JP3431096B2 - Nonwoven laminated net, manufacturing method and product using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a non-woven fabric laminated reticulated body having a flame retardant property, an excellent cushioning property, a heat resistance durability and a vibration absorption property, which is recyclable, and a method for producing the reticulated nonwoven fabric. The present invention relates to products such as futons, furniture, beds, cushioning materials for vehicles, and manufacturing methods.

[0002]

2. Description of the Related Art At present, as a cushion material for furniture, beds, trains, automobiles, etc., urethane foam, non-elastic crimped fiber wadding,
In addition, resin cotton or hard cotton to which non-elastic crimped fibers are adhered is used.

However, although the foamed-crosslinked urethane has very good durability as a wadding layer or a cushioning material, it has poor moisture permeability and heat storage property and is apt to be stuffy.
Moreover, since it is not thermoplastic, it becomes difficult to recycle, and when it is incinerated, the damage to the incinerator is large and the cost for removing the toxic gas is high. For this reason, landfilling has become more frequent, but it is difficult to stabilize the ground, and there is a problem that landfilling sites are limited and costs increase. Further, although it has excellent processability, it also has a problem of pollution of chemicals used during manufacturing. In addition, since the fibers are not fixed in the thermoplastic polyester fiber wadding, the form may collapse during use, the fibers may move, and the crimp may cause a decrease in bulkiness and elasticity. become.

As a resin cotton in which polyester fibers are adhered with an adhesive, for example, a rubber-based adhesive is used, Japanese Patent Application Laid-Open No.
0-11352, JP-A 61-141388, JP-A 61-141391 and the like. Further, as a method using a cross-linkable urethane, JP-A-61-1377
No. 32 publication and the like. These cushion materials have inferior durability, and also have problems such as not being recyclable because they are neither thermoplastic nor single composition, and there are problems such as complexity of processability and pollution of chemicals used during manufacturing. .

Polyester hard cotton, for example, JP-A-58-3
1150, JP-A-2-154050, JP-A-3-220354, etc., but since an amorphous polymer having a brittle adhesive component of the heat-bonding fiber used is used (for example, JP-A-58). -136828, Japanese Patent Application Laid-Open No. 3-
However, there is a problem in that durability is poor such that the bonded portion is brittle and the bonded portion is easily broken during use and the form and elasticity are reduced. As an improved method, a method of entanglement treatment has been proposed in Japanese Patent Laid-Open No. 4-245965, but there is a problem that the brittleness of the bonded portion is not solved and the elasticity is largely reduced. In addition, there is complexity during processing. Further, there is a problem that the bonded portion is hard to be deformed and soft cushioning is hard to be imparted. For this reason, the polyester elastomer that is soft even at the bonded portion and recovers even if it is deformed to some extent
A heat-bonding fiber using a non-elastic polyester as a core component is disclosed in JP-A-4-240219, and a cushion material using the fiber is disclosed in WO-91 / 19032, JP-A-5-155651. It is proposed in Japanese Patent Laid-Open No. 5-163654. The adhesive component used in this fiber structure has a polyalkylene glycol content of 30 to 50 as a soft segment of polyester elastomer.
Wt%, 5% terephthalic acid as the acid component of the hard segment
It contains 0 to 80 mol% and is used as another acid component composition
As in the fiber described in Japanese Patent Publication No. 0-1404, isophthalic acid is contained to increase the amorphous property, and the melting point is 180.
The temperature is below ℃, and the heat-bonded part is well formed with a low melt viscosity to form an ameber-shaped bonded part, but it is easy to plastically deform, and because the core component is an inelastic polyester, plastic deformation especially under heating Becomes remarkable, and there is a problem that the heat resistance and compression resistance are lowered. As an improved method for these, Japanese Patent Laid-Open No.
No. 163654 proposes a structure consisting only of a polyester elastomer containing isophthalic acid as a sheath component and a heat-bonding composite fiber using an inelastic polyester as a core component. Plastic deformation becomes significant, the heat resistance and compression resistance deteriorate, and there is a problem in using it for a wadding layer or a cushion material. On the other hand, there is a method in which a silicone oil is added to a base material of hard cotton to lower the friction coefficient of fibers to improve the durability and improve the texture.
It is proposed in Japanese Patent No. 158094. However, there is a problem with the adhesiveness of the heat-adhesive fiber and the durability is poor, so it is not preferable for use in a wadding layer or cushioning material.

A thermoplastic olefin network used for civil engineering work 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 durability is extremely poor and it cannot be used as a wadding layer or cushion material. In addition, Japanese Patent Publication No. 3-1766
No. 6 discloses a method in which ejection filaments having different fineness are fused to each other to form a mold, but the mesh structure is not suitable as a cushion material. Japanese Examined Patent Publication No. 3-55583 discloses that
A method of thinning only a very surface with a thinning device such as a rotating body before cooling is described. With this method, the surface cannot be flattened and a thick thin linear layer cannot be formed. Therefore, it does not provide a comfortable cushioning material. Japanese Patent Application Laid-Open No. 1-207462 discloses a vinyl chloride floor mat, but it is not preferable as a wadding material or a cushioning material because it has poor compression recovery at room temperature and remarkably poor heat resistance. is there. Note that no consideration is given to flame retardancy in the above-mentioned structure.

[0007]

To solve the above problems,
Uses a non-woven fabric laminated net made of thermoplastic elastic resin suitable for cushioning material that has excellent heat resistance and durability, shape retention and cushioning properties, and has vibration resistance, and cushioning properties. The purpose is to provide products such as bedding, furniture, beds, and cushions for vehicles.

[0008]

[Means for Solving the Problems] Means for solving the above problems, that is, in the present invention, the soft segment amount (A% by weight) and the phosphorus content (Bppm) are 60A + 200 ≦ B ≦ 1.
The continuous filaments having a fineness of 100,000 denier or less and made of a thermoplastic elastic resin satisfying the relationship of 00000 are bent and brought into contact with each other to fuse most of the contact portions , and both surfaces are flattened. and on one or both sides of the three-dimensional mesh-like body, double of two kinds of thermoplastic elastomeric resin
Non- woven fabric layer in which synthetic short fibers form a three-dimensional structure and are fused and integrated is laminated and joined to give an apparent density of 0.01 g / cm ³
To 0.2 g / cm ³ of non-woven fabric laminated network, multi-row nozzle with multiple orifices, soft segment amount (A wt%) and phosphorus content (Bppm) 60A + 200 ≦ B ≦ 1
A thermoplastic elastic resin satisfying the relationship of 00000 is distributed to each nozzle orifice, and the melting point of the thermoplastic resin is 10
It is discharged downward from the nozzle at a melting temperature higher by -80 ° C., and in a molten state, they are brought into contact with each other and fused to form a three-dimensional structure, sandwiched by a take-up device and cooled in a cooling tank, and then single-sided. or composite short fibers made of two thermoplastic elastomeric resin on both sides by spreading laminating web which is three-dimensional, a method of non-woven fabric laminated net-like body thermoformed while compressing further the nonwoven fabric laminate meshwork Is a product using.

The thermoplastic elastic resin in the present invention means, as the soft segment, an ether type glycol, a polyester type glycol, a polycarbonate type glycol or a long chain hydrocarbon having a molecular weight of 300 to 5,000. Polyester elastomer obtained by block-copolymerizing an olefinic compound having a carboxylic acid or a hydroxyl group at the terminal, a polyamide elastomer, a polyurethane elastomer,
Examples include polyolefin elastomers. By using a thermoplastic elastic resin, it becomes possible to regenerate by remelting, and thus recycling becomes easy. For example, as the polyester 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 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'dicarboxylic acid. At least one of alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid dimer acid, and dicarboxylic acids selected from ester-forming derivatives thereof Seeds and aliphatic diols such as 1.4 butanediol, ethylene glycol, trimethylene glycol, tetremethylene glycol, pentamethylene glycol and hexamethylene glycol, 1.1 cyclohexane Alicyclic diols such as dimethanol and 1,4-cyclohexane dimethanol, or these Of at least one diole component selected from the ester-forming derivatives thereof and polyethylene glycol having an average molecular weight of about 300 to 5,000.
It is a ternary block copolymer composed of at least one of polyalkylenediol such as propylene, 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 the above dicarboxylic acids, diol, and polyester diol such as polylactone having an average molecular weight of about 300 to 5,000. .
Considering heat adhesion, hydrolysis resistance, stretchability, heat resistance, etc., terephthalic acid as dicarboxylic acid, or naphthalene 2.6 dicarboxylic acid, 1.4 butanediol as diole component, and poly The alkylene diol is particularly preferably a terpolymer block copolymer of polytetramethylene glycol or the terpolymer block copolymer of polylactone as the polyester diol. In a special case,
You can also use a kotatsu that has a polysiloxane-based soft segment introduced. Also, the thermoplastic elastomer resin of the present invention includes those obtained by blending the above elastomer with a non-elastomer component, those obtained by copolymerization, those obtained by softening the polyolefin component, and the like. As a polyamide elastomer, the hard segment includes nylon 6, nylon 66, nylon 610, nylon 612,
Polyethylene glycol, polypropylene glycol, polytetramethylene glycol having an average molecular weight of about 300 to 5000 is used as the soft segment in the skeleton of nylon 11, nylon 12, etc. and their copolymerized nylon.
A block copolymer composed of at least one kind of polyalkylenediol such as ethylene oxide-propylene oxide copolymer may be used alone or in combination of two or more kinds. Furthermore, blends of non-elastomer components and copolymers thereof can be used in the present invention.
The polyurethane-based elastomer is (A) number average molecular weight of 1000 to 60 in the presence or absence of a usual solvent (dimethylformamide, dimethylacetamide, etc.).
00 has a hydroxyl group-terminated polyether and / or polyester, and (B) an organic diisocyanate-based polyisocyanate as a main component.
As a typical example, a polyurethane elastomer in which a chain-extended polyamine having a diamine (C) as a main component is added to a prepolymer which is a group having a hydroxyl group can be exemplified. The polyester or polyether of (A) has an average molecular weight of about 1,000.
To 6000, preferably 1300 to 5000, polybutylene adipate copolyester, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycol composed of ethylene oxide-propylene oxide copolymer, etc. Polyalkylenedio-
Are preferred, and as the polyisocyanate of (B),
Although a conventionally known polyisocyanate can be used, an isocyanate mainly composed of diphenylmethane 4,4 ′ diisocyanate may be used, and if necessary, a conventionally known triisocyanate and the like may be added in a small amount. (C)
As the polyamine, a known diamine such as ethylenediamine or 1.2-propylenediamine is mainly used, and if necessary, a trace amount of triamine or tetraamine may be used in combination. These polyurethane elastomers are used alone or
You may use it in mixture of 2 or more types. The melting point of the thermoplastic elastic resin of the present invention is preferably 140 ° C. or higher at which heat resistance and durability can be maintained, and it is more preferable to use a resin having a melting point of 160 ° C. or higher because heat resistance and durability are improved. Since the reticulated body of the present invention contains a phosphorus compound in order 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 to improve heat resistance and durability, if necessary. The antioxidant is preferably a hindered antioxidant, which includes a hindered phenol type and a hindered amine type, and does not contain nitrogen.
It is particularly preferable to add 1% to 5% of a dophenol-based antioxidant to suppress thermal decomposition, since 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.
As described above, it is more preferably 30% by weight or more, preferably 80% by weight or less, and more preferably 70% by weight or less in view of heat resistance and sag resistance. That is, the soft segment content of the component having the function of absorbing vibrations 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. .

In the flame-retardant reticulate material of the present invention, the phosphorus content (Bppm) in the thermoplastic elastic resin is 60A + 200≤B≤10 with respect to the soft segment content (A% by weight).
It is necessary to satisfy the relationship of 0000. If it is not satisfied, the flame retardance is poor, which is not preferable. 100000ppm
If it exceeds the range, the plastic deformation due to the plasticizing effect becomes large and the heat resistance of the thermoplastic elastic resin is deteriorated, which is not preferable. The preferred phosphorus content (Bppm) is the soft segment content (A
Weight%), 30A + 1800 ≦ B ≦ 100,000
And the more preferable phosphorus content (Bppm) is 16A + 2600 with respect to the soft segment content (A weight%).
≦ B ≦ 50000. For flame retardancy, there is a method to add a high level of flame retardancy by adding a large amount of halides and inorganic substances, but when burning, a large amount of toxic halogen gas with a small lethal amount is generated, and there is a problem of poisoning during fire. There is a large damage to the incinerator during incineration, which is not preferable. In the present invention, the halide content is at least 1% by weight or less, preferably the halide content is 0.5% by weight or less, more preferably the halide-free content. As the phosphorus-based flame retardant of the present invention, for example, in the case of a polyester-based thermoplastic elastic resin, a flame-retardant in the hard segment portion during resin polymerization is described, for example, in JP-A-51-82392. [2.3-di (2-hydroxyethoxy) -carbonylpropyl] 9-10-dihydro-
A method of preparing a polyester-based thermoplastic elastic resin in which a carboxylic acid such as 9-oxa-10-phosphaphenalene-10-oxylo is copolymerized as a part of the acid component of the hard segment, or a thermoplastic elastic resin is used in a subsequent step. For example, the flame retardancy can be imparted by adding a phosphorus compound such as the existing chemical substance number (3) -3735. Other flame retardants capable of imparting flame retardancy include various phosphoric acid esters, phosphorous acid esters, phosphonic acid esters (the above phosphoric acid esters containing a halogen element as necessary), or polymers derived from these phosphorus compounds. It can be illustrated. In the present invention, various modifiers, additives, colorants and the like can be added to the thermoplastic elastic resin as needed. The flame-retardant reticulate material of the present invention contains phosphorus in order to impart flame retardancy. The reason is, as described above, from the viewpoint of safety, cyan gas, halogen gas, etc. generated in a fire. The goal is to minimize the lethal dose of toxic gases. Therefore, the combustion gas toxicity index of the flame-retardant reticulate material 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 material and the wadding layer, it is preferable to use a polyester-based thermoplastic elastic resin for recycling without separation.

The thermoplastic elastic resin constituting the nonwoven fabric laminated network of the present invention preferably has an endothermic peak below the melting point in the melting curve measured by a differential scanning calorimeter. Those having an endothermic peak below the melting point have significantly improved heat resistance and sag resistance than those having no endothermic peak.
For example, a preferable polyester-based thermoplastic resin of the present invention contains 90 mol% or more of terephthalic acid or naphthalene 2.6 dicarboxylic acid having rigidity in the acid component of the hard segment, more preferably terephthalic acid or 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 a polyalkylene diol, preferably Average molecular weight is 5
00 or more and 5000 or less, particularly preferably 1000 or more and 3
When 000 or less of polytetramethylene glycol is copolymerized in an amount of 15% by weight or more and 70% by weight or less, more preferably 30% by weight or more and 60% by weight or less, terephthalate having rigidity in the acid component of the hard segment Acid and naphthalene 2.
6 When the content of dicarboxylic acid is high, the crystallinity of the hard segment is improved, the plastic deformation is less likely to occur, and the heat resistance and fatigue resistance are improved, but the temperature after melting heat bonding is lower than the melting point by at least 10 ° C or more. The annealing treatment improves the heat resistance and sag resistance. After applying compressive strain,
The ring further improves the heat resistance and sagging resistance. The endothermic peak is more clearly expressed in the melting curve measured by a differential scanning calorimeter of the linear structure of the network structure treated as described above at a temperature of room temperature or higher and melting point or lower. If annealing is not performed, no endothermic peak appears in the melting curve above room temperature and below the melting point. By analogy with this, it is considered that the annealing causes rearrangement of the hard segments and formation of pseudo-crystallization-like cross-linking points to improve the heat resistance and sag resistance. (This treatment is defined as pseudo crystallization treatment.) This pseudo crystallization treatment effect is also effective for polyamide elastic resin and polyurethane elastic resin.

According to the present invention, continuous filaments having a fineness of 100,000 denier or less made of a phosphorus-containing thermoplastic elastic resin are bent and brought into contact with each other to fuse most of the contact portions , and both surfaces are fused. Flattened three-dimensional mesh
It is a laminated component. The net-like body is taken up with the filaments in a molten state.
And the like sandwiched device, both sides are flattened (hereinafter
Below, this may be referred to as substantially flattening.
It ) Is and, two on one side or both sides of the mesh body
The non-woven fabric layers in which the composite short fibers made of the thermoplastic elastic resin of above form a three-dimensional structure and are fused and integrated are laminated and joined.
It The apparent density of the non-woven fabric laminate is 0.01 g / cm
³ to 0.2 g / cm ³ . The function of the cushion material is
The cushion layer is made up of a layer that thickens the basic fineness and makes it a little harder to support the body shape, and a layer that slightly increases the density with a component with good vibration damping properties to absorb the vibration and block the vibration, and the surface layer is the fineness As a soft layer with a narrower number of constituent fibers, it gives a comfortable touch to the buttocks by a proper subduction and evenly distributes the pressure distribution in the buttocks and absorbs vibrations that could not be absorbed by the cushion layer and By integrating the layer that blocks the vibration of the resonance portion, it is possible to integrally deform and absorb stress and vibration, and improve the sitting comfort. In the present invention, the function of the cushion layer is given to the net-like body formed with the fused three-dimensional three-dimensional structure made of the thermoplastic elastic resin, and the function of the surface layer is given to the short fiber nonwoven fabric made of the thermoplastic elastic resin, It is a non-woven fabric laminated reticulate body that can be joined and integrated to impart a preferable cushioning material function. The short fiber non-woven fabric having a surface layer function which constitutes the laminated reticulate body of the present invention is a soft layer and provides a comfortable buttocks touch due to a proper depression. Therefore, the fineness of the thermoplastic elastic resin is 20 denier or less. Composed of short fibers. When it exceeds 20 denier, the apparent density of the short fiber non-woven fabric can impart a preferable surface layer function to 0.01 g / cm ³ or more and 0.05 g / cm ³ or more.
When the number is ³ or less, the number of constituents is reduced, the feature as a dense structure is not exhibited, and the comfortable touch is impaired, which is not preferable. Further, in the case where the short fiber is a non-elastic resin, the larger the fineness, the greater the mechanical deformation of the non-elastic resin against the compression deformation, and the larger the damage , the lower the sag resistance ,
On the other hand, if the fineness is too small, the bulkiness decreases, the deformation response deteriorates, and the function of the surface layer decreases. The fineness of the short fibers is preferably 1 denier to 10 denier, and more preferably 3 denier to 6 denier. Further, the short fibers made of the thermoplastic elastic resin are three-dimensionally structured, and most of the contact portions are substantially fused and integrated by heat bonding (preferably all the contact points are fused and integrated). By making the non-woven fabric flat, the local pressure of the buttocks is received on the surface, the pressure distribution is uniformly dispersed, and the short fibers whose thermo-adhesive component is thermoplastic elastic resin form a three-dimensional structure. Since it is fused and integrated, the entire structure deforms while the thermal bonding point undergoes large deformation and absorbs the deformation stress by energy conversion, and when the deformation stress is released, the rubber elasticity of the thermoplastic elastic resin causes Since it has a function to easily restore the original form, it has good sag resistance. Further, the damage to the cushion layer can be gradually reduced, and the sag resistance of the entire structure is improved. If they are not fused and integrated, the shape cannot be maintained, the local pressure is received by the surface, the pressure distribution cannot be evenly distributed, and the entire structure is deformed and energy conversion is not possible. Inferior and not preferable. Since the surface layer is composed of short fibers made of thermoplastic elastic resin with good vibration absorption, it also functions as a layer that cuts off the vibration of the resonance part of the human body by absorbing the vibration that could not be absorbed by the cushion layer. Support When the short fiber is made of a thermoplastic non-elastic resin, it cannot follow local deformation stress, so that the structure is destroyed due to stress concentration and recovery is poor, which is not preferable. Further, since the thermoplastic non-elastic resin has a poor vibration absorbing property, it is not preferable because it has a poor function as a layer for blocking vibration. The thickness of the short fiber non-woven fabric layer is not particularly limited, but is preferably 3 mm to 30 mm and particularly preferably 5 mm to 20 mm so that the surface layer function can be exhibited. On the other hand, the mesh body having a cushion layer function is a three-dimensional three-dimensional structure in which continuous filaments made of a thermoplastic elastic resin are fused at most of the contact portions, and are fused and integrated, and both sides are substantially flat. Since the vibration absorption function of the thermoplastic elastic resin absorbs and attenuates most of the vibrations given from the outside, the surface of the reticulate body is substantially absorbed even when a large deformation stress is locally applied. Since most of the contact portion is flattened and fused, and the surface is joined with the short fiber non-woven fabric at the surface, it receives the deformation stress at the surface of the mesh body and disperses the deformation stress and develops the body shape holding function. Since the filaments made of thermoplastic elastic resin form a three-dimensional three-dimensional structure and are fused and integrated, the entire structure deforms to absorb the deformation stress by energy conversion, and the deformation stress is released. And thermoplastic elastic resin Is good sag resistance so easily have the ability to recover to original shape by elasticity. In the net-like body composed of the filaments made only of the known inelastic resin,
When subjected to a large deformation that cannot be absorbed by the surface layer, it does not have rubber elasticity, so plastic deformation occurs due to compressive deformation and recovery does not occur, resulting in poor durability. When the surface of the reticulate body is not substantially flattened, the local external force transmitted from the short fiber non-woven fabric is selectively transmitted to the filaments and bonding points of the surface, resulting in stress concentration. There is a possibility that fatigue due to stress concentration may occur due to such external force and the sag resistance may deteriorate. When the filaments are made of thermoplastic elastic resin, the entire structure is deformed in the three-dimensional structure portion, so stress concentration is relieved. However, in the non-elastic resin, stress is concentrated at the bonding point and structural damage is caused. It will not occur and will not recover. Furthermore, if the surface is not substantially flattened and has irregularities, the buttocks feel a foreign substance when sitting, which is unfavorable for sitting. When the linear shape is not continuous, the adhesive point becomes a stress transmission point in a net having a large fineness, so that remarkable stress concentration occurs at the adhesive point, resulting in structural destruction and poor heat resistance and durability. If they are not fused, the shape cannot be maintained and the structure does not deform integrally, resulting in a fatigue phenomenon due to stress concentration and poor durability, and at the same time deforming the shape and making it impossible to maintain the body shape, which is not preferable. . The more preferable degree of fusion in the present invention is that most of the portions where the filaments are in contact are fused, and most preferably all the contact portions are in fusion. Thus, continuous filaments made of a thermoplastic elastic resin having good vibration absorption and elastic recovery form a three-dimensional three-dimensional structure in which most of the contact portions are fused, and the fusion is integrated so that the surface is substantially flat. The reticulated body with the integrated cushioning layer function receives the deformation stress transmitted from the surface layer composed of the short-fiber non-woven fabric made of thermoplastic elastic resin on the surface to improve the dispersion of the stress and improve the stress applied to each linear shape. The entire structure is deformed to absorb the deformation stress by improving the cushioning property to support the buttocks and recovers when the stress is released, and the vibration transmitted from the frame also has the vibration absorption and elastic recovery properties. The cushion layer made of a good thermoplastic elastic resin absorbs and blocks vibrations of the resonance part of the human body, so that the sitting comfort and durability can be improved. For this purpose, the fineness of the filament formed of the thermoplastic elastic resin having good vibration absorption and elastic recovery forming the reticulated body of the present invention is 100,000 denier or less. When the apparent density is 0.2 g / cm ³ or less, 10,000
If it exceeds 0 denier, the number of constituents is reduced, density unevenness is caused, and a structure having poor durability is partially formed. Fatigue due to stress concentration increases and durability is deteriorated, which is not preferable. The preferable fineness of the filament made of the thermoplastic elastic resin of the present invention is 100 denier or more, because if the fineness is too thin, the anti-compression property becomes too low and the stress absorbability due to deformation is lowered. Is not more than 50,000 denier which does not impair the denseness of the structural surface. More preferably 5
It is not less than 00 denier and not more than 10,000 denier. When the apparent density of the reticulate body of the present invention is 0.005 g / cm ³ , the repulsive force is lost, and the vibration absorbing ability and the deformation stress absorbing ability become insufficient, which may make it difficult to develop the cushion function. If it is cm ³ or more, the repulsive force may be too high and the sitting comfort may be poor, so it is easy to develop the function as a cushion body by taking advantage of the vibration absorption capacity and the deformation stress absorption function 0.01 g / cm ³ or more 0.20 g / Cm ³ or less is preferable, and more preferably 0.03 g / cm ³ or more and 0.1.
It is not more than 08 g / cm ³ . As a preferred embodiment, a method in which the reticulate body in the present invention has a different fineness laminated structure in which a linear shape having a different fineness is combined with an apparent density to have an optimum configuration can be selected. The thickness of the reticulate body of the present invention is not particularly limited, but if the thickness is less than 5 mm, the stress absorbing function and the stress dispersing function are deteriorated. 10mm thickness
It is above, more preferably 20 mm or more. The apparent density as a laminated net body in which the net body of the present invention and the short fiber non-woven fabric are integrally bonded is 0.01 g / cm ³ to 0.2 g /
It is cm ³ . If it is less than 0.01 g / cm ³ , the cushioning function such as body shape retention and vibration absorption is deteriorated, which is not preferable. If it exceeds 0.2 g / cm ³ , the impact resilience becomes large and the sitting comfort becomes poor, which is not preferable. Preferred apparent density is ^{0.02g / cm 3 ~0.1g / cm 3} , more preferably ^{0.03g / cm 3 ~0.06g / cm 3} .

The cross-sectional shape of the filaments of the reticulate body of the present invention is not particularly limited, but a hollow cross-section or a deformed cross-section is particularly preferable because it can impart preferable anti-compression property (repulsive force) and touch. The anti-compression property can be adjusted by the fineness and the modulus of the material used to make the fineness fine, or in the soft material the hollowness and the irregularity can be increased to adjust the gradient of the initial compression stress, and the fineness can be made slightly thicker or slightly. A material with a high modulus lowers the hollow ratio and the degree of irregularity to provide anti-compression property with a comfortable sitting feeling. As another effect of the hollow cross section and the irregular cross section, by increasing the hollow ratio and the degree of irregularity, if the same anti-compression property is given, the weight can be further reduced, and the energy saving can be achieved when it is used for the seat of an automobile or the like. If it is a futon or the like, it will be easier to handle when raising and lowering. As another preferable method for imparting preferable anti-compression property (repulsive force) and touch, there is a method of forming the filament of the reticulated body of the present invention into a composite structure. Examples of the composite structure include a score core structure, a side-by-side structure, and a combination structure thereof. However, in particular, 50% or more of the linear surface is softly heat-treated in order to form a three-dimensional three-dimensional structure capable of energy-converting and recovering vibration and deformation stress that cannot be energy-converted even if the thermoplastic elastic resin layer is largely deformed. Examples thereof include a sheath core structure or a side-by-side structure occupied by a plastic elastic resin, and a combination thereof. That is, see
In the score structure, the sheath component is a thermoplastic elastic resin with a large soft segment content that facilitates energy conversion of vibrations and deformation stresses, and the core component is a thermoplastic elastic resin with a small soft segment content to provide anti-compression properties. By giving it, it is possible to give a comfortable touch to the buttocks due to a proper depression. In the side-by-side structure, the melt viscosity of a thermoplastic elastic resin with a high soft segment content that facilitates energy conversion of vibration and deformation stress is made lower than that of a thermoplastic elastic resin with a low soft segment content that exhibits anti-compressibility. A structure in which the proportion of thermoplastic elastic resin occupying a linear surface and having a large amount of soft segment is increased (metaphorically, a structure in which a thermoplastic elastic resin is arranged in an eccentric sheath-core structure) ), The proportion of the thermoplastic elastic resin occupying the linear surface and having a large soft segment content is 80
% Or more is particularly preferable, and most preferably, it is a sheath core in which the proportion of the thermoplastic elastic resin having a large soft segment content occupying the linear surface is 100%. When the proportion of the thermoplastic elastic resin with a large soft segment content that occupies the linear surface is large, the flowability when melting and fusing is high, so there is the effect of strengthening the adhesion, and the structure deforms as a unit. In this case, the fatigue resistance against stress concentration at the bonding points is improved, and the heat resistance and durability are further improved.

A net-like body made of a thermoplastic elastic resin and a short fiber non-woven fabric made of a thermoplastic elastic resin are joined and integrated,
Since it is a non-woven laminate reticulated body whose both sides are substantially flattened, other reticulate bodies, non-woven fabrics, knitted fabrics, hard cotton, films, foams, metal, etc. A heat-bonding component (heat-bonding non-woven fabric, heat-bonding fiber, heat-bonding film, heat-bonding resin, etc.) or an adhesive is used to form an integrally laminated structure, and it is used as a vehicle seat, a ship seat, a vehicle, a ship,
When obtaining products such as hospital and other commercial and household beds, furniture chairs, office chairs, duvets, etc., the contact area with the surface to be adhered can be widened, resulting in a wider adhesive area and strong adhesive bonding. A product with good durability can be obtained. In this case, since a flame-retardant integrally laminated structure can be obtained by using a flame-retardant heat-bonded body, the present invention is a particularly preferred embodiment. In addition, by performing the above-mentioned pseudo crystallization treatment at any stage from the stage of forming the net body and the laminated net body into the product, the component made of the thermoplastic elastic resin in the structure was measured by a differential scanning calorimeter. It is more preferable that the melting curve has an endothermic peak at a temperature of room temperature or higher and melting point or lower because the heat resistance and durability of the product is remarkably improved. When the filaments of the reticulated body forming the non-woven fabric laminated network of the present invention have a composite structure, or by laminating the non-woven fabric layer of the thermoadhesive fiber made of the thermoplastic elastic resin, the back surface of the non-woven fabric reticulated body is heated. An adhesive function can also be added, and a reinforcing material and the like can be integrated into a thermal adhesive structure. For example, in the score structure,
The thermoplastic elastic resin containing a large amount of soft segment that facilitates energy conversion of the vibration and deformation stress of the core component is used as the thermal adhesive component, and the thermoplastic elastic resin containing a small amount of soft segment showing the anticompressibility of the core component is reticulated. The function of the heat-bonding layer can also be imparted by using a high-melting-point component having a shape retaining function and having a melting point of the heat-bonding component lower than that of the high-melting-point resin by 10 ° C. or more. Also,
The short-fiber non-woven fabric of the surface layer of the laminated structure of the present invention is composed of a heat-bonding fiber having a low-melting point thermoplastic elastic resin having a high soft segment content that easily converts energy of vibration and deformation stress into a heat-bonding component. The heat-bonding function can be imparted also by that. The melting point of the heat-adhesive component forming the filaments or fibers in the laminated reticulate body that is preferable for exhibiting the heat-adhesive function is 15 ° C. to 80 ° C. lower than the melting point of the high-melting component, more preferably 20 ° C. to 60 ° C. It has a low melting point. The non-woven fabric laminated network of the present invention having a heat-bonding function has a substantially flat surface, and most of the contact portions are fused,
Since the contact area with the surface of the object to be heat-bonded, such as a mesh, a non-woven fabric, a knitted woven fabric, a hard cotton, a film, a foam, and a metal, can be widened, the heat-bonded area can be widened, and a new molded body and vehicle can be firmly heat-bonded. Seats, seats for ships, vehicles, ships, hospital beds, and other commercial and household beds, furniture chairs, office chairs,
You can get futon products. In addition, by performing pseudo crystallization at any stage until new molded products and products are commercialized, the filaments made of the thermoplastic elastic resin in the structure are melted by a differential scanning calorimeter. It is more preferable to make the curve have an endothermic peak at a temperature of room temperature or higher and melting point or lower because a product with significantly improved heat resistance and durability can be provided. When the adherend is adhered in a stretched state at the time of heat-bonding, the adhered body does not relax the stretched state due to the rubber elasticity of the adhesive layer, so that the adherend can be a molded body having tension and less likely to wrinkle.

Next, the manufacturing method of the present invention will be described. According to the manufacturing method of the present invention, the soft segment amount (A% by weight) and the phosphorus content (Bppm) are 60 A compared with the multi-row nozzle having a plurality of orifices.
A thermoplastic elastic resin satisfying the relationship of + 200 ≦ B ≦ 100,000 is distributed to each nozzle orifice, and at a melting temperature higher than the melting point of the thermoplastic resin by 10 ° C. or more and less than 80 ° C.,
After being discharged downward from the nozzle, and in a molten state, they are brought into contact with each other and fused to form a three-dimensional structure, sandwiched by a take-up device and cooled in a cooling tank, and then one side or both sides are made of thermoplastic elastic resin. It is a method of manufacturing a non-woven laminate network in which short-length fibers are opened and three-dimensionalized webs are laminated, and thermoformed while being compressed, and preferably thermoplastic is used in the process leading to commercialization after cooling and integral molding. It is a method for producing a nonwoven fabric laminated network and a product which are annealed at a temperature of at least 10 ° C. or lower than the melting point of the elastic resin. In the present invention, as described above, the phosphorus-containing thermoplastic elastic resin can be added by a method of adding a phosphorus compound at the time of polymerization and copolymerization, or a method of adding a phosphorus compound after polymerization and mixing and kneading. The mixing and kneading can be performed by using a twin-screw kneading extruder or a single-screw extruder having a kneading function such as a dullage, a pin, or the like, which can be performed before melt extrusion or during melt extrusion. If a fixed amount of flame retardant can be supplied, kneading at the time of melt extrusion is the cheapest method. Solid flame retardant can be easily mixed with resin and supplied to the extruder so as not to segregate.However, liquid flame retardant is supplied to the kneading extruder in a fixed amount while liquid flame retardant is also measured separately. It is most desirable to take the method of kneading while supplying. For example, a method of quantitatively supplying a liquid flame retardant through a vent hole of a twin-screw kneading extruder can be exemplified. With such a method, the soft segment amount (A% by weight) and the phosphorus content (Bppm) are 6
A phosphorus content satisfying the relation of 0A + 200 ≦ B ≦ 100,000 is added to the thermoplastic elastic resin, and then a reticulate body is formed. The reticulate body is obtained by melting a thermoplastic elastic resin by using a general melt extruder, supplying the multi-row nozzle having a plurality of orifices, and discharging the resin downward from the orifices. The melting temperature at this time is 20 ° C. to 80 ° C. from the melting point of the thermoplastic elastic resin.
℃ is a high temperature. 80 ° C from the melting point of the thermoplastic elastic resin
If the melting temperature is higher than this, thermal decomposition will be remarkable and the rubber elasticity of the thermoplastic elastic resin will be deteriorated, which is not preferable. On the other hand, unless the temperature is higher than the melting point of the thermoplastic elastic resin by 10 ° C. or more, melt fracture occurs and normal filament formation cannot be performed. Further, when the filament is formed by looping after discharge and is brought into contact and fused. The temperature may be lowered and the filaments may not be fused to each other, resulting in a network having insufficient adhesion, which is not preferable. The preferred melting temperature is 20 ° C to 60 ° C above the melting point
Higher temperatures, more preferably 25 ° C to 40 ° C above the melting point. The shape of the orifice is not particularly limited, but may be a hollow cross section (for example, a triangular hollow shape, a round hollow shape, a shape with a protrusion, etc.) and / or an irregular cross section (for example, a triangular, Y-shaped, star-shaped cross-section secondary mode). In addition to the above effects, it is difficult for the three-dimensional structure formed by the discharge filaments in the molten state to relax the flow, and on the contrary, the flow time at the contact point is maintained for a long time to strengthen the adhesion point. It is particularly preferable because it can be When heating for adhesion as described in Japanese Patent Application Laid-Open No. 1-2075, the three-dimensional structure is easily relaxed, a planar structure is formed, and a three-dimensional three-dimensional structure becomes difficult, which is not preferable. As an effect of improving the properties of the reticulate body, the apparent bulk can be increased, the weight can be reduced, the anti-compression property can be improved, and the elasticity can be improved, which is difficult to obtain. The hollow section has a hollow ratio of 8
If it exceeds 0%, the cross section tends to be crushed, so that it is preferably 10% or more and 70% or less, more preferably 20% or more and 60% or less so that the effect of weight reduction can be exhibited. The pitch between the holes of the orifice needs to be a pitch with which the loop formed by the line can sufficiently contact. The pitch between holes is shortened for a dense structure, and the pitch between holes is lengthened for a coarse structure. The pitch between the holes of the present invention is preferably 3 mm to 20 mm, more preferably 5 mm to 10 mm. In the present invention, different densities and different fineness 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 also changed, or a method in which the pitch between both rows and 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 principle that the discharged amount of molten thermoplastic elastic resin extruded from the same nozzle at a constant pressure becomes smaller for the orifice with larger pressure loss, is used. It is possible to manufacture a reticulated structure composed of filaments of different fineness by using a nozzle having at least a plurality of rows having different cross-sectional areas of orifices in a section in the longitudinal direction. Then, discharge downward from the nozzle,
While forming a loop, they are brought into contact with each other in a molten state and fused to form a three-dimensional structure, and are sandwiched by a take-up net, and the winding winding filaments in the molten state on the surface of the mesh body are bent by 45 ° or more. After deforming to flatten the surface and at the same time form a structure by adhering the contact points with the discharge line that is not bent, a cooling medium (usually using room temperature water can increase the cooling rate, It is preferable because it is cheap in terms of cost), and is rapidly cooled to obtain the three-dimensional three-dimensional net-structured net-like body of the present invention. The distance between the nozzle surface and the take-off point is preferably at least 40 cm or less to prevent the discharge filament from being cooled and the contact portion not being fused. If the discharge amount of the discharge line is 5g / hole or more, 10cm-40
cm is preferable, and 5 cm to 20 cm is preferable when the discharge amount of the discharge filament is less than 5 g / hole. The thickness of the net-like body is determined by the opening width (interval between the take-up nets) of the take-up net sandwiching both surfaces of the three-dimensional structure in the molten state. In the present invention, the opening width of the take-up net is set to 5 mm or more for the above reason. Next, it is drained and dried, but if a surfactant or the like is added to the cooling medium, draining and drying may be difficult, or the thermoplastic elastic resin may swell, which is not preferable. still,
The desired loop diameter and wire diameter can be determined by the distance between the nozzle surface and the take-up conveyor installed on the cooling medium that solidifies the resin, the melt viscosity of the resin, the hole diameter of the orifice and the discharge amount, and the like. A pair of take-up conveyors with adjustable spacing installed on the cooling medium sandwiches and holds the melted discharge filaments to fuse the portions that are in contact with each other and continuously draw in the cooling medium to solidify. By adjusting the distance between the conveyors when forming the body, the thickness can be adjusted while the fused net-like body is in a molten state, and a desired thickness can be obtained. If the conveyor speed is too high, the formation of contact points may be insufficient, or the contact point may be cooled until the fusion point is sufficiently formed, resulting in insufficient fusion of the contact portion.
Further, if the speed is too slow, the melt will stay too much and the density will increase, so it is necessary to set the conveyor speed suitable for the desired apparent density. Next, in the production method of the present invention, it is joined and integrated with a short fiber non-woven fabric having a surface layer function. A short fiber having a fineness of 20 denier or less, which is made of a thermoplastic elastic resin, is a known composite spinning obtained by individually melting a low-melting point thermoplastic elastic resin as a heat-bonding component and a high-melting point thermoplastic elastic resin as a core component. Thus, a spun yarn can be obtained by spinning and stretching. However, in this method, since the heat-adhesive component has a low melting point, heat setting at a high temperature cannot be performed at the time of stretching, so that only a high shrinkage rate of 30% to 80% can be obtained. Dimensional defects occur. In the present invention, in order to solve this problem, it is preferable to obtain the finished yarn at a stretch by reducing the shrinkage rate to 10% or less by high-speed spinning at 3000 m / min or more. Next, crimping is applied and cut into a desired cut length to obtain short fibers. Although the composite form of the short fibers used in the present invention is not particularly limited, it is preferable that the low melting point component occupies 50% or more of the surface of the fiber in the side-by-side or the score, since the function as the heat-bonding fiber is required. The low melting point component is 1 on the surface of the fiber.
It is more preferable to occupy at least 00%. The short fibers thus obtained are provided with an opening web having a three-dimensional opening structure with a card or the like, which is laminated and compressed on the surface of the reticulated body and bonded and integrated by thermoforming, or once opened. It is also possible to laminate and compress only the above to form a structure by thermoforming to form a short fiber non-woven fabric, and then join and integrate the net body and the short fiber non-woven fabric. In this case, a thermal adhesive layer or an adhesive may be separately used between the reticulate body and the short fiber non-woven fabric for bonding and integration, or the thermal rebonding function of the reticulate body or the short fiber non-woven fabric may be used for bonding and integration. Good. As a preferred method of the present invention, the laminated reticulate body obtained by cooling the reticulate body once or by integrally molding the reticulated body at a temperature of at least 10 ° C. or lower than the melting point of the thermoplastic elastic resin in any step leading to commercialization. A more preferable production method is to obtain a laminated reticulate body or a product by performing a pseudo-crystallization treatment by annealing. Pseudo-crystallization treatment temperature is
At least 10 ° C. lower than the melting point (Tm), Tan δ
The temperature is higher than the α dispersion rising temperature (Tαcr). By this treatment, the heat-resistant sag resistance is remarkably improved as compared with the one having no endothermic peak (having no endothermic peak) having an endothermic peak below the melting point. The preferred pseudo-crystallization treatment temperature of the present invention is (Tαcr + 10 ° C) to (Tm-20 ° C).
Is. If it is pseudo-crystallized by simple heat treatment, heat resistance and sag resistance are improved. However, it is more preferable to impart compressive deformation of 10% or more and anneal to significantly improve the heat resistance and sag resistance. Further, when the reticulate body is once cooled and then subjected to a drying step, the pseudo crystallization treatment can be simultaneously performed by setting the drying temperature to the annealing temperature. Also, a pseudo crystallization treatment can be separately performed in the process of commercialization. Then, it is cut into a desired length or shape and used as a cushion material.

When the non-woven fabric laminated network of the present invention is used as a cushion, it is necessary to select the resin to be used, the fineness, the loop diameter and the bulk density depending on the purpose of use and the site of use. For example, in order to impart a soft touch, moderate depression and bulging with tension, it is preferable to have a low density and fine fineness and a fine loop diameter. Low frequency, moderate hardness and linear change of hysteresis at the time of compression to improve body retention, and to maintain durability, medium density, thick fineness,
It is preferable to have a structure in which a layer having a rather large loop diameter and a layer having a low density, a fine fineness, and a fine loop diameter are laminated and integrated.
Further, it can be used for vehicle seats, boat seats, beds, chairs, furniture, etc. by molding it into a shape suitable for the purpose of use by using a molding die or the like to the extent that the three-dimensional structure is not impaired, and then covering the side fabric as it is. . Of course, it is also possible to use it in combination with other materials such as a different mesh body, a hard cotton cushion material composed of a short fiber aggregate, a non-woven fabric or the like so as to meet the required performance in relation to the application. In addition, other than the resin manufacturing process, the molded product is processed from the manufacturing process to the extent that performance is not deteriorated, and at any stage of commercialization, it becomes flame retardant, insecticidal, antibacterial, heat resistant, water / oil repellent, colored, aroma, etc. It is possible to perform the processing such as the addition of chemicals to add the function.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples.

The evaluations in the examples were carried out by the following methods. 1. Melting point (Tm) and endothermic peak below melting point T * 50 manufactured by Shimadzu Corporation, DSC50 type differential thermal analyzer was used, and the endothermic peak ( Melting peak) temperature was determined. 2. Heat the Tαcr polymer to a melting point of + 10 ° C to a thickness of approximately 300 μm.
Film was prepared and measured using a Vibron DDVII type manufactured by Orientec Co., Ltd. at a rate of 110 Hz and a heating rate of 1 ° C./min. Tan δ (the ratio of the imaginary elastic modulus M ″ to the real part M ′ of the elastic modulus M ″ / The rising temperature of α dispersion corresponding to the transition temperature from the rubber elastic region to the melting region of M ′). 3. Apparent density The sample is cut into a size of 15 cm x 15 cm, the heights at four locations are measured, the volume is calculated, and the weight of the sample is divided by the volume. (Average value of n = 4) 4. Fineness of the filaments Each filament portion is cut out from 10 locations, embedded in acrylic resin, the cross section is cut out to prepare a section, and a cross-section photograph is obtained. The cross-sectional area (Si) of each part is obtained from the cross-sectional photograph of each part. In addition, a piece obtained in the same manner was dissolved in acrylic resin with acetone, degassed in vacuum, and a density gradient tube was used to 40 ° C.
Determine the specific gravity (SGi) measured in. Then, a linear weight of 9000 m is obtained from the following equation. (Unit: cgs) Fineness = [(1 / n) ΣSi × SGi] × 9000000 5. Whether or not the fusion-bonded sample is fused by visual judgment Is it not possible to pull the fibers adhering together by hand to separate them? It is judged that something that does not come off is fused. 6. Flame-retardant By the F-MVSS302 method, those satisfying the flame-retardant standard (extinguishing the flame in 60 seconds or less) were judged as pass, and those not satisfying the criteria were judged as fail. 7. Combustion gas toxicity index Shown as an integrated value of the values obtained by dividing each combustion gas amount (mg) measured by the method of JIS-K-7217 by the lethal dose (mg / 10 liter) after 10 minutes of inhalation. 8. Heat resistance and durability (residual strain at 70 ° C) A sample was cut into a size of 15 cm × 15 cm, compressed by 50%, left in dry heat at 70 ° C for 22 hours, then cooled to remove compression strain and left for 1 day ( b) is obtained, and is calculated from the thickness (a) before processing by the following equation, that is, (ab) / a × 100. Unit% (average value of n = 3) 9. Cyclic compression strain sample is cut into a size of 15 cm × 15 cm, and is 50% in a room at 25 ° C. 65% RH with a Shimadzu Servo Pulser.
The thickness (b) after leaving the sample for 20,000 times after repeating compression recovery at a cycle of 1 Hz up to the thickness of 1 is calculated from the thickness (a) before the treatment, that is, (ab) / ax Calculated from 100. Unit% (average value of n = 3) 10. Sit comforting The nonwoven fabric laminated mesh cut into the shape of the bucket sheet is put in the female mold for thermoforming and compressed by the oyster mold to be packed 160
Thermoforming for 5 minutes with hot air at ℃ to 230 ℃
The side cushion of TOYOBO HEIM made polyester moquette was put on the cushion shaped like a toe, and it was set on the seat frame, and four side stoppers were placed on the seat and six on the back. A seat was prepared, and a paneler was allowed to sit on the seat prepared in a room at 30 ° C. and RH 75%, and the following evaluation was performed. (N
= 5) (1) Feeling on the floor: The "dosun" when sitting and the degree of feeling when hitting the floor were qualitatively and qualitatively evaluated. Not felt; ◎, hardly felt; ○, slightly felt; △, felt; × (2) Feeling of stuffiness: Feeling stuffy when sitting for 2 hours and the buttocks and the part of the crotch that contacts the seat inside the crotch Qualitatively evaluated. Almost no feeling: ◎, slightly stuffy; ○, slightly stuffy; △, significantly stuffy; × (3) How long you can sit in the seat within 8 hours: within 1 hour; × within 2 hours; △ within 4 hours;
○ 4 hours or more; ◎ (4) A qualitative qualitative evaluation was performed on the degree of waist fatigue when the user sat in the seat for 4 hours. None; ◎, almost no tiredness; ○, slightly tired; △, very tired; × (5) Overall evaluation: 4 points in the evaluation of (1) to (4), 3 points in ○, 2 points in △ Points, x = 1 point and 12 points or more without △; very good (◎), 12 points or more with △; good (○), 10 points or more without x; somewhat bad Those including (Δ) and ×; evaluated as bad (×).

Examples 1 and 2 Dimethyl terephthalate (DMT) or dimethyl naphthalate (DM) was used as the polyester elastomer.
N) and 1.4 butanediol (1.4 BD) were charged with a small amount of a catalyst, and after transesterification by a conventional method, polytetramethylene glycol (PTMG) was added and polycondensation was performed while heating and depressurizing. -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.

[0020]

[Table 1]

Orifice shapes having a staggered arrangement with a hole-to-hole pitch of 10 mm in the width direction and a hole-to-hole pitch of 5 mm on the nozzle effective surface of 50 cm in width and 5 cm in length are 2 mm in outer diameter and 1.6 in inner diameter.
The resulting thermoplastic elastic resin raw material (A-1 and A-
2) and 2) are separately supplied in a fixed amount by an extruder having two kneading functions, and the existing chemical substance number (3) -37 is used as a flame retardant.
35 was added so as to have a phosphorus content of 10000 ppm and melted, and A-1 and A-2 were made just before the orifice so that A-1 became the sheath component and A-2 became the core component (see Su /
Core: 50/50 weight ratio) Dispensed, at a melting temperature of 245 ° C., single hole discharge rate 2 g / min (A-1: 1 g / min, A-2:
1 g / min), the cooling water is placed below the nozzle surface 10 cm, and stainless steel endless nets with a width of 60 cm are arranged in parallel at intervals of 5 cm so that a part of the pair of take-up conveyors appears on the water surface. Then, the melted discharge line is bent to form a loop, and the contact portion is fused.
A two-dimensional network structure is formed, and both surfaces of the molten network structure are sandwiched by a take-up conveyor-at a speed of 1 m / min.
A net made of a phosphorus-containing thermoplastic elastic resin obtained by pulling into cooling water at 5 ° C. and solidifying to melt and flatten both surfaces and then cutting to a predetermined size has a cross-sectional shape of a sheath core structure. Triangular rice ball type hollow cross section with a hollowness of 38%, fineness of 9000 denier, and an average apparent density of 0.045 g / cm ³ and a phosphorus content of 10,000 p
It was pm (60A + 200 = 2780ppm). Separately, the thermoplastic elastic resin A-1 is individually melted by a conventional method so that the thermoplastic elastic resin A-1 becomes the sheath component and A-2 becomes the core component, and is dispensed immediately before the orifice, and each discharge is performed. In a 50/50 weight ratio, 1.6 g / min per hole (0.
8 g / min: 0.8 g / min) at a spinning temperature of 245 ° C., a spinning speed of 3500 m / min, a fineness of 4.1 denier, and a shrinkage rate of 6% at a dry heat of 160 °. Then, a mechanical crimp was applied by a crimper in a tow shape and cut into 64 mm to obtain a short fiber made of a thermoplastic elastic resin having a sheath core cross section. A web obtained by pre-opening the short fibers with an opener and then opening with a card was laminated to have a basis weight of 1000 g / m ^{2, and} was laminated to the reticulated body to give an apparent density of 0.05 g / m ^2. cm
The mixture was compressed to ³ and heat-treated with hot air at 180 ° C. for 5 minutes and then cooled to obtain a laminated structure having flat surfaces on both sides. Next, Table 2 shows the characteristics of the flame-retardant laminated network of the present invention obtained by compressing 10% of the thickness and performing pseudo-crystallization treatment with hot air at 100 ° C. for 20 minutes. As is clear from Table 2, Example 1 is a laminated reticulate body that takes advantage of the characteristics of the soft elastic resin, and thus has excellent heat resistance and durability at room temperature, is comfortable to sit on, has a nonwoven fabric, and has a combustion gas toxicity index. It was a cushion material with low safety. It can be seen that the seat created for evaluation also has excellent performance.

[0022]

[Table 2]

Example 2 20 mol% of dimethyl isophthalate (DMI) and DMT
Table 1 shows the formulation of the 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.
A nozzle having a circular cross section with a hole diameter of 1 mm was used for the orifice, and only A-3 was used as a single component, and the phosphorus content was 9000.
The reticulate body obtained in the same manner as in Example 1 except that the flame retardant was added so as to be in ppm was a solid round cross section with a fineness of 9000 deniers.
The average apparent density is 0.
046g / cm ³ , phosphorus content 9000ppm (60A + 2
00 = 3320 ppm). Then, the properties of the laminated network obtained in the same manner as in Example 1 are shown in Table 2. As is clear from Table 2, Example 2 is a cushion with high heat resistance and durability at room temperature that can be used practically, has excellent sitting comfort, has flame retardancy, and has a low toxicity index of combustion gas and high safety. It is clear that the seats made for evaluation are excellent because they are made of wood.

Example 3 As a polyurethane 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. Table 3 shows the formulation of the polyether urethane polymer after kneading, pelletizing and vacuum drying.

[0025]

[Table 3]

The thermoplastic elastic resin thus obtained (seed component:
B-1, core component: B-2) with a phosphorus content of 12,000 pp
A flame-retardant was added so that the melting point became m, and the melting temperature was 220 ° C.
The cross-sectional shape of the score structure is a triangular rice ball type hollow cross section with a hollow ratio of 40%, a fineness of 9800 denier, an average apparent density of 0.047 g / cm ³ , and a phosphorus content of 12000 ppm.
It was (60A + 200 = 3260ppm). On the other hand,
The properties of the composite fiber obtained in the same manner as in Example 1 except that B-1 was the sheath component, B-2 was the core component, and the spinning temperature was 235 ° C. were that the fineness was 4.5 denier, The shrinkage ratio at 150 ° C. was 3%. This composite fiber was formed into a laminated web of 1000 g / m ^{2 in} the same manner as in Example 1, laminated with the mesh, heat-treated with hot air at 160 ° C. for 5 minutes and then cooled to obtain a laminated structure having flat both sides. . Then 10% of thickness
Table 2 shows the properties of the laminated network of the present invention obtained by compression and quasi-crystallization for 20 minutes with hot air at 100 ° C. Example 3 is a cushioning material with high safety, which is a laminated reticulated body that takes advantage of the characteristics of soft urethane, has excellent heat resistance, durability at room temperature, and comfortable to sit on, has flame retardancy, and has a low toxicity index of combustion gas. there were. It can be seen that the seat created for evaluation is also excellent.

Comparative Example 1 Polyethylene terephthalate (PE having an intrinsic viscosity of 0.63)
T) The reticulate body used in Comparative Example 1 obtained in the same manner as in Example 2 except that the 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 , phosphorus content 5000 ppm (60 A + 200 =
200 ppm). Next, 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 has flame retardancy, but has poor heat resistance and durability due to the reticulated body made of non-elastic polyester,
It is a cushion material that is hard and uncomfortable to sit on, even though a short fiber non-woven fabric whose thermo-adhesive component is a thermoplastic elastic resin is used for the surface layer.

Comparative Example 2 A reticulate body obtained in the same manner as in Example 2 except that a flame retardant was added so that the phosphorus content was 200 ppm was formed from filaments having a solid round cross section and a fineness of 9000 denier. And an average apparent density of 0.046 g / cm ³ and a phosphorus content of 200 pp
It was m (60A + 200 = 3320ppm). Next, Table 2 shows the characteristics of the laminated network obtained in the same manner as in Example 2 except that the pseudo crystallization treatment was not performed. Comparative Example 2 is an example of a cushioning material which is made of a thermoplastic elastic resin and therefore is comfortable to sit on, but is poor in heat resistance and durability and fails in flame retardancy.

Comparative Example 3 Example 2 was repeated except that a take-up conveyor net was placed 60 cm below the nozzle surface and no pseudo-crystallization treatment was performed after the take-up conveyor net was taken.
Table 2 shows a part of the properties of the reticulate body obtained by the same method as described above.
The flame retardancy, apparent density, residual strain at 70 ° C., repeated compressive strain, and sitting comfort were not evaluated because the adhesive state is poor and it is difficult to adhere to the non-woven fabric and the shape retention is poor. Comparative Example 3 is an example that is not suitable for a cushioning material because its shape is not fixed.

Comparative Example 4 A reticulate body obtained in the same manner as in Example 2 except that a flame retardant was added so that the phosphorus content was 121,000 ppm was formed from filaments having a solid round cross section and a fineness of 9000 denier. The average apparent density is 0.046 g / cm ³ , and the phosphorus content is 121000 ppm (60 A + 200 = 3320 pp).
m). Next, Table 2 shows the characteristics of the laminated network obtained in the same manner as in Example 2 except that the pseudo crystallization treatment was not performed. In Comparative Example 4, the phosphorus content is too large, and thus the flame-retardant property is passed, but the characteristics of the thermoplastic elastic resin are deteriorated, the sitting comfort is slightly inferior, and the heat resistance and durability are significantly inferior. It is an example of a material.

Comparative Example 5 Using a nozzle having a width of 50 cm and a length of 5 cm and having an orifice diameter of 1 mm in a staggered arrangement with a hole-to-hole pitch of 4 mm in the width direction and a hole-to-hole pitch of 3 mm in the length direction, a single hole was used. Of a filament obtained in the same manner as in Example 2 except that the discharge rate was 0.012 g / min, a take-up conveyor net was placed 5 cm below the nozzle surface, and the rate was 1.5 m / min. Fineness is 4
0 denier, apparent density 0.008 g / cm ³ , phosphorus content 9000 ppm (60A + 200 = 3320 ppm)
The apparent density of the laminated mesh is 0.00
Table 2 shows the characteristics of the laminated reticulate body prepared in the same manner as in Comparative Example 2 except that the composition was compressed to 9 g / cm ³ . Although Comparative Example 5 passes the flame retardancy, it is also a case where a dense reticulate body having a fine linear fineness is used as the cushion layer, and the apparent density is too low to cause large depressions and a feeling of flooring, resulting in a comfortable sitting feeling. It was a slightly inferior cushion material.

Comparative Example 6 Obtained in the same manner as in Example 2 except that the discharge rate per single hole was 3 g / min, the take-up conveyor net speed was 0.3 m / min, and no pseudo-crystallization treatment was performed. Streak fineness of 13
000 denier, the average apparent density of the reticulate body is 0.21.
g / cm ³ , phosphorus content 9000ppm (60A + 200 =
Table 3 shows the characteristics of the laminated reticulated body produced in the same manner as in Example 2 except that the reticulated body of 3320 ppm) was used and the pseudo crystallization treatment was not performed. Since Comparative Example 6 had a high apparent density, it was a cushioning material having a good touch but a little inferior sitting comfort, and insufficient heat resistance and durability.

Comparative Example 7 A nozzle having a width of 50 cm and a length of 5 cm and having a staggered arrangement of holes with a pitch of 10 mm in the width direction and a pitch of 20 mm between the holes in the length direction was used as a nozzle having a diameter of 2 mm to form a single hole. Discharge at a rate of 25 g / min per nozzle, nozzle surface 30 cm
The fineness of the filament obtained in the same manner as in Example 2 was 11 except that a take-up conveyor net was arranged below and the take-up was carried out at 1 m / min.
At 3000 denier, the average apparent density is 0.154 g.
/ Cm ³ , phosphorus content 9000ppm (60A + 200 = 3
Table 2 shows the characteristics of the laminated reticulated body prepared in the same manner as in Example 2 except that the reticulated body of 320 ppm) was used and the pseudo crystallization treatment was not performed. Comparative Example 5 was a cushioning material having a remarkably fineness and a density unevenness, and therefore passing flame retardancy, but having poor heat resistance and durability and a little poor sitting comfort.

Comparative Example 8 A filament obtained in the same manner as in Example 2 except that the pseudo crystallization treatment was not performed had a fineness of 9100 denier and an average apparent density of 0.
045g / cm ³ , phosphorus content 9000ppm (60A + 2
00 = 3320 ppm) reticulate body and 4-manufactured by Toyobo Co., Ltd.
Non-pseudo-crystallization treatment using 44-EE7 was performed, but a short-fiber non-woven fabric in which the thermo-adhesive fiber made of a thermoplastic inelastic resin was laminated in the same manner as in Example 2 was laminated on the surface layer, and joined and integrated. The characteristics of are shown in Table 2. In Comparative Example 8, since the cushion layer was made of the thermoplastic elastic resin, the cushioning material was comfortable to sit on, but was slightly poor in heat resistance and durability.

Comparative Example 9 The linear fineness obtained in the same manner as in Example 2 was 9000 denier, and the average apparent density of the reticulate body was 0. 0, except that the spacing (opening width) of the take-up conveyor net was 15 cm. 043 g / cm
³ , phosphorus content 9000ppm (60A + 200 = 332
Table 2 shows the characteristics of the laminated structure produced in the same manner as in Example 2 except that the reticulate body whose surface (0 ppm) was not substantially flattened was used and the pseudo crystallization treatment was not performed. Comparative Example 9 was a cushioning material having a somewhat inferior durability because of its low apparent density because of its uneven surface, poor thermal adhesion, and a slightly inferior sitting comfort with a feeling of foreign matter. .

Example 4 The non-woven laminate network obtained in Example 1 was cut into a length of 120 cm, quilted every 5 cm in thickness, 120 cm in width and 50 cm in length, and put in a side cloth of 120 cm in width and 200 cm in length to form a mattress. It was created. Place this mattress on the bed and
The panel comfort was sensory-evaluated by allowing 4 panelists to use it in a room at 5 ° C RH 65% for 7 hours. The bed is covered with sheets and the comforter is 1.8 kg down / feather: 90/1.
0 was used as batting, and the pillow was worn by the paneler every day. As a result of the evaluation, the bed was a bed which had no feeling of flooring, had a moderate depression, and did not feel stuffy and had a comfortable sleeping comfort. For comparison, a density of 0.04 g / cm ³ and a thickness of 10
Create a similar mattress with a cm urethane foam plate,
As a result of placing it on a bed and evaluating the comfort of the bed, it was a bed with a low feeling of flooring but a large degree of sinking and a slight stuffiness, which was uncomfortable to sleep.

Example 5 The non-woven fabric laminated net body obtained in Example 1 was prepared to have a width of 38 cm and a length of 40.
The corner was cut into a shape with 10 cm of the corner, and the polyester moquette used for sitting comfort evaluation was set on the side of the office chair frame, and the commercially available polyurethane was used for the cushion. Compared to a chair, it provides a comfortable sitting 4
As a result of evaluation by sitting for a while, the stuffy feeling, the feeling of flooring, and the time to be able to stand while sitting were remarkably excellent in those using the flame-retardant laminated reticulate body of the present invention.

[0038]

EFFECTS OF THE INVENTION The cushion layer is a net-like body in which the filaments made of a phosphorus-containing thermoplastic elastic resin having a good vibration and stress absorbing property form a three-dimensional three-dimensional structure and are fused and integrated and the surface is substantially flattened. The nonwoven fabric laminated structure of the present invention, in which a short fiber nonwoven fabric made of a thermoplastic elastic resin having good vibration and stress absorption is bonded and integrated as a surface layer, has a vibration insulating property, heat resistance durability, bulkiness, and comfortable stuffiness for sitting. A highly safe cushioning material that is difficult, flame-retardant, and has a low combustion gas toxicity index, and is provided with the above-mentioned preferable characteristics by covering the side material as it is or in combination with other materials. It is possible to provide products such as seats for ships, seats for vehicles, ships, beds for business use in hospitals and hotels, cushions for furniture, bedding and the like. Furthermore, it is also useful as an interior material and a heat insulating material for vehicles and building materials.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI D01F 6/92 304 D01F 6/92 304H // D01F 6/00 6/00 A 6/62 303 6/62 303D 6/86 301 6/86 301B (56) Reference JP-A-7-52332 (JP, A) JP-A-6-207317 (JP, A) JP-A-6-173115 (JP, A) JP-A-5-272043 (JP, A) JP 55-17527 (JP, A) JP 1-213454 (JP, A) JP 58-109670 (JP, A) JP 58-149362 (JP, A) Actual flat 1-16326 (JP, U) Actual development 2-18300 (JP, U) Actual development 2-18371 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) D04H 1 / 00-18 / 00 B68G 1/00-15/00 B32B 1/00-35/00 D01D 1/00-13/02 D01F 1/00-13/04

Claims (6)

(57) [Claims] 1. The soft segment amount (A wt%) and phosphorus content (Bppm) are 60A + 200 ≦ B ≦ 100,000.
The fineness of the thermoplastic elastic resin satisfying the above relation is 10
Continuous filaments of 0000 denier or less are bent and brought into contact with each other to fuse most of the contact portions , and
On one or both sides of the three-dimensional net-like body surface is flattened, two thermoplastic made of an elastic resin composite short fiber nonwoven layer which is fused integrally to form a three-dimensional structure has been bonded laminated Apparent density 0.01g / cm ³ to 0.2g
/ Cm ³ non-woven laminate network. 2. The non-woven fabric laminated reticulate body according to claim 1, wherein the cross-sectional shape of the continuous filaments is a hollow cross section and / or a modified cross section. 3. The non-woven fabric laminated reticulate body according to claim 1, wherein the thermoplastic elastic resin constituting the continuous filament has an endothermic peak at a temperature of room temperature or higher and melting point or lower in a melting curve measured by a differential scanning calorimeter. 4. A soft segment amount (A% by weight) and a phosphorus content (Bppm) from a multi-row nozzle having a plurality of orifices.
Of 60 A + 200 ≦ B ≦ 100,000 is distributed to each nozzle orifice, and the mixture is discharged downward from the nozzle at a melting temperature 10 to 80 ° C. higher than the melting point of the thermoplastic resin. While contacting each other in the state and fusing to form a three-dimensional structure, after sandwiched by a take-up device and cooled in a cooling tank, 2 on one side or both sides
A method for producing a non-woven laminate network in which composite short fibers made of thermoplastic elastic resins of different types are opened, three-dimensional webs are laminated, and thermoformed while being compressed. 5. The method for producing a non-woven fabric reticulated body according to claim 4, wherein annealing is performed at a temperature of at least 10 ° C. or lower than the melting point of the thermoplastic elastic resin in the step of integrally molding after cooling and commercialization. 6. A vehicle seat, a ship seat, a vehicle, a ship, a hospital bed, etc. for commercial and household beds, furniture chairs, office chairs, etc., which use the nonwoven fabric laminated mesh according to claim 1. And the product described in any of the futons.