JP3351491B2 - Flame-retardant laminated net, 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 laminated net having excellent flame resistance, excellent cushioning properties, heat resistance and vibration absorption, and being recyclable. The present invention relates to products and manufacturing methods such as futons, furniture, beds, and cushioning materials for vehicles using a body.

[0002]

2. Description of the Related Art At present, foamed urethane, inelastic crimped fiber-filled cotton,
Resin cotton and hard cotton to which inelastic crimped fibers are bonded are used.

[0003] However, foamed-crosslinked urethane is extremely good in durability as a wadding layer and a cushion material, but is inferior in moisture permeability and heat storage, so that it is easily stuffed.
In addition, when the incinerator is incinerated because it is not thermoplastic and is difficult to recycle, the incinerator is greatly damaged and toxic gas removal is costly. 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, in the case of the cotton filled with thermoplastic polyester fiber, since the space between the fibers is not fixed, the shape at the time of use collapses, the fiber moves, and the crimp set causes a decrease in bulkiness and a decrease in elasticity. become.

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-61-141391. Further, JP-A-61-1377 discloses a method using a crosslinkable 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, because the adhesive component of the heat-bonding fiber used is a brittle amorphous polymer. -136828, JP-A-3-
There is a problem that the adhesive portion is brittle and the durability is poor such that the adhesive portion is easily broken during use and the form and elasticity are reduced. As an improved method, a method of performing confounding treatment has been proposed in Japanese Patent Application Laid-Open No. 4-245965, but there is a problem that the brittleness of the bonded portion is not solved and the elasticity is greatly reduced. In addition, there is also complexity in processing. Further, there is a problem that the bonded portion is hardly deformed and it is difficult to provide soft cushioning. For this reason, the adhesive is soft and the polyester elastomer recovers even if deformed to some extent.
Japanese Patent Application Laid-Open No. 4-240219 discloses a thermal bonding fiber using an inelastic polyester as a core component, and WO-91 / 19032, Japanese Patent Application Laid-Open No. 5-156561 discloses a cushioning material using the fiber. It has been proposed in, for example, JP-A-5-163654. When the adhesive component used in this fiber structure is a soft segment of polyester elastomer, the content of polyalkylene glycol is 30 to 50.
5% by weight of terephthalic acid in the acid component of the hard segment
0-80 mol%, and as another acid component composition
In the same manner as the fiber described in JP-A No. 0-1404, isophthalic acid is contained to increase the amorphousness, and the melting point is also 180.
℃ or lower and low melt viscosity to improve the formation of the heat-bonded part to form an amoeboid bonded part, but plastic deformation is easy, and the core component is inelastic polyester, so plastic deformation especially under heating And there is a problem that heat resistance and compression resistance decrease. As these improved methods, Japanese Patent Application Laid-Open
JP-A-163654 proposes a structure composed of only a polyester elastomer containing isophthalic acid as a sheath component and a heat-adhesive conjugate fiber using an inelastic polyester as a core component. Plastic deformation is remarkable, heat resistance and compression resistance are reduced, and there is a problem in using it for wadding layers and cushion materials. On the other hand, Japanese Patent Application Laid-Open No. Sho 63-163 discloses a method in which a silicone oil agent is applied to a hard cotton base material to reduce the friction coefficient of the fiber, thereby improving durability and improving texture.
It has been proposed in US Pat. However, there is a problem in the adhesiveness of the heat-bonding fiber, and the durability is inferior.

A thermoplastic olefin network used for civil engineering is disclosed in JP-A-47-44839. However, unlike a cushion made of fine fibers, the surface is uneven and the touch is poor, and since the material is olefin, the heat resistance is remarkably inferior and cannot be used as a wading layer or a cushion material. In addition, 3-1766
Japanese Patent Application Laid-Open No. 6-204, there is a method in which discharge filaments having different fineness are fused to each other to form a molding, but this is a net-like structure that is not suitable for a cushion material. In Japanese Patent Publication No. 3-55583,
A method is described in which only the very 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, the cushioning material does not provide a comfortable sitting comfort. JP-A-1-207462 discloses a floor mat made of vinyl chloride. However, since it has poor compression recovery at room temperature and extremely poor heat resistance, it is not preferable as a wading material or a cushion material. is there. In addition, the structure mentioned above does not consider the flame retardance at all.

[0007]

SUMMARY OF THE INVENTION In order to solve the above problems,
A flame-retardant laminated net made of thermoplastic elastic resin and thermoplastic inelastic resin suitable for cushioning material that blocks vibration, has excellent heat resistance, shape retention, cushioning properties, and is resistant to stuffiness and flame retardancy. It is an object of the present invention to provide a product and a product such as a futon, furniture, a bed, and a vehicle cushion using the flame retardant laminated net.

[0008]

Means for solving the above-mentioned problems, ie, the present invention is directed to a method for producing a resin having a soft segment content (A weight%) and a phosphorus content (Bppm) of 60A + 200 ≦ B ≦ 1.
A continuous line of 100,000 denier or less, made of a thermoplastic elastic resin layer satisfying the relationship of 00000 and a thermoplastic inelastic resin having a phosphorus content of 1000 to 2000 ppm, is meandered and brought into contact with each other to form the contact portion. Each of the reticulated bodies forming a three-dimensional three-dimensional structure in which most of the above-mentioned fusing are laminated and fused, both surfaces thereof are substantially flattened, and the apparent density is 0.01 to 0.2 g / cm. ³ , a flame-retardant laminated net, characterized by a soft segment amount (A weight%) from a multi-row nozzle having a plurality of orifices
And the phosphorus content (Bppm) is 60A + 200 ≦ B ≦ 100
000 and a thermoplastic inelastic resin having a phosphorus content of 1000 ppm or more and 20000 ppm or less are distributed to each nozzle orifice so as to be in each layer, and 10 to 120 ° C. higher than the melting point of the thermoplastic resin. At the melting temperature, the liquid is discharged downward from the nozzle, and is brought into contact with each other in a molten state and fused to form a three-dimensional structure.
This is a product using a flame-retardant laminated net which is sandwiched by a take-off device and cooled in a cooling tank, and a product using the flame-retardant laminated net.

In the present invention, the thermoplastic elastic resin is a polyether-based glycol, polyester-based glycol, polycarbonate-based glycol or long-chain hydrocarbon having a molecular weight of 300 to 5000 as a soft segment. Polyester-based elastomer, polyamide-based elastomer, polyurethane-based elastomer, which is obtained by block-copolymerizing an olefinic compound having a carboxylic acid or a hydroxyl group at a terminal.
And polyolefin-based elastomers. By using a thermoplastic elastic resin, regeneration becomes possible by re-melting, so that recycling becomes easy. For example, as a polyester-based elastomer, a polyester ether block copolymer having a thermoplastic polyester as a hard segment and a polyalkylenediol as a soft segment, or a polyester ester having an aliphatic polyester as a soft segment A block copolymer can be exemplified. More specific examples of polyester ether block copolymers 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 1.4 cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid dimer acid, and at least one dicarboxylic acid selected from ester-forming derivatives thereof; Species and aliphatic diols such as 1.4 butanediol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 1.1 cyclohexane Alicyclic diols such as dimethanol and 1,4-cyclohexane dimethanol, or these At least one diol component selected from the group consisting of ester-forming derivatives and polyethylene glycol having an average molecular weight of about 300 to 5,000.
A triblock copolymer composed of at least one of polyalkylenediols such as ethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide-propylene oxide copolymer. The polyester ester block copolymer is a ternary block copolymer composed of at least one of each of the above dicarboxylic acids, diols, and polyester diols such as polylactone having an average molecular weight of about 300 to 5,000. .
In consideration of thermal adhesion, hydrolysis resistance, stretchability, heat resistance, etc., terephthalic acid or naphthalene 2.6 dicarboxylic acid as a dicarboxylic acid, 1.4 butanediol as a diol component, poly As the alkylenediol, a triblock copolymer of polytetramethylene glycol or a terpolymer of polyester is particularly preferable. In a special case,
Those having a polysiloxane-based soft segment introduced can also be used. The thermoplastic elastomer resin of the present invention also includes those obtained by blending the above-mentioned elastomer with a non-elastomer component, copolymerized product, and polyolefin-based component made into a soft segment. As the polyamide-based elastomer, the hard segments include nylon 6, nylon 66, nylon 610, nylon 612,
Nylon 11, nylon 12, etc. and their copolymerized nylon are used as the skeleton, and the soft segment includes polyethylene glycol, polypropylene glycol, polytetramethylene glycol having an average molecular weight of about 300 to 5000,
A block copolymer composed of at least one kind of polyalkylenediol such as an ethylene oxide-propylene oxide copolymer may be used alone or as a mixture of two or more kinds. Further, those in which a non-elastomer component is blended or copolymerized can be used in the present invention.
As the polyurethane elastomer, (A) a number average molecular weight of 1000 to 60 in the presence or absence of a usual solvent (dimethylformamide, dimethylacetamide, etc.)
The polyether and / or polyester having a hydroxyl group at the terminal of 00 and (B) a polyisocyanate containing an organic diisocyanate as a main component are reacted at both ends with isocyanate.
As a typical example, (C) a polyurethane elastomer obtained by chain extension with a polyamine containing a diamine as a main component can be exemplified. The polyester and polyethers of (A) have an average molecular weight of about 1000
And 6000, preferably 1300 to 5000, such as polybutylene adipate copolymerized polyester, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and glycols composed of ethylene oxide-propylene oxide copolymer. Polyalkylene dio-
And the polyisocyanate (B) is preferably
A conventionally known polyisocyanate can be used, but an isocyanate mainly composed of diphenylmethane 4.4 'diisocyanate may be used, and a small amount of a conventionally known triisocyanate may be added if necessary. (C)
As the polyamine, mainly known diamines such as ethylenediamine and 1.2 propylenediamine may be used, and trace amounts of triamine and tetraamine may be used in combination as needed. These polyurethane elastomers can be used alone or in combination.
You may mix and use more than one type. 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. The reticulated body of the present invention contains a phosphorus-based compound to impart flame retardancy,
Since the thermal stability is slightly inferior to that containing no flame retardant, it is particularly preferable to add an antioxidant or the like as necessary to improve heat resistance and durability. The antioxidant is preferably a hindered antioxidant, which includes a hindered phenol and a hindered amine, and a nitrogen-free hindered antioxidant.
It is particularly preferable to add 1% to 5% of a dofenol-based antioxidant to suppress thermal decomposition because the generation of toxic gas with a small lethal amount during combustion can be suppressed. The soft segment content of the thermoplastic elastic resin constituting the component having the function of absorbing vibration and stress, which is the object of the present invention, is preferably 15% by weight.
The content is more preferably 30% by weight or more, and is preferably 80% by weight or less, more preferably 70% by weight or less from the viewpoint of heat and sag resistance. That is, the soft segment content of the component having the function of absorbing vibration and stress of the elastic network of the present invention is preferably 15% by weight or more and 80% by weight or less, more preferably 30% by weight or more and 70% by weight or less. .

The flame-retardant network of the present invention has a phosphorus content (Bppm) in the thermoplastic elastic resin of 60 A + 200 ≦ B ≦ 10 with respect to the soft segment content (A weight%).
0000 must be satisfied. Unsatisfactory results in poor flame retardancy, which is not preferred. 100000ppm
Exceeding the range is not preferred because the plastic deformation due to the plasticizing effect increases and the heat resistance of the thermoplastic elastic resin deteriorates. The preferred phosphorus content (Bppm) is the soft segment content (A
30A + 1800 ≦ B ≦ 100,000
The more preferable phosphorus content (Bppm) is 16A + 2600 with respect to the soft segment content (A weight%).
≦ B ≦ 50,000. There is a method of imparting high flame retardancy by adding a large amount of halides and inorganic substances, but a large amount of toxic halogen gas with a small lethal amount is generated at the time of combustion, and the problem of poisoning in a fire is reduced. Yes, the incinerator is greatly damaged during incineration, which is not preferable. In the present invention, the content of the halide is at least 1% by weight or less, preferably the content of the halide is 0.5% by weight or less, and more preferably no halide is contained. As the phosphorus-based flame retardant of the present invention, for example, in the case of a polyester-based thermoplastic elastic resin, at the time of resin polymerization, as a flame retardant in a hard segment portion, for example, 10 described in JP-A-51-82392. [2,3-di (2-hydroxyethoxy) -carbonylpropyl] 9,10-dihydro.
A method in which a carboxylic acid such as 9, oxa, 10 phosphaphenylene, or 10 oxylo is copolymerized as a part of an acid component of a hard segment to obtain a polyester-based thermoplastic elastic resin, For example, flame retardancy can be imparted by adding a phosphorus compound such as existing chemical substance number (3) -3735. In addition, examples of the flame retardant capable of imparting flame retardancy include various phosphates, phosphites, phosphonates (the above-mentioned phosphates containing a halogen element as necessary), or polymers derived from these phosphorus compounds. Can be illustrated. In the present invention, various modifiers, additives, coloring agents and the like can be added to the thermoplastic elastic resin as needed. The flame-retardant network of the present invention contains phosphorus for imparting flame retardancy. This is because, as described above, from the viewpoint of safety, cyan gas, halogen gas, etc. generated at the time of fire. The purpose of the present invention is to minimize the amount of toxic gas with low lethality. For this reason, the toxicity index of the combustion gas of the flame-retardant network of the present invention is preferably 6 or less, more preferably 5.5 or less. In addition, since polyester fibers are often used for the side layer and the wadding layer, it is preferable to use a polyester-based thermoplastic elastic resin so that the polyester fiber can be recycled without separation.

The thermoplastic elastic resin constituting the flame-retardant laminated net of the present invention preferably 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 the like. The content of naphthalene 2.6 dicarboxylic acid is 95 mol% or more, particularly preferably 100 mol%, and after transesterification of the glycol component, polymerization is carried out to a required degree of polymerization, and then as polyalkylenediol, preferably Average molecular weight of 5
00 or more and 5000 or less, particularly preferably 1000 or more and 3 or less
When the amount of polytetramethylene glycol of 000 or less is copolymerized in the range of 15% by weight to 70% by weight, more preferably 30% by weight or more and 60% by weight or less, terephthalic acid having rigidity in the acid component of the hard segment is obtained. Acid and naphthalene 2.
If the content of 6-dicarboxylic acid is large, the crystallinity of the hard segment is improved, the plastic segment is hardly deformed, and the resistance to heat resistance is improved. When the annealing treatment is performed, heat resistance and sag resistance are further improved. After applying compression strain,
Ringing further improves heat resistance and sag resistance. An endothermic peak more clearly appears at a temperature between room temperature and the melting point in the melting curve of the filaments of the network structure treated by a differential scanning calorimeter. When no annealing is performed, an endothermic peak does not appear in the melting curve from room temperature to the melting point. By analogy with this, it is considered that the annealing may cause rearrangement of the hard segments, form pseudo-crystallization-like cross-linking points, and improve heat resistance and sag resistance. (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.

In the present invention, the thermoplastic inelastic resin is
Examples thereof include polyester, polyamide, and polyolefin. For example, in the case of polyester, polyethylene terephthalate (PET), polyethylene naphthalate (PE)
N), polycyclohexylene dimethylene terephthalate (PCHDT), polycyclohexylene dimethylene naphthalate (PCHDN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyaryle And copolymerized polyesters thereof. For polyamides, polycaprolactam (N
Y6), polyhexamethylene adipamide (NY66),
Examples include polyhexamethylene sebacamide (NY6-10). Examples of the polyolefin include polypropylene (PP) and polybutene-1 (PB-1). In the present invention, the glass transition temperature is at least 4
It is preferable to use one at 0 ° C. or higher. As the thermoplastic inelastic resin used in the present invention, polyester is often used for the side material of the cushioning material, so as a cushioning material that can be recycled without being separated when discarded,
Polyesters such as PET, PEN, PBN, and PCHDT which also have good heat resistance are particularly preferred. Furthermore, PET, PE
Flame-retardant polyesters (hereinafter abbreviated as flame-retardant polyesters) which are polycondensed with N, PBN, PCHDT or the like and copolymerized with a phosphorus-containing ester-forming compound or containing a phosphorus-containing flame retardant are preferred. JP-A-51-82392, JP-A-55-7888, and JP-B-55-416.
No. 10 publication and the like. Although vinyl chloride has self-extinguishing properties, it emits a large amount of toxic gas when burnt, and is not preferred for use in the present invention.

The flame-retardant net according to the present invention has a phosphorus content of 1000 ppm or more and 20,000 in the thermoplastic inelastic resin.
It contains less than ppm. If it is less than 1000 ppm, the flame retardancy is insufficient, and if it exceeds 200,000 ppm, the plastic deformation due to the plasticizing effect becomes large, and the heat resistance of the thermoplastic inelastic resin is not preferable. The preferred phosphorus content is 2
000 ppm or more and 10000 ppm or less, more preferably 3000 ppm or more and 8000 ppm. There is a method of imparting high flame retardancy by adding a large amount of halides and inorganic substances, but a large amount of toxic halogen gas with a small lethal amount is generated at the time of combustion, and the problem of poisoning in a fire is reduced. Yes, the incinerator is greatly damaged during incineration, which is not preferable.
In the present invention, the content of the halide is at least 1% by weight or less, preferably the content of the halide is 0.5% by weight or less, and more preferably no halide is contained. As the phosphorus-based flame retardant of the present invention, for example, in the case of a polyester-based thermoplastic inelastic resin, at the time of resin polymerization,
As a flame retardant, for example, 10 [2.3-di (2-hydroxyethoxy) -carbonylpropyl] 9.10.dihydro-9.9 described in JP-A-51-82392 and the like.
A method of preparing a polyester-based thermoplastic inelastic resin obtained by copolymerizing a carboxylic acid such as oxa · 10 phosphaphenylene · 10-oxylo as a part of an acid component, or a method of converting a thermoplastic inelastic resin into a post-process using, for example, existing chemicals. Substance number (3) -3
Flame retardancy can be imparted by adding a phosphorus compound such as 735. In addition, examples of the flame retardant capable of imparting flame retardancy include various phosphates, phosphites, phosphonates (the above-mentioned phosphates containing a halogen element as necessary), or polymers derived from these phosphorus compounds. Can be illustrated. In the present invention, various modifiers, additives, coloring agents and the like can be added to the thermoplastic elastic resin as needed. The flame-retardant network of the present invention contains phosphorus in order to impart flame retardancy. The reason for this is as described above.
From the viewpoint of safety, it is an object to minimize the amount of toxic gas with a small lethal amount such as cyan gas and halogen gas generated in a fire. For this reason, the toxicity index of the combustion gas of the flame-retardant network of the present invention is preferably 6 or less, more preferably 5.5 or less. In addition, since polyester fibers are often used for the side layer and the wadding layer, it is preferable to use a polyester-based thermoplastic elastic resin so that the polyester fiber can be recycled without separation.

In the present invention, the fineness is less than 100,000 denier.
The lower continuous filaments meander and contact each other
Formed a three-dimensional structure with most of the contact parts fused
Phosphorus-containing thermoplastic elastic resin layer and phosphorus-containing thermoplastic inelastic resin
The layers are fused together and both sides are substantially flattened.
Hanging density is 0.01 g / cm^ThreeTo 0.2g / cm^ThreeFlame retardant
It is a flexible laminated network. The function of the cushioning material is
Layers and vibrations that are thicker and slightly harder to maintain body shape
With a component with good damping properties, increase the density a little and absorb
Comfortable buttocks touch by blocking movement and moderate sinking
Layer that gives uniform distribution of pressure on the buttocks
By maintaining body shape, stress and vibration can be changed
It can be shaped and absorbed to improve sitting comfort. Departure
Ming, the function of the cushion is made of thermoplastic elastic resin
The fused three-dimensional three-dimensional structure is formed on the reticulated body,
Made of thermoplastic inelastic resin for function of body shape fused
A three-dimensional three-dimensional structure is formed on a net-like body, which is joined together.
Flame retardant that can be added to provide the function of a preferred cushioning material
It is a laminated net. The laminated mesh of the present invention has a continuous filament.
Form a three-dimensional structure and fuse and integrate at most of the contact area
Laminated thermoplastic elastic resin layer and thermoplastic inelastic resin layer
Layered and substantially flat on both sides,
Vibration given by the thermoplastic elastic resin
Most of the vibrations are absorbed and attenuated and act as a vibration isolation layer.
Deformation even when a large deformation stress is applied locally
Stress is applied to the contact area when the surface of the mesh is substantially flattened.
The surface of a mesh consisting mostly of fused thermoplastic elastic resin
Receives the deformation stress and disperses the deformation stress.
Deformation occurs in the conductive resin layer, and the entire structure that is fused and integrated changes.
Shape and convert energy to absorb most deformation stress,
Deformation that could not be absorbed by the thermoplastic elastic resin layer
Three-dimensional network structure fused and integrated via a conductive elastic resin layer
Deforms as a whole while retaining its shape
Avoids stress concentration on individual filaments in layers composed of
Absorbs stress even within the elastic limit of thermoplastic inelastic resin filaments.
The thermoplastic inelastic resin shows anti-compression properties
Deformation within the range not exceeding the elastic limit and the stress is released
The thermoplastic inelastic resin filament layer also recovers elasticity,
The elastic resin layer also exhibits rubber elasticity and easily recovers its original shape
Therefore, it has good sag resistance and resists stress during compression.
Deformation distortion changes linearly, low rebound when sitting
With a moderate sinking while supporting the buttocks with force, it is with a floor
Develops a function to maintain body shape without giving a feeling. Thermoplastic elastic resin
A net consisting of only
The present invention solves the disadvantages that can be
Was. Net-like structure composed of filaments consisting only of known inelastic resin
Since the body does not have rubber elasticity when subjected to large deformation,
Durability due to compression deformation causes plastic deformation and no recovery
Is inferior. The surface of the mesh is not substantially flattened
In this case, the local external force is
May be selectively transmitted to the
Such external force causes fatigue due to stress concentration.
In some cases, sag resistance may decrease. Note that externally
When the layer to which the shape stress is transmitted is made of thermoplastic elastic resin
Is the stress concentration because the whole structure is deformed in the three-dimensional structure part
It is relaxed, but when it consists only of inelastic resin,
As the stress concentrates on the bonding point, structural failure occurs and it does not recover
Become. Furthermore, the surface is not substantially flattened and is convex.
Concavity gives a feeling of foreign body to the buttocks when sitting
Becomes worse, which is not preferable. In addition, the line shape is not continuous
In the case of a mesh with a large fineness, the point of adhesion is
Causes significant stress concentration at the bonding point, causing structural destruction.
The heat resistance and durability are inferior. When not fused
Cannot maintain the shape and the structure does not deform
As a result, fatigue phenomena occur due to stress concentration, resulting in poor durability.
Sometimes, the shape is deformed and it becomes impossible to maintain
Not good. The more preferred degree of fusion in the present invention is that
Most of the contacting parts are in a fused state.
Also preferably, all the contact portions are in a fused state. Scratch
The three-dimensional solid structure where the contact part of the continuous filament is mostly fused
Vibration absorption and elastic recovery by forming a structure and fusion bonding
Good thermoplastic elastic resin layer and thermoplastic non-compressive
The layer of elastic resin is laminated and fused and integrated, and the surface is substantially
The net with flattened cushioning function is
The deformation stress transmitted from the surface is received by the surface and the dispersion of the stress is
Better, reduce the stress applied to each line,
While retaining, the entire structure is deformed to absorb the deformation stress, and
Improves cushioning to support the buttocks, relieves stress
And the vibration transmitted from the frame is
The thermoplastic elastic resin part with good recovery properties absorbs
Improves sitting comfort and durability to cut off vibration at the resonance part
Can be done. Thermoplastic elastic resin layer and thermoplastic non-plastic
If the elastic resin layer is not fusion bonded, the entire structure
Since it does not deform with the body, it undergoes thermoplastic deformation when subjected to shear deformation
The conductive layer may be broken, which is not preferable. This purpose
The fineness of the filaments forming the network of the present invention is a thermoplastic elasticity.
100000 d for both the thermoplastic resin layer and the thermoplastic inelastic resin layer.
It is less than the nail. 0.2g / cm apparent density^Threeless than
In this case, the number of components exceeds 100,000 denier.
Structure that is less durable and has partially uneven durability due to density unevenness
And increased fatigue due to stress concentration, reducing durability
Is not preferred. Stria constituting the net of the present invention
If the fineness is too small, the anti-compression property will be too low
100 denier or less because stress absorption due to deformation decreases
Above. The preferred range of the thermoplastic elastic resin layer is anti-compression
300 denier or more, which is easy to produce
50,000 denier that does not impair the compactness of the structure due to the lower part
Less than More preferably, 500 denier or more, 1
It is less than 0000 denier. Thermoplastic inelastic resin layer
The preferred range is 500 denier, in which the effect of the anti-compression property is easily exerted.
Or more, the compactness of the structural surface is impaired due to the decrease in the number of components.
Not more than 50,000 denier. More preferably 1
It is not less than 000 denier and not more than 10,000 denier.
The apparent density of the reticulated body of the present invention depends on the thickness of the thermoplastic elastic resin layer.
0.005g / cm for both thermoplastic and inelastic thermoplastic layers^ThreeThen anti
Loss of power, insufficient vibration absorption capacity and deformation stress absorption capacity
And it may be difficult to achieve the cushion function.
0.25g / cm^ThreeAbove is repulsion too high and sitting
Because the ground may be bad, vibration absorption capacity and deformation stress
Utilizing the absorption function, the function as a cushion body is expressed
0.01g / cm^Three0.20g / cm or more^ThreeThe following
Preferably, more preferably, 0.03 g / cm^Three0.0 or more
8g / cm^ThreeIt is as follows. The mesh in the present invention has a fineness.
Optimum configuration by combining different linear shapes with apparent density
A method of forming a laminated structure with different fineness is also selected as a preferred embodiment.
You can choose. The thickness of the mesh body of the present invention is not particularly limited.
However, if the thickness of the thermoplastic elastic resin layer is less than 5 mm, it will absorb stress.
The preferred thickness is the force
Surface function and vibration and deformation stress absorption function
The minimum thickness is 10 mm or more, more preferably 20 mm.
mm or more. The thickness of the thermoplastic inelastic resin layer is
5mm or more that can exhibit durability, and the thickness of the mesh is 50mm
If the thickness is such that the function of the thermoplastic elastic resin layer can be
It is preferably 30 mm or less, more preferably 10 mm or less.
Above, less than 20 mm. The mesh body of the present invention is fusion-bonded.
The apparent density as a multilayered reticulated body is 0.01 g / cm^ThreeOr
0.2g / cm^ThreeIt is. 0.01 g / cm^ThreeLess than body
Cushion functions such as mold holding and vibration absorption are reduced.
Not preferred. 0.2g / cm ^ThreeBeyond the point of impact resilience
It is not preferable because it becomes difficult to sit comfortably. Preferred
The apparent density is 0.02g / cm^Three~ 0.1g / cm^ThreeIn
More preferably 0.03 g / cm^Three~ 0.06g / cm
^ThreeIt is.

The cross-sectional shape of the filaments of the mesh body of the present invention is not particularly limited, but a hollow cross-section or an irregular cross-section is particularly preferable because preferable compression resistance (repulsive force) and touch can be imparted. The anti-compression property can be adjusted by fineness and the modulus of the material used to make the fineness thinner.For soft materials, the hollowness and irregularity can be increased to adjust the gradient of the initial compressive stress, and the fineness can be made slightly thicker. A material with a high modulus reduces the hollowness and the degree of irregularity, and imparts good compression resistance to comfortable sitting. 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 compression resistance is imparted, the weight can be further reduced, and when used for a seat of an automobile or the like, energy saving can be achieved. In the case of a futon, the handling at the time of raising and lowering is improved. As another preferable method capable of imparting a preferable anti-compression property (repulsive force) and a touch, there is a method of forming a reticular filament of the present invention into a composite structure. Examples of the composite structure include a core-score structure or a side-by-side structure, and a combination structure thereof. However, in order to form a three-dimensional three-dimensional structure in which vibration and deformation stress, which cannot convert energy even if the thermoplastic elastic resin layer undergoes large deformation, can be recovered by converting the energy into energy, 50% or more of the linear surface is soft heat. Examples thereof include a core-score structure or a side-by-side structure occupied by a plastic elastic resin, and a combination thereof. That is,
In the score structure, the sheath component is a thermoplastic elastic resin with a large soft segment content that can easily convert vibration and deformation stress into energy, and the core component is a thermoplastic elastic resin with a small soft segment content to improve anti-compression properties. By giving it, it is possible to give a comfortable touch to the buttocks by moderate sinking. In the side-by-side structure, the melt viscosity of a thermoplastic elastic resin with a large soft segment content that can easily convert vibration and deformation stress into energy is made lower than the melt viscosity of a thermoplastic elastic resin with a small soft segment content that exhibits anti-compression properties. A structure in which the proportion of thermoplastic elastic resin with a large soft segment content occupying a linear surface is increased (figuratively, a structure in which thermoplastic elastic resin is arranged on an eccentric sheet-core structure sheet) The ratio of the thermoplastic elastic resin having a large soft segment content occupying a linear surface
% Is particularly preferred, and most preferably a scoring score when the proportion of the thermoplastic elastic resin having a large soft segment content occupying a linear surface is defined as 100%. When the ratio of the linear surface of the thermoplastic elastic resin having a large soft segment content occupies a large proportion, the fluidity when melting and fusing is high, so that the adhesion becomes strong, and the structure is integrally deformed. In this case, fatigue resistance against stress concentration at the bonding point is improved, and heat resistance and durability are further improved.

Since the laminated net formed by fusion bonding the thermoplastic elastic resin layer and the thermoplastic inelastic resin layer is substantially flat on both sides, the laminated net and other nets, non-woven fabrics and knitted fabrics are formed. Other adhesive components (such as heat-bonded non-woven fabric, heat-bonded fiber, heat-bonded film, heat-bonded resin) and adhesives for bonding with heat-bonded materials such as cotton, film, foam, metal, etc. To obtain products such as vehicle seats, marine seats, commercial and household beds for vehicles, ships, hospitals, etc., furniture chairs, office chairs, futons, etc. , Because the contact area with the surface of the adherend can be widened,
It is possible to obtain a product having a large bonding area and strong bonding and good bonding durability. In this case, the use of a flame-retardant heat-bonded body can provide a flame-retardant integrated laminated structure, and is a particularly preferred embodiment of the present invention. In addition, by performing the above-mentioned pseudo-crystallization treatment at any stage from the formation of the laminated network to the product, the melting curve of the thermoplastic elastic resin component in the structure measured with a differential scanning calorimeter is higher than room temperature. It is more preferable to have an endothermic peak at a temperature lower than the melting point, since the heat resistance of the product is remarkably improved. The filament of the thermoplastic elastic resin layer of the laminated network body of the present invention is formed into a composite structure, and a low melting point thermoplastic elastic resin having a high soft segment content that facilitates energy conversion of vibration and deformation stress is used as a heat bonding component. The use of a thermoplastic elastic resin having a small soft segment content as the shape-retaining component can impart a thermal bonding function. In order to provide a preferable thermal bonding function, for example, in a core-score structure, a thermoplastic elastic resin having a large soft segment content that facilitates energy conversion of vibration and deformation stress of a sheath component is used as a thermal bonding component, and a core component is used as a core component. A structure in which a thermoplastic elastic resin having a small soft segment content is used as a high melting point component to have a function of holding a net-like form, by using a material in which the melting point of the heat bonding component is lower than the melting point of the high melting point resin by 10 ° C. or more. The function of the heat bonding layer can be provided. The preferred melting point of the heat bonding component is a melting point 15 to 50 ° C. lower than the melting point of the high melting component, and more preferably a melting point 20 to 40 ° C. lower. The laminated network of the present invention having a heat bonding function, which is a preferred embodiment, has a substantially flat surface, and most of the contact portions are fused, so that the network, a nonwoven fabric, a knitted woven fabric, a hardened Cotton, film,
Since the area of contact with the surface of the object to be bonded such as foam or metal can be increased, the area of thermal bonding is increased, and a new molded body and a vehicle seat, a boat seat, a vehicle, a boat, etc. Hospital and other commercial and household beds, furniture chairs,
Office chairs and futon products can be obtained.
In addition, by performing pseudo-crystallization treatment at an arbitrary stage until a new molded product and product are commercialized, the melting line measured by a differential scanning calorimeter was used to measure the filaments of the thermoplastic elastic resin in the structure. It is more preferable that the curve has an endothermic peak at a temperature between room temperature and the melting point, since a product having significantly improved heat resistance and durability can be provided. If the adhered body is adhered in the stretched state during heat bonding, the adhered body is stretched due to the rubber elasticity of the adhesive layer, so it is stretched.
A molded article that does not easily wrinkle can be formed.

Next, the production method of the present invention will be described. According to the production method of the present invention, the soft segment amount (A weight%) and the phosphorus content (Bppm) are 60 A from a multi-row nozzle having a plurality of orifices.
+ 200 ≦ B ≦ 100,000 thermoplastic elastic resin and phosphorus content from 1000ppm to 20,000p
pm-containing thermoplastic inelastic resin is distributed to each nozzle orifice so as to form each layer, and discharged downward from the nozzle at a melting temperature higher than the melting point of the thermoplastic resin by 10 ° C. or more and less than 120 ° C. This is a method of producing a flame-retardant laminated mesh body which is brought into contact with each other in a molten state and fused to form a three-dimensional structure, sandwiched by a take-off device and cooled by a cooling tank, and is preferably integrally molded after cooling. This is a method for producing a flame-retardant laminated net and an article which are annealed at a temperature of at least 10 ° C. below the melting point of the thermoplastic elastic resin in a process leading to commercialization. In the present invention, the phosphorus-containing thermoplastic elastic resin and the phosphorus-containing thermoplastic elastic resin can be, as described above, a method in which a phosphorus compound is added during polymerization and copolymerized, or a method in which the compound is added after polymerization and mixed and kneaded. Mixing and kneading can be carried out using a twin-screw kneading extruder or a single-screw extruder having a kneading function such as dalmage or pin, and can be selected to be performed before melt extrusion or at the time of melt extrusion. If the flame retardant can be supplied at a constant rate, kneading during melt extrusion is the cheapest method. It is easy if the solid flame retardant is dry-mixed with the resin and fed to the extruder to prevent segregation.However, the liquid flame retardant is supplied to the kneading extruder quantitatively while the liquid flame retardant is separately measured. It is most desirable to adopt a method of kneading while supplying. For example, a method of quantitatively supplying a liquid flame retardant from a vent hole of a twin-screw kneading extruder can be exemplified. In this way, the soft segment amount (A weight%) and the phosphorus content (Bpp
m) satisfying the relationship of 60A + 200 ≦ B ≦ 100000 when the thermoplastic elastic resin and the phosphorus content are 100
0 ppm to 20000 ppm is added to the thermoplastic inelastic resin to form a network. The reticulated body uses a multi-component extruder, and the thermoplastic elastic resin and the thermoplastic inelastic resin are separately melted for each single component, and the thermoplastic elastic resin is formed on one side or both sides of the reticulated body on the back surface of the nozzle. And the thermoplastic inelastic resin is distributed to other portions and discharged below the orifice. In the score,
The core component is supplied from the center, and the sheath component is merged and discharged from around the core component. In side-by-side, each component is merged from right and left or front and rear and discharged. In a preferred embodiment of the present invention, for example, in the case of an orifice having a circular cross section in which the effective width in the longitudinal direction is 50 mm, the pitch between the holes in the row in the width direction of the nozzle is constant at 10 mm, and the pitch between the rows is constant at 5 mm, When the resin layer is arranged on one side, it is distributed in the first to seventh rows, and when arranged on both sides, it is distributed in the first to sixth rows and the tenth to eleventh rows. And preferably, at the same melting temperature of 10 ° C. or more and 120 ° C. or less from the melting point of each component, the discharge amount at which each component layer has a desired apparent density, for example, the single-hole discharge amount is The portion of the thermoplastic elastic resin layer is 2.5 g / min, and the portion of the thermoplastic inelastic resin layer is 2 g / min. And discharge it from each orifice downward. The melting temperature at this time is a temperature higher by 10 ° C. to 120 ° C. than the melting point of the thermoplastic resin. If the melting temperature is higher than the melting point of the low melting point component by more than 120 ° C., the thermal decomposition is remarkable, and the properties of the thermoplastic resin are undesirably reduced. On the other hand, if the melting point is not higher than the melting point of the high melting point component by 10 ° C. or more, melt fracture occurs, making it impossible to form normal filaments.
When contacting and fusing while forming a wire, the temperature of the filaments decreases, and the filaments may not fuse with each other, resulting in a network having insufficient adhesion, which is not preferable. A preferred melting temperature is a temperature 20 ° C. to 100 ° C. higher than the melting point of the low melting point component, more preferably a temperature 30 ° C. to 80 ° C. higher than the melting point, a temperature 15 ° C. to 40 ° C. higher than the melting point of the high melting point component, more preferably Discharge is performed at the same melting temperature that is 20 ° C. to 30 ° C. higher than the melting point. A preferred melting temperature is a temperature 20 ° C. to 100 ° C. higher than the melting point of the low melting point component, more preferably a temperature 30 ° C. to 80 ° C. higher than the melting point, a temperature 15 ° C. to 40 ° C. higher than the melting point of the high melting point component, more preferably Discharge is performed at the same melting temperature that is 20 ° C. to 30 ° C. higher than the melting point. In the case of composite spinning, if the melting temperature difference immediately before merging is not 10 ° C. or less, abnormal flow may occur and the formation of a composite form may be impaired. Although the shape of the orifice is not particularly limited, a hollow cross section (for example, a shape having a triangular hollow, a round hollow, a hollow with a projection, or the like) and a modified cross section (for example, a triangular, Y-shaped, star-shaped, etc. In addition to the above-described effects, the three-dimensional structure formed by the melted discharge filaments is less likely to flow, and conversely, the flow time at the contact point is maintained longer to strengthen the bonding point. It is particularly preferred because it can be 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 properties of the net-like body, the apparent bulk can be increased and the weight can be reduced, and the compression resistance and the resilience can be improved. In the case of a hollow cross section, if the hollow ratio exceeds 80%, the cross section is likely to be crushed.
0% or less, more preferably 20% or more and 60% or less. The pitch between the holes of the orifices must be such that the loop formed by the linear shape 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 mm, more preferably 5 mm to 10 mm. From a more preferred embodiment of the present invention, when the number of components is increased by the thermoplastic elastic resin layer, for example, the pitch between the first to sixth rows is 5 mm, and the pitch between the tenth and eleventh rows is If the total discharge amount of each component is changed to 6.67 mm and the same amount is discharged, the apparent density of the thermoplastic elastic resin layer becomes 0.05.
5 g / cm ^3, and 0.067 g / cm ^3, increased the apparent density of the thermoplastic non-elastic resin layer 2 fold configuration number without changing leave 0.041 g / cm ^3, and about 1.5 times A dense thermoplastic elastic resin layer can be formed. Of course, the cushion properties can be optimized by changing the pore density of a specific portion of the thermoplastic inelastic resin layer. In the present invention, different densities and different finenesses can be obtained as desired. A 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 the pitch between both rows and between holes is also changed. Also, if the pressure loss difference at the time of discharge is given by changing the cross-sectional area of the orifice, the discharge amount that is extruded from the same nozzle at a constant pressure from the same nozzle will decrease as the orifice with a larger pressure loss becomes smaller. Among them, a net-like structure composed of different fineness filaments between rows can be manufactured. For example, from the 7th column to 9 as described above
When distributing the thermoplastic inelastic resin to the rows, the orifice diameter in the seventh to eighth rows is set to 0.7 mm, the pitch between the holes is set to 5 mm, and the orifice diameter in the other rows is set to 1.0 mm. By forming two elastic resin layers, it is possible to improve sitting comfort and dispersion of deformation stress. Next, the nozzle is discharged downward from the nozzle, and while being formed into a loop, they are brought into contact with each other in a molten state and fused to form a three-dimensional structure. The wire is sandwiched between the nets, and the surface of the reticulated body is bent and bent at least 45 ° to deform and flatten the surface, and at the same time, the structure is formed by bonding the contact points with the unbent discharge lines. After formation, the laminated network is continuously cooled by a cooling medium (usually, it is preferable to use water at room temperature because the cooling rate can be increased and the cost is reduced), thereby forming a three-dimensional three-dimensional network structure of the present invention. Get. It is preferable that the distance between the nozzle surface and the take-up point is at least 40 cm or less to prevent the discharge filament from being cooled and the contact portion from being fused.
10 cm or more when the discharge amount of discharge line is as large as 5 g / min or more.
It is preferably 40 cm, and in the case where the discharge amount of the discharge filament is as small as 5 g / min or less, it is preferably 5 cm to 20 cm. The thickness of the laminated network is determined by the opening width (interval between the take-off nets) of the take-off net that sandwiches both sides of the molten three-dimensional structure. In the present invention, the opening width of the take-up net is set to 5 mm or more for the above-described reason. 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. Next, it is cut into a desired length or shape and used as a cushion material. The desired loop diameter and wire diameter can be determined by the distance between the nozzle surface and a take-off conveyor provided on a cooling medium for solidifying the resin, the melt viscosity of the resin, the hole diameter of the orifice, and the discharge amount. A pair of take-up conveyors with adjustable intervals installed on the cooling medium sandwich the discharge lines in the molten state and stop and fuse the parts in contact with each other, while continuously drawing into the cooling medium and solidifying. When the structure is formed, by adjusting the interval between the conveyors, the thickness can be adjusted while the fused net is in a molten state, and a desired thickness can be obtained. If the conveyor speed is too high, the contact point may be insufficiently formed, or the contact point may be cooled until the fusion point is sufficiently formed, and the fusion of the contact portion 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. As a preferred method of the present invention, a pseudo-crystallization treatment by annealing is performed at a temperature of at least 10 ° C. below the melting point of the thermoplastic elastic resin in an arbitrary step from molding to product after cooling once, and then forming a laminated network. Obtaining a body or product is a more preferred process. 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 with those without the pseudo-crystallization treatment (without the endothermic peak). The preferred pseudo-crystallization temperature of the present invention is (T
αcr + 10 ° C.) to (Tm−20 ° C.). Pseudo crystallization by simple heat treatment improves heat set resistance. However, it is more preferable to perform annealing by giving a compression deformation of 10% or more, since the heat set resistance is remarkably improved. In the case where 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. In addition, a pseudo crystallization process can be separately performed in a process of commercialization.

When the flame-retardant laminated net of the present invention is used as a cushion, it is necessary to select the resin, fineness, loop diameter, and bulk density to be used depending on the purpose of use and the site of use. For example, in order to provide a soft touch and a moderate sunk and firm bulge, it is preferable to use a low-density, fine fineness and a small loop diameter. To reduce the frequency, moderately change the hardness and the hysteresis at the time of compression linearly to improve body shape retention and maintain durability, medium density and thick fineness,
It is preferable to adopt a structure in which a layer having a relatively large loop diameter and a layer having a low density, a fine fineness and a small loop diameter are laminated and integrated.
Further, it can be formed into a shape suitable for the purpose of use using a molding die or the like to the extent that the three-dimensional structure is not impaired, and can be used as a vehicle seat, a boat seat, a bed, a chair, furniture, or the like by directly covering the side ground. . Of course, it is also possible to use in combination with other materials, for example, a different net-like material, a hard cotton cushion material composed of a short fiber aggregate, a nonwoven fabric, or the like in order to meet the required performance in relation to the application. In addition to the resin manufacturing process, the product is processed into a molded product from the manufacturing process to the extent that the performance is not degraded, and flame retardation, antibacterial and antibacterial, heat resistance, water and oil repellency, coloring, fragrance etc. The function can be imparted by processing such as adding a drug.

[0019]

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. Endothermic peak at melting point (Tm) and below the melting point The endothermic peak (melting peak) was obtained from an endothermic curve measured at a heating rate of 20 ° C./min using a Shimadzu TA50 / DSC50 differential thermal analyzer. -H) The temperature was determined. 2. Heat the Tαcr polymer to the melting point + 10 ° C and make the thickness about 300μm.
And a Tan δ (ratio M ″ / tan δ (imaginary elastic modulus M ″ and real part M ′ of elastic modulus) measured at 110 Hz and at a heating rate of 1 ° C./min using a Vibron DDVII model manufactured by Orientec. M ′) is the rise temperature of α-dispersion corresponding to the transition point temperature from the rubber elastic region to the melting region. 3. Apparent density The sample is cut into a size of 15 cm × 15 cm, the height of four places is measured, the volume is determined, and the weight of the sample is indicated by a value obtained by reducing the weight by the volume. (Average value of n = 4) 4. Fineness of filaments Each filamentous portion is cut out from 10 places of the sample, and the cross section is cut out by embedding with an acrylic resin 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 dissolved in an acrylic resin with acetone, degassed in vacuo, and heated at 40 ° C. using a density gradient tube.
The specific gravity (SGi) measured in is obtained. Next, the linear weight of 9000 m is obtained from the following equation. (Unit cgs) Fineness = [(1 / n) ΣSi × SGi] × 90000000 5. Fusion Check whether the sample is fused by visual judgment. It is judged that what is not separated is fused. 6. Flame Retardancy Those that satisfy the flame retardancy standard (extinguish flame in 60 seconds or less) according to the F-MVSS302 method are judged as pass, and those that do not meet the criteria are judged as fail. 7. Toxicity index of combustion gas It indicates the integrated value of the value obtained by dividing each combustion gas amount (mg) measured by the method of JIS-K-7217 by lethal dose (mg / 10 liters) for inhalation for 10 minutes. 8. Heat resistance and durability (70 ° C residual strain) A sample was cut into a size of 15 cm × 15 cm, compressed by 50%, allowed to stand in dry heat at 70 ° C for 22 hours, cooled to remove the compressive strain, and removed after 1 day of thickness ( b) is calculated, and is calculated from the thickness (a) before the processing according to the following equation, that is, (ab) / a × 100. Unit% (average value of n = 3) 9. Repetitive compressive strain A sample was cut into a size of 15 cm × 15 cm, and 50% in a RH chamber at 25 ° C. and 65% with a Shimadzu servo pulsar.
The compression recovery is repeated at a cycle of 1 Hz until the thickness of the sample reaches 20,000 times, the thickness (b) of the sample after standing for 1 day is determined, and the thickness (a) before the treatment is calculated from the following formula, that is, (ab) / a × Calculated from 100. Unit% (average value of n = 3) 10. Sitting comfort Using a known composite spinning machine, a thermoplastic elastic resin A-1 described later is used as a sheath component and A-2 is used as a core component by a known composite spinning machine. Melted individually and distributed immediately before the orifice, and the spinning temperature is 245 at a 50/50 weight ratio, with 1.6 g / min per hole (0.8 g / min: 0.8 g / min).
At a spinning speed of 3500 m / min, a yarn with a denier of 4.1 denier and a shrinkage of 8% at 160 ° C dry heat was converged and mechanically crimped in a tow-like crimper. And 64
The resultant was cut into mm to obtain a heat-bonded fiber made of a thermoplastic elastic resin having a cross-section of the core. The matrix fiber is obtained by distributing PET having intrinsic viscosity of 0.63 and 0.56 at a weight ratio of 50/50 by a conventional method, and discharging amount of 3.0 g / min (1.5 g / min) per single hole.
Min .: 1.5 g / min.) At a spinning temperature of 285 ° C. from a C-type orifice, and spinning at a spinning speed of 1300 m / min. It was cut into 64 mm, and a three-dimensional crimped yarn having 6 deniers and an initial tensile resistance of 38 g / denier obtained by expressing crimping at 160 ° C. in dry heat was obtained. The obtained heat-bonding fiber (30% by weight) and the base material fiber (70% by weight) were mixed and opened.
The card web obtained by pre-spreading in step (1) and then opening with a card is cut into a bucket sheet shape by laminating a card web laminated to a basis weight of 500 g / m ² on the thermoplastic elastic resin layer side. Alternatively, the apparent bulk density of the molded cushion is set to 0.05 g / cm ³ on the thicker side of the thermoplastic elastic resin layer.
Into a female mold for thermoforming, compressed with a male mold, packed, and heat-bonded with hot air at 200 ° C. for 5 minutes to form a cushion formed into a bucket sheet. Cover the polyester moquette, and set it on the seating frame to make a seat with four seats and six backrests at the back, 30 ° C RH7
A panel was seated on a seat prepared in a 5% room, and the following evaluation was performed. (N = 5) (1) Feeling of flooring: The degree of feeling "hit" when sitting and hitting the floor was sensually evaluated qualitatively. Not felt; ◎, almost felt; ○, slightly felt; △, felt; × (2) Feeling of stuffiness: After sitting for two hours, sensationally felt that the part in contact with the buttocks and the inner part of the crotch was stuffy. It was qualitatively evaluated. Almost no: ◎, slight stuffiness; ○, slight stuffiness; △, noticeable stuffiness; × (3) How long to be patient in 8 hours or less: 1 hour; × within 2 hours; △ within 4 hours;
○: 4 hours or more; ◎ (4) The degree of waist fatigue when seated in a seat for 4 hours was qualitatively evaluated sensoryly. None; ◎, hardly tired; ○, slightly tired; △, very tired; × (5) Overall evaluation: 4 points of ◎ from (1) to (4), ○
Is 3 points, Δ is 2 points, and × is 1 point, 12 points or more do not contain Δ; very good (◎), 12 points or more include Δ; good (○), 10 points or more are × Was evaluated as poor (x), poor x (x), and poor (x).

Example 1 Dimethyl terephthalate (DMT) or dimethyl naphthalate (DM) was used as a polyester elastomer.
N) and 1.4 butanediol (1.4 BD) were charged with a small amount of a catalyst, transesterified by a conventional method, and polytetramethylene glycol (PTMG) was added. -Forming a terester block copolymer elastomer, then adding 2% of an antioxidant,
Table 1 shows the formulation of the thermoplastic elastic resin raw material obtained by mixing, kneading, pelletizing, and vacuum drying at 50 ° C. for 48 hours.

[0022]

[Table 1]

In the nozzle effective surface having a width of 50 cm and a length of 5 cm, the pitch between the holes in the width direction is set to 5 mm for 1 to 6 rows, 10 mm for 9 to 9 rows, and 6.67 mm for 10 and 11 rows. The orifice shape in a staggered arrangement with a pitch between holes in the direction of 5 mm is a 2 mm outer diameter, 1.6 mm inner diameter and a triple bridge hollow-forming nozzle, and the obtained thermoplastic elastic resin raw material (A
-1 and A-2) are separately supplied in a constant amount by two extruders having a kneading function, and an existing chemical substance number (3) -3735 is added as a flame retardant so as to have a phosphorus content of 10000 ppm. Is melted, and dimethyl terephthalic acid is added as an acid component to 10 [2.3-di (2-hydroxyethoxy) -carbonylpropyl] 9.10-dihydro-9.oxa.
10 phosphaphenylene / 10 oxylo in an amount of 10000 ppm in terms of phosphorus content and 1.4 parts in the glycol component
BD was charged with a small amount of a catalyst, transesterified by a conventional method, and subjected to polycondensation while increasing the temperature and pressure to obtain a relative viscosity of 1.0.
Is melted by an extruder, and A-1 and A-2 are immediately before the orifice so that A-1 is a sheath component and A-2 is a core component (seise / core: (50/50 weight ratio)
From the first row to the sixth, tenth, and eleventh rows, PB
T is distributed from the seventh column to the ninth column, and at a melting temperature of 265 ° C., the discharge amount of the first to sixth columns is 758 g / min, the discharge amount of the seventh to ninth columns is 304 g / min, The discharge amount of the 10th and 11th columns is discharged below the nozzle at 253 g / min.
Cooling water is placed 10 cm below the nozzle surface, and a pair of take-up conveyors are placed in parallel with stainless steel endless nets having a width of 60 cm at intervals of 5 cm so as to partially emerge above the water surface. While forming a meandering loop and fusing the contact portions while sandwiching both sides of the laminate having a three-dimensional network structure, the laminate is drawn into cooling water at 25 ° C. at a speed of 1 m per minute, and then solidified at 100 ° C. Table 2 shows the characteristics of the multilayer net obtained by pseudo-crystallization treatment in a hot air dryer for 20 minutes and then cutting to a predetermined size. The reticulated body of the thermoplastic elastic resin layer on the surface of Example 1 was formed of a triangular diaper-shaped hollow cross-section having a sheath-core structure, a hollow ratio of 38%, and a fineness of 5600 denier. Average apparent density 0.055 g / cm ³ , phosphorus content 9000 ppm
(60A + 200 = 2780 ppm), the net of the thermoplastic elastic resin layer on the back side has a triangular diaper-shaped hollow cross section having a sea-core structure, a hollow ratio of 38%, and a fineness of 750.
It is formed of 0 denier filaments, has an average apparent density of 0.067 g / cm ³ and a phosphorus content of 9000 ppm (60 A
+ 200 = 2780 ppm), and the mesh of the intermediate thermoplastic inelastic resin layer has a triangular tapered hollow cross section with a hollow ratio of 40% and a fineness of 9000 denier. The apparent density was 0.041 g / cm ³ , the phosphorus content was 9000 ppm, and the average apparent density of the entire laminated and integrated laminated network was 0.053 g / cm ³ . Table 2
As is clear from the above, Example 1 has a cushioning function that is excellent in heat resistance, durability at room temperature, and sitting comfort because of a laminated net structure utilizing characteristics of a soft elastic resin and characteristics of a slightly hard elastic resin. It was a highly safe cushioning material having flammability and low combustion gas toxicity index. It can be seen that the seat created for evaluation also has excellent performance.

[0024]

[Table 2]

Example 2 Dimethyl isophthalate (DMI) 20 mol% and DMT
Table 1 shows the formulation of a polyester-based thermoplastic elastic resin obtained in the same manner as in Example 1 by charging 80 mol% and 1.4 butanediol (1.4 BD) with a small amount of a catalyst.
The orifice has a round cross-section with a diameter of φ1 mm. The nozzle has a round cross-section with a diameter of φ1 mm. The pitch between holes in the width direction is 10 mm, and the pitch between holes in the length direction is 5 mm. Using A-3 as a thermoplastic elastic resin,
A flame retardant was added so as to have a phosphorus content of 9000 ppm, and the mixture was distributed from the first row to the seventh row and discharged at a discharge rate of 710 g / min to obtain a thermoplastic inelastic resin in the same manner as in Example 1. A-3 layer network of a multilayer network obtained in the same manner as in Example 1 except that PBT having a phosphorus content of 9000 ppm was distributed from the 8th to 11th rows and discharged at a discharge rate of 410 g / min. Is a solid round section with a fineness of 9000 denier, an average apparent density of 0.044 g / cm ³ and a phosphorus content of 9000 p
pm (60A + 200 = 3320 ppm), the net of the PBT layer has a solid round cross section of 9100 denier, an average apparent density of 0.047 g / cm ³ and a phosphorus content of 9000 pp.
m, the average apparent density of fused and integrated is 0.045 g /
Table 2 shows the characteristics of the laminated net having a size of cm ³ . As is clear from Table 2, the heat resistance and the durability at room temperature are practically usable in Example 2, the body shape retention is improved, the cushioning function is excellent in sitting comfort, the flame retardancy is high, and the combustion is incombustible. It is a highly safe cushioning material with a low gas toxicity index, and the seats created for evaluation are also excellent.

Example 3 Polyurethane-based elastomer, 4,4'-diphenylmethane diisocyanate (MDI), PTMG, and 1.4BD as a chain extender were added and polymerized, and then 2% of an antioxidant was added and mixed. After kneading, pelletizing and vacuum drying, the formulation of the polyether urethane polymer is shown in Table 3.

[0027]

[Table 3]

The obtained thermoplastic elastic resin (seed component:
B-1; core component: B-2) with phosphorus content of 12,000 pp
m, and the thermoplastic elastic resin obtained in the same manner as in Example 1 except that the flame retardant was added so as to obtain a B-1 and B-1
Table 2 shows the properties of the laminated net obtained in the same manner as in Example 1 except that B-2 was used as the core component. In Example 3, the linear cross-sectional shape on the surface side of the composite thermoplastic elastic resin layer of B-1 and B-2 is a triangular diaper-shaped hollow cross section having a sea core structure, a hollow ratio of 40%, and a fineness of 6200 denier. , With an average apparent density of 0.055 g / cm ³ and a phosphorus content of 12,000 pp
m (60A + 200 = 3260 ppm), the back side is a triangular diaper-shaped hollow cross section having a sea-score structure with a hollow core of 40%, a fineness of 8300 denier, and an average apparent density of 0.066 g / cm. ³ with phosphorus content of 12000p
pm (60A + 200 = 3260 ppm), intermediate PB
The T layer has a fineness of 9000 denier, an average apparent density of 0.041 g / cm ³ , a phosphorus content of 10000 ppm, and an average apparent density of 0.053 of the whole of the fused and integrated network.
g / cm ³ . In addition, B-1 is used as a sheath component, and B-
2 was used as a core component, and the fineness was 4.5 denier and the shrinkage at 150 ° C was 9 obtained in the same manner as in the production of the heat-bonded fiber prepared in the evaluation of sitting comfort except that the spinning temperature was 200 ° C. %
The sitting comfort was evaluated in the same manner as the evaluation method of the sitting comfort except that the heat-bonded fiber was used. Example 3 is a laminated net using urethane as a thermoplastic elastic resin, which has excellent heat resistance, durability at room temperature, and a cushion function with excellent sitting comfort, is flame-retardant, and has a low toxicity index of combustion gas. It was a highly cushioning material. It turns out that the seat made for evaluation is also excellent.

Comparative Example 1 Polyethylene terephthalate having an intrinsic viscosity of 0.63 (PE
T) The network used in Comparative Example 1 obtained in the same manner as in Example 2 except that only a single component was used and a flame retardant was added so that the phosphorus content was 5000 ppm, and the melting temperature was 280 ° C, Fineness 8800 denier, apparent density 0.047
g / cm ³ and the phosphorus content was 5000 ppm. Then
Table 2 shows the properties of the laminated network obtained in the same manner as in Example 2 except that the pseudo-crystallization treatment was not performed. Comparative Example 1 is a cushioning material which has flame retardancy, but is poor in heat resistance and durability due to a mesh body made of inelastic polyester, and is hard and has poor sitting comfort.

Comparative Example 2 Flame retardant was added to A-3 so that the phosphorus content was 200 ppm.
In addition, the same as Example 2 except that the pseudo-crystallization treatment was not performed.
A-layer net of the laminated net obtained in the above step is a solid round cross section.
With a fineness of 9000 denier and an average apparent density of 0.04
4g / cm^ThreeWith a phosphorus content of 200 ppm (60A + 200 =
3320 ppm), the mesh of the PBT layer is
Degree 9100 denier, average apparent density 0.047g
/cm^ThreeWith phosphorus content of 9000 ppm, fusion-integrated average
Has an apparent density of 0.045 g / cm ^ThreeOf Laminated Network
Are shown in Table 2. As is clear from Table 2, Comparative Example 2 was sitting
Comfortable, but inferior in heat resistance and durability, thermoplastic elastic
If the flame retardancy of the oily layer is insufficient, the flame retardancy will also be rejected.
It is an example of a cushion material.

Comparative Example 3 The flame retardancy of the multilayer network obtained in the same manner as in Example 2 except that pseudo crystallization was not performed using PBT having a phosphorus content of 100 ppm was rejected. This is an example in which the laminated network does not become flame-retardant unless the thermoplastic inelastic resin is made flame-retardant even if the thermoplastic elastic resin is flame-retardant.

Comparative Example 4 Example 2 was repeated except that the take-up conveyor net was arranged 60 cm below the nozzle surface and the pseudo-crystallization treatment was not performed after the take-up conveyor net.
Since the reticulated body obtained by the same method as in Example 1 has a poor adhesion state and is difficult to adhere to the nonwoven fabric and has poor form retention, the flame retardancy, apparent density, 70 ° C residual strain, repeated compression strain, and sitting comfort are evaluated. Not. Comparative Example 4 is an example that is not suitable for a cushion material because the form is not fixed.

Comparative Example 5 A-3 was difficult to have a phosphorus content of 121000 ppm.
Example except that the fuel was added and the pseudo-crystallization treatment was not performed.
The A-3 layer obtained in the same manner as in Example 2 had a solid round section and a fineness of 900
It is formed from 0 denier filaments and has an apparent density of
0.044g / cm ^Three, Phosphorus content 121000 ppm (6
0A + 200 = 3320 ppm) and the network of the PBT layer is
9100 denier fine solid round section, average apparent density
Is 0.047 g / cm^ThreeWith phosphorus content of 9000ppm, fusion
The integrated average apparent density is 0.045 g / cm^ThreeProduct
There was a layer network. Comparative Example 5 has a large phosphorus content in the A-3 layer.
Too good, the flame retardancy is passed, but the characteristics of thermoplastic elastic resin
Deterioration, seating comfort is slightly inferior, heat resistance and durability are remarkable
This is an example of an inferior cushioning material.

Comparative Example 6 A laminated network obtained in the same manner as in Example 2 except that PBT having a phosphorus content of 21,000 ppm was polymerized was used. The A-3 layer had a solid round cross section and a fineness of 9000 denier. It is formed from filaments, has an apparent density of 0.044 g / cm ³ , a phosphorus content of 9000 ppm (60A + 200 = 3320 ppm), and has a solid round cross-section with a fineness of 9100 denier.
The laminated net had an average apparent density of 0.047 g / cm ³ , a phosphorus content of 21000 ppm, and an average apparent density of 0.045 g / cm ³ integrated by fusion. Comparative Example 6
This is an example of a cushion material in which the phosphorus content of the BT layer is too large and the flame retardancy is passed, but the properties of the thermoplastic inelastic resin are deteriorated, the sitting comfort is slightly inferior, and the heat resistance and durability are extremely inferior. .

Comparative Example 7 Discharge was performed at a discharge rate of 3 g / min per single hole, the speed of the take-off conveyor net was set to 0.3 m / min, and the same procedure as in Example 2 was performed except that the pseudo-crystallization treatment was not performed. A-line fineness is A-
Each of the three layers and the PBT layer has a fineness of 13,000 denier, an average apparent density of the network of 0.21 g / cm ³ , and a phosphorus content of 90.
Table 2 shows the characteristics of the laminated network at 00 ppm (60A + 200 = 3320 ppm). Comparative Example 6 had a high apparent density, so that the cushioning material was good in touch but slightly inferior in sitting comfort and insufficient in heat resistance and durability.

COMPARATIVE EXAMPLE 8 A nozzle having an orifice diameter of 2 mm in a staggered arrangement having a pitch between holes in the width direction of 10 mm and a pitch between holes in the length direction of 20 mm was formed on the effective surface of a nozzle having a width of 50 cm and a length of 5 cm. A-3 is distributed in the third row, and PBT is distributed in the fourth to seventh rows, and discharged at a discharge rate of 25 g / min per single hole.
The fineness of the filaments obtained in the same manner as in Example 2 except that the take-up conveyor net was arranged below and taken at 1 m / min and not subjected to the pseudo-crystallization treatment was 113000 denier, and the average apparent density Table 2 shows the characteristics of the laminated net having a weight of 0.157 g / cm ³ . Comparative Example 8 is a cushioning material that passes the flame retardancy, but has a remarkably large fineness and a density unevenness, and thus has poor heat resistance and durability, and has a slightly worse sitting comfort.

Comparative Example 9 140 g / min of A-3 was supplied to the first to seventh rows and 80 g / min of copolymerized PBT was supplied to the eighth to eleventh rows, and a take-off conveyor net was placed 5 cm below the nozzle surface. A obtained in the same manner as in Example 2 except that the
The laminated mesh having a fineness of 1800 denier and an apparent density of 0.009 g / cm ³ in both the -3 layer and the PBT layer passes the flame retardancy, but the density is too low and the sitting comfort is extremely poor, and the heat resistance is high. The cushioning material had insufficient properties and durability.

Comparative Example 10 Using a take-up conveyor having a take-up conveyor net having an uneven surface, the filament fineness of the A-3 layer obtained in the same manner as in Example 2 except that the pseudo-crystallization treatment was not performed was 9000 denier. The average apparent density of the reticulated body was 0.043 g / cm ³ , and the phosphorus content was 9
000 ppm (60A + 200 = 3320 ppm), P
The laminated network having a BT layer fineness of 9100 deniers, an average apparent density of 0.047 g / cm ³ , a phosphorus content of 9000 ppm, and a fusion-integrated average apparent density of 0.045 g / cm ³ is a reticulated body. The surface is uneven, so the apparent density is low but the durability is inferior, and the thermal adhesion is insufficient,
The cushioning material was inferior in sitting comfort with a foreign body sensation.

Example 4 The flame-retardant laminated net obtained in Example 1 was cut into a piece having a length of 120 cm, and the heat-bonded fiber and the base fiber used for the evaluation of sitting comfort were mixed and opened at a weight ratio of 40/60. The woven web is laminated and compressed so that the apparent density becomes 0.05 g / cm ^3.
Hot-adhesive molding with hot air at 00 ° C, thickness 6cm, width 120cm,
Quilted every 50cm, width 120cm, length 20
Mattresses were made by placing them in a side yard of 0 cm. The mattress was set on a bed, and four panelists used it for 7 hours in a room at 25 ° C. and 65% RH for sensory evaluation of sleeping comfort. In addition, sheets were hung on the bed, the comforter was made of batting 1.8 kg of down / feather: 90/10, and the pillow was worn by the paneler 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 similar mattress was made of a urethane foam plate having a density of 0.04 g / cm ³ and a thickness of 10 cm, and was placed on a bed to evaluate the sleeping comfort. It was an uncomfortable bed that felt stuffy.

Example 5 The flame-retardant laminated net obtained by laminating and thermoforming the nonwoven fabric obtained in Example 4 was cut into a shape having a width of 38 cm, a length of 40 cm and a corner of 10 cm to provide a comfortable seat. The polyester moquette used for evaluation was placed on the side of the office chair frame, and compared with the office chair using a commercially available polyurethane cushion, sitting comfort was evaluated for 4 hours. The feeling of flooring and the time during which the patient can stand while sitting was remarkably excellent in the case of using the flame-retardant laminated net of the present invention.

[0041]

According to the present invention, a striated layer made of a phosphorus-containing thermoplastic elastic resin having good vibration and stress absorption and a striated layer made of a phosphorus-containing thermoplastic inelastic resin having anti-compression properties form a three-dimensional structure. The flame-retardant laminated mesh body with a flattened surface that is fused and integrated is a vibration-insulating property, heat-resistant and durable, bulky, comfortable to sit, is not easily stuffed, and is flame-retardant. Is a low safety cushioning material, covering the side land as it is, or in combination with other materials, vehicle seats, marine seats, vehicles, marine, hospitals and the like that have been given the preferred characteristics described above Products such as beds for business use such as hotels, cushions for furniture, bedding products and the like can be provided. Further, it is also useful for interior materials and heat insulating materials for vehicles and building materials.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI D04H 3/16 D04H 3/16 (58) Field surveyed (Int.Cl. ⁷ , DB name) D04H 1/00-18/00 B68G 1/00-15/00 B32B 1/00-32/00 D01F 1/00-13/04

Claims (6)

(57) [Claims] 1. The amount of soft segment (A weight%) and phosphorus content (Bppm) are 60A + 200 ≦ B ≦ 100,000.
And a phosphorus content of 10 which satisfies the relationship of
Consisting of 00 to 2000 ppm of a thermoplastic inelastic resin,
The continuous filaments each having a density of 100,000 denier or less are meandered and brought into contact with each other to form a three-dimensional three-dimensional structure in which most of the contact portions are fused. Is virtually flattened,
A flame-retardant laminated net having an apparent density of 0.01 to 0.2 g / cm ³ . 2. The flame-retardant laminated net according to claim 1, wherein the cross section of the continuous filament is a hollow cross section or an irregular cross section. 3. The flame-retardant laminated net according to claim 1, wherein the thermoplastic elastic resin constituting the continuous filament has an endothermic peak in a melting curve measured by a differential scanning calorimeter at a temperature from room temperature to a melting point. . 4. A multi-segment nozzle having a plurality of orifices has a soft segment amount (A weight%) and a phosphorus content (Bpp).
m) A thermoplastic elastic resin satisfying the relationship of 60A + 200 ≦ B ≦ 100000 and a thermoplastic inelastic resin having a phosphorus content of 1,000 ppm or more and 20,000 ppm or less are distributed to each nozzle orifice so as to be in each layer, and the thermoplastic resin is At a melting temperature of 10 to 120 ° C. higher than the melting point, it is difficult to be discharged downward from the nozzle, contacted with each other in a molten state and fused to form a three-dimensional structure, sandwiched by a take-off device, and cooled in a cooling tank. A method for producing a laminated flammable network. 5. The flame-retardant laminated net according to claim 4, wherein annealing is performed at a temperature of at least 10 ° C. below the melting point of the thermoplastic elastic resin in a step of forming the product after cooling and integrally forming the product. 6. A vehicle seat, a boat seat, a commercial or household bed, a furniture chair, office work, etc., using the flame-retardant laminated net according to claim 1. The product according to any of the chairs and futons.