti-compression property is imparted, it becomes possible to reduce the weight, and when used for seats of automobiles and the like, it is possible to save energy, In the case of a futon or the like, handleability at the time of raising and lowering is improved.

The average apparent density of the reticulated structure of the present invention is 0.005 g / cm which can exhibit the function as a cushion material.
^{3 ~0.02g} / cm ³ is preferable. 0.005 g / cm ³
If it is less than 0.20 g / cm ³ , the resilience is unsuitable because the resilience will be lost, and if it exceeds 0.20 g / cm ³ , the resilience will be too high and the sitting comfort will be poor. The more preferable apparent density of the present invention is 0.01 to 0.10 g / cm ³ , particularly preferably 0.03 to 0.06 g / cm ³ . Thus, the reticulated structure of the present invention can change the apparent density of each layer composed of the filaments having different fineness to give preferable characteristics. For example, in the case of a surface layer with a small fineness and a basic layer with a large fineness, the density of the surface layer with a fineness is slightly increased to increase the number of components, reduce the stress applied to one filament, and reduce the dispersion of stress. By improving the cushioning that supports the buttocks, it improves sitting comfort, and the basic layer with a large fineness is made thicker and slightly harder among them, with a layer that absorbs vibration and maintains body shape In order to make the surface in contact with the frame a more dense structure, the fineness is supplemented slightly to increase the density, so that the vibration and repulsive stress received from the frame surface are transmitted uniformly to the cushion layer, so that the entire cushion layer can convert energy. In addition, the sitting comfort can be improved and the durability of the cushion can be improved. In addition, in order to increase the thickness and tension of the side of the seat, the fineness can be made slightly thinner partially to increase the density. As described above, the density and fineness of each layer can be arbitrarily selected according to the purpose. In addition, the thickness of each layer of the network structure is not particularly limited, but is preferably 3 mm or more, and more preferably 5 mm or more, in which the function as the cushion body is easily exhibited.

In the present invention, the surface of the structure may have a surface layer in which a meandering line is bent at least 30 ° in the middle, the surface is substantially flattened, and most of the contact portions are fused. preferable. As a result, the contact points of the filaments on the surface of the mesh structure are greatly increased to form an adhesion point, so that the local external force of the buttocks when sitting can be received by the structure without giving a foreign body feeling to the buttocks. The surface structure is deformed as a whole and the entire internal structure is also deformed to absorb the stress, and when the stress is released, the rubber elasticity of the elastic resin is developed and the structure can recover to its original form I can do it. If it is not substantially flattened, it may give a foreign body sensation to the buttocks, apply a local external force to the surface, and selectively cause stress concentration up to the striated and adhesive points on the surface. In the case of an external force, a filament formed by combining a thermoplastic elastic resin and a flame-retardant polyester may cause fatigue due to stress concentration and reduce sag resistance. When the surface is flattened, no wadding layer is used, or a very thin wadding layer is laminated, and the surface is covered with side lands, for seats or chairs or beds for automobiles, railways, etc., for sofas, and for futons. Can be used as a cushion mat. However, when the surface is not flattened, it is necessary to form a seat or a cushion mat by laminating a relatively thick (preferably 10 mm or more) wadding layer on the surface of the net-like structure and covering the wadding layer with side lands. If necessary, adhesion to the wadding layer or adhesion to the side layer is easy when the surface is flat, but when the surface is not flattened, the adhesion is incomplete due to unevenness.

Next, the production method of the present invention will be described. The network structure of the present invention is distributed before each nozzle orifice so that the thermoplastic elastic resin and the flame-retardant polyester can be compounded, and is higher than the melting point of the low melting point component of the thermoplastic resin by 125 ° C. or less, Discharges downward from the nozzle at a melting temperature higher than the melting point of the component by 10 ° C. or more, and the composite discharge lines in a molten state are meandered and brought into contact with each other to fuse most of the contact portions to three-dimensionally. This is a method for producing a flame-retardant composite network structure in which the structure is formed, sandwiched by a take-off device, and then cooled in a cooling tank to form a network structure. The thermoplastic elastic resin and the flame-retardant polyester are separately melted by using a general melt extruder, and are mixed and discharged so as to be compounded immediately before the orifice in the same manner as in a general compound spinning method. In the sheath core, the core component is supplied from the center, and the sheath component is discharged from around the core component. In side-by-side, the components are combined and discharged from the left, right, front and rear. The melting temperature at this time is not preferable unless it is melted at a high temperature within 125 ° C. from the melting point of the low melting point component, because thermal decomposition becomes remarkable and the properties of the thermoplastic resin deteriorate. If the melting temperature is not higher than the melting point of the high melting point component by 10 ° C. or more, melt fracture occurs and normal filament formation cannot be performed. In the case of side-by-side, the adhesion of the filaments may be poor. A preferred melting temperature is 20 ° C to 100 ° C higher than the melting point of the low melting point component, more preferably 30 ° C to 80 ° C, and 10 ° C to 40 ° C higher than the melting point of the high melting point component, more preferably 20 ° C to 3 ° C.
Merge and discharge at the same melting temperature, which is higher by 0 ° C. Unless the melting temperature difference immediately before merging is set to 10 ° C. or less, abnormal flow may occur and the formation of a composite form may be impaired. The shape of the orifice is not particularly limited, but may be an irregular cross section (for example, a triangular shape, a Y shape, a star shape, etc. in which the second moment of area is high) or a hollow cross section (for example, a triangular hollow shape, a round hollow shape, a hollow shape with a projection, etc.). By doing so, the three-dimensional structure formed by the molten discharge filaments is difficult to alleviate the flow, and conversely, the flow time at the contact point can be kept long and the bonding point can be strengthened, which is particularly preferable. In the case of heating for bonding described in Japanese Patent Application Laid-Open No. 1-2075, it is not preferable because the three-dimensional structure is easily relaxed, and it becomes difficult to form a three-dimensional structure. As the effect of improving the characteristics of the structure,
The apparent bulk can be increased, the weight can be reduced, the compression resistance can be improved, and the elasticity can be improved. When the hollow ratio exceeds 80% in the hollow cross section, the cross section is likely to be crushed.
More preferably, it is 20% or more and 60% or less. The pitch between the holes of the orifices must be such that the loop formed by the filaments can sufficiently contact. The pitch between holes is shortened for a dense structure, and the pitch between holes is increased for a dense structure. The pitch between the holes of the present invention is preferably 3 mm to 20 m.
m, more preferably 5 mm to 10 mm. In the present invention, different densities and different finenesses can be obtained 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, or a method in which both the pitch between rows and between holes are also changed. Also, if the pressure loss difference at the time of discharge is given by changing the cross-sectional area of the orifice, a principle is used in which the discharge amount at which the molten thermoplastic elastic resin is extruded from the same nozzle at a constant pressure becomes smaller as the pressure loss of the orifice increases. Different fineness can be achieved. Then, the two-dimensional three-dimensional structure in the molten state is sandwiched between both sides of the take-off net, and the melted winding wire in the molten state on both sides is bent and deformed by 30 mm or more to flatten the surface and at the same time, the discharge wire that is not bent is formed. After the structure is formed by bonding the contact points of the above, it is quenched continuously with a cooling medium (usually, water at room temperature is preferably used because the cooling rate can be increased and the cost is reduced), and the three-dimensional structure of the present invention is obtained. A three-dimensional network structure is obtained. Then, drying with water is performed. However, if a surfactant or the like is added to the cooling medium, draining or drying becomes difficult, and the thermoplastic elastic resin may swell, which is not preferable. As a preferred method of the present invention, a pseudo crystallization treatment is performed after cooling once. The pseudo-crystallization treatment temperature is at least 10 ° C. lower than the melting point (Tm) and is equal to or higher than the α dispersion rise temperature (Tαcr) of Tan δ. This treatment has an endothermic peak below the melting point and significantly improves heat resistance and sag resistance as compared to those that do not pseudo crystallize (have no endothermic peak). The preferred pseudo crystallization treatment temperature of the present invention is (Tαcr + 10 ° C.) to (Tm−20 ° C.).
Although heat proofing and sagging resistance can be improved by pseudo-crystallization by simple heat treatment, heat proofing and sagging resistance can be significantly improved by annealing once by applying a compression deformation of 10% or more after cooling. More preferred. In addition, when a drying step is performed after cooling once, the pseudo crystallization treatment can be performed at the same time by setting the drying temperature to the annealing temperature. Further, a pseudo crystallization treatment can be separately performed. Then, it is cut into a desired length or shape and used as a cushion material. The distance between the nozzle surface and the take-off conveyor installed on the cooling medium that solidifies the resin, the melt viscosity of the resin,
The desired loop diameter or fiber diameter can be determined by the hole diameter of the orifice and the discharge amount. By sandwiching and stopping a discharge line in a molten state by a pair of take-up conveyors with adjustable intervals installed on the cooling medium, the parts that are in contact with each other are fused and continuously drawn into the cooling medium and solidified to form a network structure. When forming the, by adjusting the interval of the conveyor,
The thickness can be adjusted while the fused net is in a molten state, and a desired thickness can be obtained. The distance between the take-up conveyor and the nozzle surface is preferably within 30 cm. If the distance is too long, the molten wire is cooled and the contact portion is not fused, which is not preferable. If the conveyor speed is too high, the formation of contact points may be insufficient, or cooling may be performed until the fusion points are sufficiently formed, and the fusion of the contact portions may be insufficient.
On the other hand, if the speed is too slow, the melt will stay too much and the density will increase, so it is necessary to set a conveyor speed suitable for the desired apparent density.

When the flame-retardant composite network structure of the present invention is used for a cushion material, it is necessary to select a resin, a fineness, a loop diameter, and a bulk density to be used depending on the purpose of use and the site of use. For example, when used for wading of the surface layer, in order to provide a soft touch and a moderate sinking and swelling with tension, it is preferable to have a low-density, fine fineness, a fine loop diameter, and as a middle-layer cushion body In order to lower the resonance frequency, linearly change the appropriate hardness and the hysteresis at the time of compression to improve body shape retention and maintain durability, medium density, large fineness, and slightly larger loop diameter are preferable. . Further, it can be formed into a shape suitable for the purpose of use by using a molding die or the like so as not to impair the three-dimensional structure and covered with side lands, and can be used for vehicle seats, marine seats, beds, chairs, furniture and the like. Of course, it can be used in combination with another material, for example, a hard cotton cushion material made of a short fiber aggregate, a nonwoven fabric, or the like so as to meet the required performance in relation to the application. In addition, it is processed into a molded product from the manufacturing process as long as the performance is not degraded even in the process other than the resin manufacturing process, and at any stage of commercialization, flame retardancy, insect repellent antibacterial, heat resistance, water repellent, oil repellent, coloring,
Processing such as addition of chemicals can be applied to impart functions such as aroma.

[0022]

The present invention will be described in detail with reference to the following examples.

The evaluation in the examples was performed by the following method. 1. Melting point (Tm) and endothermic peak below melting point The endothermic peak (melting peak) temperature is determined from an endothermic curve measured at a heating rate of 20 ° C./min using a Shimadzu TA50 / DSC50 differential thermal analyzer. Was. 2. Heat the Tαcr polymer to the melting point + 10 ° C to a thickness of about 300 µm.
And a Tan δ (ratio M ″ / tan δ (imaginary elastic modulus M ″ and real modulus M ′ of elastic modulus) measured at 110 Hz at a heating rate of 1 ° C./min using Orientec Vibron DDVII type. The rise temperature of α-dispersion corresponding to the transition point temperature of the rubber elastic region to the melting region of M ′) was determined. 3. Apparent density The sample was cut into a size of 15 cm x 15 cm, the height was measured at four locations to determine the volume, and the value was obtained by dividing the weight of the sample by the volume. (Average value of n = 4) 4. Fineness of filaments Each filamentous portion is cut out from 10 places of the sample, embedded in acrylic resin, and a cross section is cut out to prepare a section to obtain a photograph of the cross section. The cross-sectional area (Si) of each part is determined from a cross-sectional photograph of each part. Further, the section obtained in the same manner was prepared by dissolving the acrylic resin in acetone, degassing in vacuo, and using a density gradient tube at 40 ° C.
The specific gravity (SGi) measured in is obtained. Next, a weight of 9000 m of the filament is obtained from the following equation. (Unit cgs) Fineness = [(1/10) ΣSi × SGi] × 90000000 5. Fusion It is judged whether or not the samples are adhered by visual judgment, and whether the adhered fibers are pulled apart by hand or not. It is judged that the thing which does not come off is fused by the judgment. 6.25% compression hardness A sample is cut into a size of 20 cm × 20 cm, and is compressed to 65% with a φ150 mm compression plate using Orientec Tensilon, and the stress at the time of 25% compression of the stress-strain curve obtained. Indicated by (Average value of n = 3) 7. Heat resistance (residual strain at 70 ° C.) A sample is cut into a size of 15 cm × 15 cm, compressed by 50%, allowed to stand in dry heat at 70 ° C. for 22 hours, and cooled to reduce compressive strain. Except for one day, the thickness (b) after standing for one day is calculated, and the thickness (a) before the treatment is calculated from the following formula, that is, (ab) / a × 100: unit% (average value of n = 3) 8. Repetitive compressive strain A sample was cut into a size of 15 cm x 15 cm, and 50% in a room at 25 ° C and 65% RH using a servo pulser manufactured by Shimadzu Corporation.
The compression recovery is repeated at a cycle of 1 Hz until the thickness of the sample reaches 20,000 times, and the thickness (b) of the sample after standing for 20,000 times is obtained for one day. From the thickness (a) before the treatment, the following formula is used: (ab) / a × 100
Calculated from: Unit% (average value of n = 3) 9. Sit comfort 30 ° C. RH 75% In a room, a paneler sits on a seat formed by buckling a polyester moquette on a cushion molded into a bucket frame on a seating frame. (N = 5) (1) Feeling of being on the floor: The degree of the feeling of hitting the floor with "doing" when sitting was qualitatively evaluated sensuously. Not felt; ◎, almost felt; ○, slightly felt; △, felt; × (2) Feeling of stuffiness: Sensitive qualitatively sensed that the part in contact with the seat inside the buttocks and thighs was humid after sitting for two hours. evaluated. Hardly felt; ◎, slightly stuffy; ○,
Slightly stuffy; △, noticeably stuffy; × (3) How much patience you can sit on the seat within 8 hours: 4 hours or more; ◎, 2-4 hours; ○, 1-2 hours; Δ: Within one hour; × (4) The degree of waist fatigue when seated in a seat for four hours was qualitatively evaluated sensuously. None; ◎, almost no fatigue; ○,
Slightly tired; △, very tired; × (5) Overall rating: 4 in evaluations (1) to (4)
Points, 3 points for ○, 2 points for Δ, 1 point for ×,
Among them, those not containing な い at 12 or more points; very good (、), those containing △ at 12 points or more; good (○), 10
It was evaluated as “not good” and “not good” (poor) and “good” (good). 10. Toxicity index of combustion gas It shows the integrated value of the value obtained by dividing each combustion gas amount (mg / g) measured by the method of JIS-K-7217 by lethal dose (mg / 10 liter) for inhalation for 10 minutes. 11. Flame retardancy The flame retardant products were evaluated by the 45 ゜ mesenamine method based on the performance test standards of flame retardant products specified by the Flameproof Product Certification Committee.

Examples 1-4 As dimethyl terephthalate (DMT) or dimethyl naphthalate (DM
N) and 1,4-butanediol (1.4BD) were charged with a small amount of a catalyst, transesterified by a conventional method, and polytetramethylene glycol (PTMG) was added. A copolymer elastomer was formed, and then 1% by weight of an antioxidant was added, mixed, kneaded, pelletized, and vacuum-dried at 50 ° C. for 48 hours.

[0025]

[Table 1]

As the polyurethane-based elastomer, 4.
4 'diphenylmethane diisocyanate (MDI) and P
TMG and 1.4 BD as a chain extender were added, polymerized, pelletized, and vacuum-dried to obtain a polyether-based urethane as a thermoplastic elastic resin raw material. The melting point of the obtained polymer is 158 ° C., the PTMG content is 54%, and Tαcr is −10.
° C. (Experiment No. A-4)

The obtained thermoplastic elastic resin and the carboxylic acid represented by Chemical Formula 1 were converted into phosphorus atoms at 2500 pp by a conventional method.
m copolymerized intrinsic viscosity 0.60, melting point 258 ° C, flame-retardant polyethylene terephthalate copolymer (hereinafter referred to as flame-retardant PET)
Are individually melted by an ordinary extruder, and the sheath is heated at a melting temperature of 278 ° C. immediately before the orifice so as to have a weight ratio of 50:50. In Examples 1, 2 and 4, the sheath is heated. The plastic elastic resin and the core are mixed and flowed so as to be flame-retardant PET. The nozzle has a pitch of 5 mm in the length direction and a pitch of 1 in the width direction on the nozzle effective surface having a width of 50 cm and a length of 5 cm.
In the first and third embodiments, the orifice shape is 0 mm. The total discharge amount is 1100 g / min from the triple bridge round hollow nozzles in the first and third embodiments, and the Y-type nozzles in the second and fourth embodiments. Cooling water is placed 12 cm below, a pair of take-up conveyors are placed on a pair of take-up conveyors at a distance of 5 cm in parallel with stainless steel endless nets with a width of 60 cm, and are taken out. Is inserted into the cooling water at 25 ° C. at a speed of 1 m per minute while solidifying, and then subjected to pseudo-crystallization treatment in a hot air drying base at 100 ° C. for 20 minutes, and then cut into a predetermined size to reduce the fineness of the filament. 90
00-9200 denier, apparent density 0.043-0.
A flame-retardant composite network of 044 g / cm ³ was obtained. Table 2 shows the properties of the obtained composite network structure. Example 1 has a hollow sheath-core type with a triangular diaper having a cross-sectional shape of a filament, has good flame retardancy, has good durability, has a moderate rebound force due to a moderate sinking and a hollow deforming effect, and is comfortable to sit. This is an example suitable for a cushioning material having good quality. In Examples 2 and 4, the cross-sectional shape of the filaments is a triangular sheath core type, has good flame retardancy, has good durability, moderate sinking and repulsive force due to the deforming effect work, and the seating comfort is good. This is an example suitable for a cushion material. Example 3 is a hollow side-by-side type in which the cross section of the filament is a triangular diaper and has good flame retardancy, good durability, moderate sinking, hollow irregularity effect, and the effect of flame-retardant PET which is an inelastic resin. This is an example suitable for a cushioning material having a firm repulsive force and a comfortable seating. The toxicity index of the combustion gas is 4.8 in Example 1, 5.1 in Example 2, 5.3 in Example 3, and 6.0 in Example 4, which are highly safe.

[0028]

[Table 2]

Examples 5 to 6 The carboxylic acid of formula 1 was converted to a phosphorus atom by a conventional method.
00 and 5000 ppm intrinsic viscosity 0.60
Flame-retardant PET with a melting point of 260 ° C and 256 ° C, respectively
The characteristics of the flame-retardant composite net having a fineness of 9000 to 9200 denier and an apparent density of 0.043 to 0.044 g / cm ³ obtained under the same conditions as in Example 2 except that It is shown in Table 2. Example 5 is a hollow sheath-core type in which the cross section of the filament is triangular diaper, and the core component is a flame-retardant PET having a low phosphorus atom content of 500 ppm, so that the flame retardancy is good and the durability is high. This is an example that is suitable for a cushioning material that has a moderate repulsive force due to a moderate sinking and a hollow deforming effect and is comfortable to sit on. Example 6 is a hollow sheath-core type in which the cross section of the filament is triangular diaper, and the core component is a flame-retardant P having a phosphorus atom content of 5000 ppm.
Since it is ET, it has good flame retardancy, satisfies the durability required for practical use, has appropriate repulsion due to appropriate sinking and hollow deforming effects, and is an example suitable for a cushioning material with good sitting comfort. The toxicity index of the combustion gas was 4 in Example 5.
8. The sixth embodiment has a high safety of 4.9.

Comparative Example 1 Polyethylene terephthalate having an intrinsic viscosity of 0.63 (PE
T) as a core component, and A-2 as a thermoplastic elastic resin as a sheath component, which are individually melted by a normal extruder at a melting temperature of 278 ° C. and a weight ratio of 50:50 immediately before the orifice. And the hole arrangement was the same as in Example 2, the hole shape was discharged from the orifice having a round cross section, and the fineness of the composite filament obtained under the same conditions as in Example 2 except that the pseudo-crystallization treatment was not performed. Is 9000 denier, apparent density 0.0
Table 2 shows the properties of the 43 g / cm ³ composite network structure. Comparative Example 1 has durability and moderate sinking, but fails in flame retardancy.

Comparative Example 2 Polyethylene terephthalate-polyethylene isophthalate copolymerized polyester (PES) containing 50 mol% of isophthalic acid and having an intrinsic viscosity of 0.65 was used as a sheath component.
The carboxylic acid represented by the chemical formula 1 is converted to a phosphorus atom by a conventional method.
500 ppm copolymerized intrinsic viscosity 0.60, melting point 258
C. as a core component and individually melted by a normal extruder at a melting temperature of 278 ° C. and a weight ratio of 50:50.
And the hole arrangement was the same as in Example 2 except that the hole shape was discharged from the orifice having a round cross-section and the pseudo-crystallization treatment was not performed. Table 2 shows the properties of the composite network having a denier of 7,500 denier and an apparent density of 0.045 g / cm ³ . Comparative Example 2 was poor in durability because of a composite network structure made of inelastic polyester having a slightly lower fineness.
This is an example that is not suitable for a cushion material that is hard and has a poor sitting comfort.

Comparative Example 3 The same nozzle as in Comparative Example 1 was used to discharge at a melting temperature of 278 ° C., and a take-up conveyor net was arranged below the nozzle surface 60 cm.
Table 2 shows some of the characteristics of the composite network obtained by the same method as in Example 2. In addition, since the obtained net-like structure had a poor bonding state and poor shape retention, the evaluation of the apparent density, the residual strain at 70 ° C., the repetitive compressive strain, and the sitting comfort was not performed. Comparative Example 3 is an example that is not suitable for a cushion material to which a body shape holding function cannot be imparted because the form is not fixed.

COMPARATIVE EXAMPLE 4 A melting point of 278 was obtained from a nozzle having a circular cross-section orifice having a pitch of 3 mm in the length direction and a pitch of 4 mm in the width direction on the effective surface of a nozzle having a width of 50 cm and a length of 5 cm. The fineness of the filaments obtained in the same manner as in Comparative Example 3 except that the total discharge amount was discharged at 50 ° C. at 50 ° C., and a take-up conveyor net was disposed 4 cm below the nozzle surface and taken up at 0.1 m / min. Are 97 denier and the apparent density is 0.025 g / cm ^3. Table 2 shows the properties of the composite network structure. Comparative Example 4 is an example in which the recovery is good because of the dense structure and the fineness is extremely small, but it is too soft to be used as a cushion material as it is.

COMPARATIVE EXAMPLE 5 A melting point of 278 was obtained from a nozzle having a round orifice having a pitch between rows of 8 mm in the length direction and a pitch between holes of 20 mm in the width direction on an effective surface of a nozzle having a width of 50 cm and a length of 5 cm. At 5600 g / min at 25 ° C, nozzle surface 25 cm
The fineness of the filament obtained in the same manner as in Comparative Example 3 was 146,000 denier, and the apparent density was 0.15 g / cm, except that the take-up conveyor net was arranged below and taken up at 1.5 m / min.
Table 2 shows the characteristics of the composite network structure of No. ³ . Comparative Example 5 is an example of a cushion material having too large a fineness and becoming hard and having a poor sitting comfort.

Comparative Examples 6 and 7 Using the same nozzle as in Comparative Example 3, the liquid was discharged at a melting temperature of 278 ° C. at a total discharge rate of 280 g / min and 1100 g / min.
Table 2 shows the characteristics of the composite network structure obtained in the same manner as in Comparative Example 3 except that a take-up conveyor net was arranged at the nozzle surface of 6 cm and 25 cm, and the take-up speed was 2.0 m / min and 0.2 m / min. Shown in In Comparative Example 6, the fineness of the filament was 23.
This is an example which is not suitable for a cushioning material which is excellent in flame retardancy and durability because it is 00 denier and has an apparent density as low as 0.0045 g / cm ³ , but is too soft and extremely uncomfortable to sit. Comparative Example 7 is an example which is not suitable for a cushioning material having a fineness of 9400 denier and a high apparent density of 0.22 g / cm ^3, which has a high apparent density of 0.22 g / cm ^3, and has a slightly inferior durability.

Example 7 The effective nozzle area was 120 cm wide and 12 cm long. The nozzle was discharged at a discharge rate of 1.98 g / min. Per hole, and the stainless steel endless net of the take-off conveyor was 140 cm wide and 12 cm in parallel. The properties, the fineness of the filaments and the average diameter of the loops of the flame-retardant composite network structure cut to 2 m in length obtained in the same manner as in Example 2 except that the fibers were taken at intervals were the same as those in Example 2. This net-like structure is cut into a width of 110 cm, and is made of flame-retardant polyester fiber.
The mattress was put in a quilted side cloth sewn to a size of 00 cm and a thickness of 12 cm. The mattress was placed on a bed, and four panelists used it for 7 hours in a room at 25 ° C. and 65% RH, and the sleeping comfort was completely evaluated. The bed was covered with sheets, the comforter was a 1.8 kg down / feather: 90/10, and the pillows were used by panelists every day. The evaluation result was a bed with a comfortable sleeping feeling without feeling of flooring, moderate sinking, and no stuffiness. For comparison, a density of 0.04 g / cm
^A similar mattress was made of a foamed urethane plate with a thickness of 10 cm at ³ , and it was installed on a bed to evaluate the sleeping comfort.
The bed had little feeling of flooring, but was deeply submerged, and the bed was a little uncomfortable to feel stuffy.

Comparative Example 8 The effective surface of the nozzle was 120 cm in width and 12 cm in length, and the width of the stainless steel endless net of the take-off conveyor was 140 cm.
The characteristics of the flame-retardant composite net structure cut to 2 m in length obtained in the same manner as in Comparative Example 2 except that it was taken out in parallel at an interval of 12 cm with the discharge amount per single hole, and the fineness of the filament and the average of the loop The diameter was the same as Comparative Example 2. This net-like structure was cut into a width of 110 cm and placed in a quilted side sewn to 110 cm in width, 200 cm in length, and 12 cm in thickness made of flame-retardant polyester fiber to prepare a mattress. The mattress was placed on a bed, and the sensory evaluation of sleeping comfort was performed in the same manner as in Example 8. As a result, it was hard to sink and the floor was large because it was hard, and the part in contact with the bed mat became sore that it awoke immediately, and The bed was stuffy and uncomfortable to sleep.

Example 8 The net-like structure obtained in Example 7 was cut to a width of 58 cm and a length of 58 cm, and a moquet made of polyester fiber was hung on the side. Four quilts were used for the seat part and two quilts were used for the back part. A cushion was put in and placed on the seat and back of the sofa, and the seating comfort was evaluated in the same manner as in Example 7. As a result, the back showed moderate rebound when leaned, and the seat had a feeling of flooring and stuffiness. It was a comfortable sofa with little feeling of tiredness and not much tired waist.

COMPARATIVE EXAMPLE 9 A cushion similar to that of Example 8 was prepared from the net-like structure obtained in Comparative Example 8, and the cushion was installed on the seat and back of the sofa.
As a result of evaluating the sitting comfort in the same way as above, the back part felt hard and foreign body feeling when leaned, and the seat part was noticeable with floor feeling and stuffiness,
The sofa was inferior in sitting comfort because the buttocks hurt and I could not sit for a long time.

Example 9 The net-like structure obtained in Example 7 was cut at 38 cm in width and 40 cm in length with rounded corners, cut over a moquette made of polyester fiber, and placed in an office chair. As a result of evaluating the sitting comfort in the same manner as in Example 8, it was found that the office chair was good in sitting comfort with almost no feeling of flooring and stuffiness and little tired waist.

[0041]

The flame-retardant composite net structure of the present invention has a three-dimensional three-dimensional net-like structured structure in which a filament formed by combining a thermoplastic elastic resin and a flame-retardant polyester is fused and integrated to further improve sitting comfort. Because it is a recyclable mesh structure suitable for a cushioning material that is resistant to stuffiness and has a suitable bulky and durable bulky and durable flame retardant, it is suitable for vehicle seats, marine seats, Can be provided for furniture cushions and bedding. It is also possible to use the flame-retardant composite net alone or in combination with other materials. Furthermore, it can be used in various applications for elastic nonwoven fabric applications.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D04H 1/00-18/00 B68G 1/00-15/00 D01D 1/00-13/02 D01F 1 / 00-13/04

Claims (12)

(57) [Claims] A fineness of a thermoplastic resin is 100 to 10
A composite structure comprising a 0000 denier filament, at least one kind of which is a thermoplastic elastic resin, and at least one kind comprising a flame-retardant polyester obtained by copolymerizing a phosphorus-containing ester-forming compound or containing a phosphorus-containing flame retardant. the reduction is continuous filament, apparent density of contacting to form a three-dimensional network structure allowed fused most of the contact portion with each other so Magarikunera is 0.005 g / cm ³ or more 0.20 g / cm ³ or less Flame-retardant composite network structure. 2. The flame-retardant polyester having a phosphorus atom content of 50.
The flame-retardant composite network structure according to claim 1, wherein the content is from 0 ppm to 10000 ppm. 3. The flame-retardant composite network structure according to claim 1, wherein the continuous and continuous composite structure is a sheath-core structure, the sheath component is a thermoplastic elastic resin, and the core portion is a flame-retardant polyester. body. 4. The flame-retardant composite network structure according to claim 1, wherein the composite structure of the continuous filaments is a side-by-side structure, and its constituent components are a thermoplastic elastic resin and a flame-retardant polyester. 5. The flame-retardant composite network structure according to claim 1, wherein the continuous filament has a hollow cross section. 6. The flame-retardant composite network structure according to claim 1, wherein the continuous filament has an irregular cross section. 7. The method according to claim 1, wherein the melting curve of the thermoplastic elastic resin constituting a part of the continuous filament has an endothermic peak at a temperature from room temperature to a melting point, which is measured by a differential scanning calorimeter (DSC). Flame retardant composite network. 8. When a loop forming the network structure is in the middle of the loop and the thickness direction of the network structure is a base line,
The flame-retardant composite network structure according to claim 1, wherein the structure is bent by 30 ° or more from the base line, most of the contact portions are fused, and the surface of the structure is substantially flattened. 9. Dispersing the thermoplastic elastic resin and the flame-retardant polyester in front of each nozzle orifice so that they can be combined with each other by 10 ° C. or more than the melting point of the high melting point component of the thermoplastic resin and the melting point of the low melting point component. The nozzles are discharged downward at a melting temperature within a temperature range that does not exceed 125 ° C. higher, and are brought into contact with each other in a molten state and fused to form a three-dimensional structure. A method for producing a flame-retardant composite network structure, comprising forming a reticulated network structure. 10. Once cooled, annealing is performed at least 10 ° C. below the melting point of the thermoplastic elastic resin.
A method for producing the flame-retardant composite network structure according to the above. 11. The method for producing a flame-retardant composite network structure according to claim 9, wherein after cooling, a compression strain of 10% or more is applied to anneal at a temperature of at least 10 ° C. below the melting point of the thermoplastic elastic resin. 12. A product according to claim 1, wherein the flame-retardant composite net structure is used for a vehicle seat, a marine seat, various beds, a furniture chair, and an office chair.