AU2021260324B2 - Three dimensional network structure body - Google Patents
Three dimensional network structure body Download PDFInfo
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- AU2021260324B2 AU2021260324B2 AU2021260324A AU2021260324A AU2021260324B2 AU 2021260324 B2 AU2021260324 B2 AU 2021260324B2 AU 2021260324 A AU2021260324 A AU 2021260324A AU 2021260324 A AU2021260324 A AU 2021260324A AU 2021260324 B2 AU2021260324 B2 AU 2021260324B2
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- dimensional network
- structure body
- network structure
- resin composition
- borosilicate glass
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- 150000002978 peroxides Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47C—CHAIRS; SOFAS; BEDS
- A47C27/00—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas
- A47C27/12—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas with fibrous inlays, e.g. made of wool, of cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B68—SADDLERY; UPHOLSTERY
- B68G—METHODS, EQUIPMENT, OR MACHINES FOR USE IN UPHOLSTERING; UPHOLSTERY NOT OTHERWISE PROVIDED FOR
- B68G3/00—Treating materials to adapt them specially as upholstery filling
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Metal-Oxide And Bipolar Metal-Oxide Semiconductor Integrated Circuits (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Rod-Shaped Construction Members (AREA)
Abstract
[Problem] To provide a three dimensional network structure body which has excellent hydrolysis resistance and in which deterioration due to atmospheric moisture is unlikely to occur when being used for an extended period of time. [Solution] A three dimensional network structure body comprising a polyester thermoplastic elastomer resin composition and having a three dimensional random loop-joined structure formed from continuous filaments, wherein the resin composition contains borosilicate glass. The borosilicate glass preferably contains B
Description
TITLE OF INVENTION Three Dimensional Network Structure Body TECHNICAL FIELD
[0001] The present invention relates to a three-dimensional network structure body suitable for cushioning materials that are used for office chairs; furniture; sofas; beddings such as beds; seats for vehicles such as those for railroads, automobiles, two wheeled vehicles, child seats, and buggies; floor mats; and mats for impact absorption such as members for prevention of collision and nipping. BACKGROUND ART
[0002] At present, "foamed-crosslinking type urethanes" are widely used as a cushioning material that is used for furniture, beddings such as beds, and seats for vehicles such as those for trains, automobiles, and two-wheeled vehicles from the standpoint of its excellent durability and workability. However, the fact that the "foamed-crosslinking type urethanes "easily get stuffy due to their inferior moisture and water permeability and air-permeability, and thermal storage properties has been a problem. Since the "foamed-crosslinking type urethanes" do not have thermoplasticity, they also have difficulty in recycling. In addition, in the case of incineration of the "foamed-crosslinking type urethanes," they may cause problems such as significant damage to incinerators, the necessity for high costs in the elimination of poisonous gases generated during incineration. For this reason, the "foamed-crosslinking type urethanes" that are no longer needed are often disposed of by landfill. However, the limitation of landfill spots due to the difficulty of stabilization of ground also causes problems of the necessity for higher costs. Besides, they may cause various problems such as pollution problems with chemicals used in the manufacturing process, residual chemicals after foaming, and associated offensive odors.
[0003] PTL 1 discloses a three-dimensional network structure body comprising continuous filaments of a thermoplastic resin composition and having a three-dimensional random loop-bonded structure. This is capable of solving various problems associated with the "foamed-crosslinking type urethanes" and has excellent cushioning performance. However, this three-dimensional network structure body has room for improvement in terms of degradation of the resin composition that constitutes the three-dimensional network structure body due to hydrolysis through long-term exposure to moisture in the air when used as a product such as bedding and a seat for vehicles.
[0004] In addition, PTL 2 discloses a three-dimensional network structure body that has excellent hydrolysis resistance during high-temperature heating and remelting. This _0 literature describes that keeping an acid value of a thermoplastic elastomer low exhibits effects of suppressing hydrolysis that occurs in a thermal processing step of heating at a high temperature close to the melting temperature or a remelting step during recycling. However, the effect of suppressing the hydrolysis of the resin caused by long-term exposure to moisture in the air was not sufficient, when used as a product. For this _5 reason, there is room for improvement in terms of suppressing the degradation of the resin composition that constitutes the three-dimensional network structure body. CITATION LIST PATENT LITERATURE
[0005] PTL 1: Japanese Patent Laying-Open No. 07-68061 PTL 2: WO 2017/065260
[0005a] The reference to any prior art in this specification is not, and should not be taken as an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge. SUMMARY OF INVENTION
[0006] The present invention has been completed in consideration of the problems of conventional technology described above and aims to provide a three-dimensional network structure body that has excellent hydrolysis resistance.
[0007] The present invention, which has been able to solve or at least substantially ameliorate the above problems, is as follows:
[1] In one embodiment, the present invention provides a three-dimensional network structure body comprising a resin composition of a thermoplastic polyester-based elastomer and having a three-dimensional random loop-bonded structure that is formed of a continuous filament, wherein the resin composition contains borosilicate glass.
[1a] In another embodiment, the present invention provides a three-dimensional network structure body comprising a resin composition of a thermoplastic polyester-based elastomer and having a three-dimensional random loop-bonded structure that is formed of
[0 a continuous filament, wherein the resin composition contains borosilicate glass, and the borosilicate glass has a mole fraction of the amount of boron atoms B (mol) to the amount of silicon atoms Si (mol) (B/Si) of 0.3 to 20.
[Ib] In a preferred aspect, the present invention provides a three-dimensional
[5 network structure body comprising a resin composition of a thermoplastic polyester-based elastomer and having a three-dimensional random loop-bonded structure that is formed of a continuous filament, wherein the resin composition contains borosilicate glass, the borosilicate glass has a mole fraction of the amount of boron atoms B (mol) to the amount of silicon atoms Si (mol) (B/Si) of 0.3 to 20, an amount of the borosilicate glass added is in the range of 0.01 to 20% by mass based on 100% by mass of the resin composition, and the three-dimensional network structure body has a boron content of no less than 15 ppm on a mass basis with respect to the three-dimensional network structure body.
[2] The three-dimensional network structure body according to [1], [la] or [1b], wherein the borosilicate glass contains B 2 0 3 , Si0 2 , and an alkali metal oxide. ADVANTAGEOUS EFFECTS OF INVENTION
[0008] The three-dimensional network structure body of the present invention has excellent hydrolysis resistance of a thermoplastic elastomer resin composition that constitutes the three-dimensional network structure body and has the property of being not easily degraded by moisture in the air when used for a long period of time. DESCRIPTION OF EMBODIMENTS
[0009] Hereinafter, the present invention will be described in detail. The three-dimensional network structure body of the present invention is formed of a resin composition containing a thermoplastic polyester-based elastomer and borosilicate glass. The three-dimensional network structure body of the present invention, when in contact with moisture in the air, consumes moisture by dissolving boron, a component of borosilicate glass contained in the resin composition, in the moisture, thereby making it possible to suppress hydrolysis of the thermoplastic elastomer resin composition.
[0010] Next, borosilicate glass will be described. Borosilicate glass refers to a composite glass containing at least diboron trioxide (B2 0 3) and silicon dioxide (Si0 2 ) as a network-forming oxide. Specific examples thereof include a composite glass containing B 2 0 3 , Si0 2 , and an alkali metal oxide. Examples of the alkali metal oxide include K20, Na20, and Li2 0. The borosilicate glass may also contain alkaline earth metal oxides such as MgO and CaO, ZnO, A1 2 0 3 , and P 2 0 5 to adjust its solubility in water. Additionally, it
- 3a - may contain Ag20, GeO2, BeF2, As2S3, CuO, TiO 2 , LaO3, ZrO2, MoO3, GeS2, and the like to the extent that its properties are not impaired.
[0011] The borosilicate glass contains a relatively large amount of B 2 0 3 . In order to more efficiently exhibit the effect of suppressing the hydrolysis of the thermoplastic polyester-based elastomer described above, the borosilicate glass preferably has a mole fraction of the amount of boron atoms B (mol) to the amount of silicon atoms Si (mol) (B/Si) of 0.3 to 20. It is preferable to adjust the B/Si mole ratio in the range of 0.3 to 20, depending on the B concentration. In the case where the B concentration is high, even if the B/Si mole ratio is small in the above range, reduced viscosity retention after heat treatment can be no less than 65%. In the case where the mole fraction (B/Si) is too small, the speed of boron elution with respect to moisture tends to be slow. For this reason, the efficiency of suppressing hydrolysis is easily reduced. Furthermore, if the content of borosilicate glass in the three-dimensional network structure body is not increased, it will be difficult to obtain the effect of suppressing the hydrolysis. On the other hand, from the standpoint of heat resistance and chemical durability of borosilicate glass, the mole fraction (B/Si) is preferably no more than 20. The mole fraction (B/Si) is more preferably 0.6 to 20, still more preferably 1.0 to 10, and particularly preferably 1.5 to 5.0.
[0012] Examples of compositional features of such borosilicate glass include those containing 50 to 80 mol% B 2 0 3 and 5 to 30 mol% Si0 2 , and those containing 20 to 50 mol% B 2 0 3 , and 5 to 15 mol% Si0 2 .
The morphology of the borosilicate glass includes polyhedral and spherical objects such as fine powders, frits, particles, and beads. The size of the polyhedral or spherical objects is preferably 0.1 to 100 pm, still more preferably 0.5 to 50 pm, and
particularly preferably 1 to 30 pm in average particle diameter. An average particle
diameter of less than 0.1 pim is not preferred because of secondary agglomeration that occurs during spinning and higher milling costs. An average particle diameter of more than 100 pm is not preferred because it induces an increase in back pressure during spinning.
[0013] Methods for manufacturing borosilicate glass generally include melt milling, in which raw materials of B 2 0 3 , SiO2 , and an alkali metal oxide are mixed at a predetermined composition ratio, melted at a high temperature, then the melt was quenched to form glass fragments, and milled with a ball mill or the like. Such borosilicate glass is available from, for example, but not limited to, Nippon Electric Glass Co., Ltd., Nippon Frit, Ishizuka Glass Co., Ltd., Koa Glass Co., Ltd., Toagosei Co., Ltd., and Potters-Ballotini Co., Ltd.
[0014] The three-dimensional network structure body of the present invention preferably has a boron content of no less than 5 ppm on a mass basis with respect to the three-dimensional network structure body. If boron is contained in the three dimensional network structure body at no less than 5 ppm on a mass basis, the borosilicate glass is easily contained in the three-dimensional network structure body uniformly. From the standpoint of suppressing the hydrolysis of the resin composition by moisture in the air, the boron content with respect to the three-dimensional network structure body is preferably no less than 10 ppm, more preferably no less than 15 ppm, particularly preferably no less than 150 ppm, and most preferably no less than 400 ppm on a mass basis. In addition, the effects of suppressing the proliferation of mites on fibers of the three-dimensional network structure body can be expected by containing no less than 10 ppm of boron in its three-dimensional network on a mass basis. On the other hand, if the boron content is too high with respect to the three dimensional network structure body, the borosilicate glass can be easily deposited on surfaces of the fibers, thus easily causing a sticky feeling when the three-dimensional network structure body is touched by hand. For this reason, the boron content with respect to the three-dimensional network structure body is preferably no more than 36,000 ppm on a mass basis. In addition, the boron content is preferably no more than 18,000 ppm, still more preferably no more than 10,000 ppm, particularly preferably no more than 5,000 ppm, and most preferably no more than 2,000 ppm from the viewpoint of minimizing influences on mechanical properties of the three-dimensional network structure body.
[0015] Next thermoplastic polyester-based elastomers used in the present invention will be described. Examples of the thermoplastic polyester-based elastomers include polyester ether block copolymers having a thermoplastic polyester as a hard segment and a polyalkylenediol as a soft segment or polyester block copolymers having an aliphatic polyester as a soft segment.
[0016] The polyester ether block copolymers are ternary block copolymers that are formed of at least one of dicarboxylic acids selected from 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, cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dimer acid, and ester-forming derivatives thereof; at least one of diol components selected from aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol, cycloaliphatic diols such as 1,1 cyclohexanedimethanol and 1,4-cyclohexanedimethanol, and ester-forming derivatives thereof; and at least one of polyalkylenediols such as glycols including polyethylene glycol, polypropylene glycol, polytetramethylene glycol or an ethylene oxide propylene oxide copolymer, the number-average molecular weight of which is no less than about 300 and no more than 5,000.
[0017] Examples of the polyester ester block copolymers include ternary block copolymers that are formed of at least one of the above dicarboxylic acids, at least one of the above diols, and at least one of polyester diols such as polylactone, the number average molecular weight of which is no less than about 300 and no more than 5,000. In consideration of heat adhesiveness, hydrolysis resistance, stretchability, heat resistance, and the like, ternary block copolymers having terephthalic acid and/or naphthalene-2,6-dicarboxylic acid as a dicarboxylic acid, 1,4-butanediol as a diol component, and polytetramethylene glycol as a polyalkylenediol, or ternary block copolymers having polylactone as a polyester diol are particularly preferred. In special cases, those with a polysiloxane-based soft segment introduced may also be used.
[0018] The thermoplastic polyester-based elastomers in the present invention also encompass those obtained by blending or copolymerizing a non-elastomer component with the thermoplastic polyester-based elastomers and those having a polyolefin-based component as a soft segment. Furthermore, those obtained by adding various kinds of additives or the like to the thermoplastic polyester-based elastomers as necessary are also encompassed.
[0019] A thermoplastic polyester-based elastomer that contains borosilicate glass is obtained, for example, as follows. The thermoplastic polyester-based elastomer is polymerized through a conventional method and once pelletized. The resulting pellets of the thermoplastic polyester-based elastomer and fine powder of the borosilicate glass are mixed at a predetermined proportion, melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of the thermoplastic polyester-based elastomer that contains the borosilicate glass. Alternatively, while the pellets of the thermoplastic polyester-based elastomer are melt-extruded with a twin-screw extruder, the fine powder of the borosilicate glass is supplied at a predetermined proportion from a side feeder installed in the extruder, and the thermoplastic polyester-based elastomer and borosilicate glass are kneaded in the extruder while being melt-extruded, cooled, pelletized, and dried to obtain a resin composition of the thermoplastic polyester-based elastomer that contains the borosilicate glass.
[0020] The amount of the borosilicate glass added is preferably in the range of 0.001 to 50% by mass based on 100% by mass of the resin composition. Iftheamountof borosilicate glass added is less than 0.001% by mass, the content of the borosilicate glass in the resin composition varies widely. If the amount of borosilicate glass added is more than 50% by mass, the high content of the borosilicate glass makes it difficult to manufacture the resin composition. The amount of the borosilicate glass added is preferably 0.01 to 20% by mass because of its variation in content and ease of manufacturing the resin compositions.
[0021] In manufacturing the resin composition, it is preferable that an antioxidant be added for the purpose of suppressing thermal degradation of the resin composition during spinning and melting, thermal degradation during thermoforming of the three dimensional network structure body, and degradation due to light. The amount of the antioxidant added is preferably no less than 0.05% by mass, more preferably no less than 0.10% by mass, particularly preferably no less than 0.20% by mass, and most preferably no less than 0.50% by mass in the case of 100% by mass of the resin composition. Examples of such antioxidants include known phenol-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants; benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, N-H type hindered amine light stabilizers, and N-CH 3 type hindered amine light stabilizers may be used in combination thereof. It is desirable that at least one or more of these additives be added.
[0022] Examples of the phenol-based antioxidants include1,3,5-tris[[3,5-bis(1,1 dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3 tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylidenebis(6-tert-butyl-m cresol), stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Sumilizer G 80, and 2,4,6 tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene.
[0023] Examples of the phosphorus-based antioxidants include 3,9-bis(octadecyloxy) 2,4, 8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4 methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10 tetrakis(1,1-dimethylethyl)-6-[(2-ethylhexyl)oxy]-12H dibenzo[d,g][1,3,2]dioxaphosphocin, tris(2,4-di-tert-butylphenyl)phosphite, tris(4 nonylphenyl)phosphite, 4,4'-Isopropylidenediphenol C12-15 alcohol phosphite, diphenyl phosphite(2-ethylhexyl), diphenyl isodecyl phosphite, triisodecyl phosphite, and triphenyl phosphite.
[0024] Examples of the thioether-based antioxidants include bis[3 (dodecylthio)propionate]2,2-bis[[3-(dodecylthio)-1-oxopropyloxy]methyl]-1,3 propanediyl, and ditridecyl 3,3'-thiodipropionate.
[0025] In addition to the antioxidants, the UV absorbers, and the light stabilizers, various additives can be added to the resin composition depending on the purpose. Examples of the additives that can be added include plasticizers of phthalic acid ester type, trimellitic acid ester type, fatty acid type, epoxy type, adipic acid ester type, and polyester type; antistatic agents; molecular regulators such as peroxides; reactive group-containing compounds such as epoxy compounds, isocyanate compounds, and carbodiimide compounds; metal deactivators; organic and inorganic nucleating agents; neutralizers; antacids; anti-microbial agents; fluorescent whitening agents; fillers; flame retardants; flame retardant aids; and organic and inorganic pigments.
[0026] The three-dimensional network structure body of the present invention is a network structure body in which random loops including continuous filaments of a resin composition of a thermoplastic polyester-based elastomer that contains borosilicate glass are bonded in a three-dimensional direction to form a steric structure.
[0027] The continuous filaments that constitute the three-dimensional network structure body of the present invention may be formed as complex filaments obtained by combination with other thermoplastic resins to the extent that the purpose of the present invention is not impaired. In the case where the filaments themselves are complexed, examples of the complexed forms include complex filaments of sheath core type, side-by-side type, eccentric sheath-core type, and the like. In the case of a sheath-core type complex filament, borosilicate glass may be contained in both sheath and core components, or borosilicate glass may be contained only in the sheath component.
[0028] The three-dimensional network structure body of the present invention can be obtained in accordance with a known method described in Japanese Patent Laying OpenNo.7-68061. For example, a resin composition of a thermoplastic elastomer that contains borosilicate glass is distributed to nozzle orifices from a multi-row nozzle having a plurality of orifices and discharged downward through the nozzle at a spinning temperature higher by no less than 20°C and less than 120°C than the melting point of the resin composition to provide continuous filaments. Then, the continuous filaments are mutually contacted in a molten state and thereby fused to form a three-dimensional structure, which is sandwiched by a take-up conveyor net, and cooled by cooling water in a cooling bath. Subsequently, they are drawn out and drained or dried to obtain a three-dimensional network structure body having both surfaces or one surface smoothed. In the case where only one surface is to be smoothed, the continuous filaments may be discharged onto an inclined take-up net, mutually contacted in a molten state, and thereby fused to form a three-dimensional structure, which may be cooled while the form of only the take-up net surface is relaxed. The obtained three dimensional network structure body can also be subjected to annealing treatment. Note that drying treatment of the three-dimensional network structure body may be performed by annealing treatment.
[0029] The cross-sectional shape of the continuous filament that constitutes the three dimensional network structure body of the present invention is not particularly limited, but when the cross section is a hollow cross section or a modified cross section, preferred compression resistance and touch characteristics can be imparted. In the thickness direction, the three-dimensional network structure body may include a fine fiber-diameter fiber main region that mainly contains fibers having relatively thin fiber diameters; a thick fiber-diameter fiber main region that mainly contains fibers having relatively thick fiber diameters; and a mixed region that contains a mixture of fine and thick fiber-diameter fibers located between the fine fiber-diameter fiber main region and the thick fiber-diameter fiber main region.
[0030] The three-dimensional network structure body of the present invention can be processed into a molded article from a resin manufacture process to the extent that its performance does not deteriorate, and also treated to impart functions such as antibacterial deodorization, deodorization, mold prevention, coloring, fragrance, flame resisting, and absorption and desorption of moisture by using a treatment process in which chemicals attached by dipping or the like.
[0031] The three-dimensional network structure body of the present invention may be formed as a laminated structure to the extent that the purpose of the present invention is not impaired. Examples of the laminated structure include a form in which the surface layer and the back surface layer are formed of filaments having different fineness and a form in which the surface layer and the back layer are formed of three-dimensional network structure bodies having different apparent densities. Examples of methods for multilayered formation include a method in which three-dimensional network structure bodies are stacked on one after another and fixed by side ground or the like, melted and fixed by heating, bounded with an adhesive, and restrained by sewing or with a band.
[0032] The three-dimensional network structure body of the present invention has excellent reduced viscosity retention after heat treatment. Here, when the coefficient of viscosity of a polymer solution is i, the coefficient of viscosity of a solvent is 10, and the concentration of a solute polymer of the polymer solution is c, the reduced viscosity asp/c is given by the formula {(i-i0)/A0}/c. The reduced viscosity retention provides a measure for relatively comparing the molecular weights of the polymers.
[0033] For example, if the resin composition of the thermoplastic polyester-based elastomer has decreased in molecular weight due to hydrolysis, the reduced viscosity of the thermoplastic polyester-based elastomer resin composition after hydrolysis is smaller than that of the thermoplastic polyester-based elastomer resin composition before hydrolysis. Therefore, resistance to hydrolysis due to long-term exposure to moisture in the air can be evaluated by changes in reduced viscosity after accelerated testing. In other words, hydrolysis resistance can be evaluated by heat-treating the three-dimensional network structure body under a high temperature and humidity atmosphere and then comparing the reduced viscosity of the resin composition that constitutes the three-dimensional network structure body before and after the treatment.
[0034] The reduced viscosity retention after heat treatment is expressed by the following formula (1), where A is the reduced viscosity of the resin composition that constitutes the three-dimensional network structure body while B is the reduced viscosity of the resin composition that constitutes the three-dimensional network structure body after heat treatment at a temperature of 800C and a relative humidity of 90 RH% for 240 hours. Reduced viscosity retention after heat treatment = (B/A) x 100 - - (1)
[0035] The greater the reduced viscosity retention after heat treatment, the smaller the decrease in molecular weight after heat treatment, which means excellent hydrolysis resistance. In other words, the reduced viscosity retention after heat treatment in the present invention is an index for evaluating the hydrolysis resistance of three dimensional network structure body. The three-dimensional network structure body of the present invention preferably has reduced viscosity retention after heat treatment of no less than 65%. If the reduced viscosity retention after heat treatment is no less than 65%, hydrolysis does not occur easily even when exposed to moisture in the air for a long period of time, which means excellent hydrolysis resistance. From the viewpoint of hydrolysis resistance, reduced viscosity retention after heat treatment is more preferably no less than 70%, still more preferably no less than 75%, particularly preferably no less than 80%, and most preferably no less than 85%.
[0036] The three-dimensional network structure body of the present invention preferably has a thickness of no less than 10 mm and more preferably no less than 20 mm. A thickness of less than 10 mm may give a bottoming feeling when it is used as a cushioning material. The upper limit of the thickness is preferably no more than 300 mm, more preferably no more than 200 mm, and still more preferably no more than 120 mm in view of manufacturing equipment.
[0037] The three-dimensional network structure body of the present invention preferably has an apparent density of no less than 0.005 g/cm3 and no more than 0.20 g/cm 3, more preferably no less than 0.01 g/cm 3 and no more than 0.18 g/cm3 , and still more preferably no less than 0.02 g/cm3 and no more than 0.15 g/cm 3 . The apparent density of smaller than 0.005 g/cm3 may fail to maintain a necessary hardness when it is used as a cushioning material. On the other hand, the apparent density exceeding 0.20 g/cm3 may make it too hard and unsuitable as a cushioning material.
[0038] With respect to the fiber diameter of the continuous filaments that constitute the three-dimensional network structure body of the present invention, a small fiber diameter may not provide a necessary hardness when used as a cushioning material. On the other hand, a too large fiber diameter may make a cushion too hard for some applications. Therefore, it is preferable to set the diameter appropriately according to the application of the cushion. The fiber diameter is preferably no less than 0.1 mm and more preferably no less than 0.2 mm. In the case of a fiber diameter of less than 0.1 mm, although denseness and soft touch are improved, it is difficult to secure a necessary hardness as a network structure body. On the other hand, the fiber diameter is preferably no more than 3.0 mm and more preferably no more than 2.5 mm. In the case of a fiber diameter of more than 3.0 mm, the hardness of the three-dimensional network structure body can be sufficiently secured, but the network structure may become coarse, leading to a deterioration of other cushioning performance.
[0039] (Effect) The three-dimensional network structure body of the present invention has excellent hydrolysis resistance so that the resin is not easily degraded by moisture in the air when used for a long period of time, and has excellent durability in long-term use. Examples
[0040] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Note that measurement and evaluation of characteristic values in Examples were performed by the following methods.
[0041] (1) Reduced Viscosity
[Adjustment of Test Solution] Pellets or three-dimensional network structure bodies to be tested are placed in a hot-air dryer set at an internal temperature of 70°C and left to dry for 25 minutes. The dried pellets or three-dimensional network structure bodies are cut into small pieces so that the length of the pellets or fibers is within 2 mm, and a sample of 0.08 0.003 g is weighed. To the resulting sample, a phenol/1,1,2,2-tetrachloroethane mixed solvent (= 60/ 40; mass ratio) was added with an accuracy of ±0.01 ml to obtain a
solution with a concentration of 0.2 g/dl. The obtained solution is heated to 70°C and stirred for 30 minutes to dissolve the sample. The solution is cooled in a water bath at 15 1°C and then left at room temperature to make a test solution.
[Measurement of Efflux Time tO of Solvent (Blank Test)] A capillary (Ubbelohde viscosity tube) automatic viscosity measuring device AVL-2C manufactured by Asahi Kasei Technosystem Corporation is used. An Ubbelohde-type viscosity tube with a capillary diameter of 0.77 mm (±2%) is used as the viscosity tube. The temperature of a thermostatic bath of an automatic viscosity measuring device and its test temperature are set to 30 ±0.1C. A phenol/1,1,2,2 tetrachloroethane mixed solvent (= 60/40; mass to weight ratio) is put in a viscosity tube. The viscosity tube is attached to the thermostatic bath and adjusted to a temperature of 30± 0.1C for 10 minutes. Subsequently, the testis started, and the efflux time (sec) of the mixed solvent is measured twice consecutively. The average of the two measurements is designated as the efflux time tO (sec) of the solvent.
[0042] [Measurement of Efflux Time tl of Test Solution] The same automatic viscosity measuring device as for the measurement of tO is used. The same viscosity tube as for the measurement of tO is used (the viscosity tube must not be changed). The temperature of a thermostatic bath of an automatic viscosity measuring device and its test temperature are set to 30 ±0.1C. The viscosity tube is washed with the test solution. The test solution is put into the viscosity tube. The viscosity tube is attached to the thermostatic bath and adjusted to a temperature of 30 0.1C for 10 minutes. Subsequently, the test is started, and the efflux time (sec) of the test solution is measured twice consecutively. The average of the two measurements is designated as the efflux time tl (sec) of the test solution.
[0043] [Calculation of Reduced Viscosity] The reduced viscosity (dl/g) is calculated from the following formula. Reduced viscosity qsp/c = (tI/tO - 1)/c tl: efflux time of test solution (sec), tO: efflux time of solvent (sec), c: test solution concentration (0.2 g/dl)
[0044] (2) Reduced Viscosity Retention After Heat Treatment From the three-dimensional network structure body before heat treatment, a test piece having a size of "5 cm x 5 cm x thickness of the three-dimensional network structure body" is cut out, placed, and sealed in a moisture-proof and light-shielded bag, and then stored at room temperature as a test piece A before heat treatment. From the three-dimensional network structure body, a test piece having a size of "10 cm x 10 cm x thickness of three-dimensional network structure body" is cut out. The test piece is placed in a thermostatic chamber with the chamber environment set at a temperature of 80°C and a relative humidity of 90 RH% and subjected to heat treatment for 240 hours. Subsequently, the test piece is removed from the 20 thermostatic chamber and cooled at room temperature for 1 hour to make a test piece B after heat treatment. The "reduced viscosity of the resin composition of the three-dimensional network structure body before heat treatment (reduced viscosity A)" is measured from test piece A using the method for measuring the reduced viscosity in (1) above. Similarly, the "reduced viscosity of the resin composition of the three dimensional network structure body after heat treatment (reduced viscosity B)" is measured from test piece B using the method for measuring the reduced viscosity in (1) above. In this case, the reduced viscosity A and reduced viscosity B are measured on the same day, using the same automatic viscosity measuring device and the same viscosity tube. Then, the reduced viscosity retention after the heat treatment was calculated using the following formula. Reduced viscosity retention after heat treatment (%)= (B/A) x 100
[0045] (3) Boron Content of Three-dimensional Network Structure Body A sample of 0.2 g was collected from the three-dimensional network structure body, 10 ml of concentrated nitric acid was added, and a microwave decomposition device (manufactured by Anton Paar GmbH; Multiwave PRO) is used for wet acid decomposition. Specifically, the temperature is raised at 700 W for 10 minutes, and the sample was held at 700 W for 50 minutes to make a solution. Subsequently, it was cooled to 40°C and made into a sample solution. This sample solution was diluted to 50 ml with ultrapure water to prepare a pretreatment solution and measured using a high-frequency inductively coupled plasma atomic emission spectrometer (manufactured by Hitachi High-Tech Science Corporation, SPECTROBLUE). The boron concentration (mg/1) of the pretreatment solution is calculated from the calibration curve prepared earlier and designated as C (mg/1). Next, after preparing a blank test solution by diluting 10 ml of concentrated nitric acid to 50 ml with ultrapure water, it is measured with the same device. The boron concentration (mg/1) of the blank test solution is calculated from the calibration curve prepared earlier and designated as D (mg/l). Then, the boron content of the three-dimensional network structure body (ppm; mass basis) was calculated using the following formula. Boron content of three-dimensional network structure body (ppm; mass basis)= (C - D) x 50/0.2
[0046] (4) Silicon Content of Three-dimensional Network Structure Body A sample of 0.2 g is collected from three-dimensional network structure body, and the sample is weighed into a platinum crucible. The sample is then pre carbonized on a hot plate to 400°C. Subsequently, it is ashed at 550°C for 8 hours using an electric furnace (manufactured by Yamato Scientific Co., Ltd., Model F0610).
After ashing, 5 ml of 5% sodium carbonate solution is added and heated on a hot plate until the water completely volatilizes. Subsequently, alkali fusion treatment is performed using a burner, and ultrapure water is added to the resulting white residue. Then, heat treatment is performed on a hot plate to ensure that the salt is completely dissolved. After that, 5 ml of 6N hydrochloric acid is added, and ultrapure water is used to prepare a pretreatment solution diluted to 25 ml. The silicon concentration (mg/1) of the pretreatment solution is calculated using a high-frequency inductively coupled plasma atomic emission spectrometer (manufactured by Hitachi High-Tech Science Corporation, SPECTROBLUE) and designated as E (mg/l). Next, 5 ml of 5% sodium carbonate solution is added to 5 ml of 6N hydrochloric acid, and a blank test solution is prepared by diluting it to 25 ml with ultrapure water. The silicon concentration (mg/1) of the blank test solution is calculated from the calibration curve prepared earlier using the high-frequency inductively coupled plasma emission spectrometer and designated as F (mg/l). Next, the silicon content (ppm; mass basis) of the three-dimensional network structure body is calculated using the following formula. Silicon content (ppm; mass basis) of three-dimensional network structure body = (E - F) x 25/0.2
[0047] (5) Melting point (Tm) Thinly sliced pellets of the thermoplastic elastomer are sealed in a test pan. Next, an endothermic peak (melting peak) temperature by crystal fusion is determined from an endothermic/exothermic curve obtained by measurement at a heating rate of 200C /min using a differential scanning calorimeter (manufactured by TA Instruments, Q200), and designated as the melting point of the thermoplastic elastomer.
[0048] (6) Acid Value A 1H-NMR measurement is performed at a resonance frequency of 500 MHz using a proton nuclear magnetic resonance spectrometer (manufactured by Bruker Corporation, NMR instrument AVANCE-500) to quantify an acid value of the thermoplastic polyester-based elastomer. The method for preparing the measurement solution is performed as follows. <Measurement i> A sample of 10 to 20 mg is dissolved in 0.12 ml of deuterated chloroform/hexafluoroisopropanol = 1/1 (volume ratio). Next, 0.48 ml of the deuterated chloroform is added and stirred well. Subsequently, the solution is then filled into an NMR tube for H-NMR measurement. <Measurement ii> To the solution after completion of measurement i, a deuterated chloroform solution prepared such that a concentration of triethylamine was to be 0.2 mol/L was added in 25 pL, and again the 1H-NMR measurement was performed. All lock solvents used were deuterated chloroform, and the number of integrations was 128. <Measurement of Acid Value> Acid values are quantified as follows. In the case where the peak at 7.27 ppm was assigned to chloroform, the peaks at 8 ppm was assigned to terephthalic acid (a), the peak at 2 ppm was assigned to 1,4-butanediol (b), the peak at 3.5 ppm was assigned to polytetramethylene glycol (c) in measurements i and ii, the peak at 7.87 to 7.96 ppm was assigned to the satellite peak of terephthalic acid (d) in measurement i, and the peak at 7.87 to 7.96 ppm was assigned to the satellite peak of terephthalic acid end and terephthalic acid (e) in measurement ii, and thus calculated. The acid values are determined from the following formula, where a to e in the parentheses are the integrated values of each peak. (f)= (a/4 x 132) + (b/4 x 88) + (c/4 x 72) Acid value (eq/ton)= ((e - d)/2 x 1,000,000)/(f) :unit meq/kg (average of n = 2)
[0049] (7) Thickness and Apparent Density of Three-dimensional Network Structure Body From the three-dimensional network structure body, four test pieces having a size of "10 cm x 10 cm x thickness of three-dimensional network structure body" were collected. The test pieces were left at room temperature under no load for 24 hours.
Subsequently, the height (mm) in the thickness direction was measured for each of the test pieces using a thickness gauge (manufactured by KOBUNSHI KEIKI CO., LTD., Model FD-80N). The average of the heights of the four test pieces is designated as the thickness (mm) of three-dimensional network structure body. The weight W (g) of each test piece is measured on an electronic balance, and the apparent density (g/cm 3) of each test piece is calculated by the following formula. The average of the apparent densities of the four test pieces is designated as the apparent density (g/cm 3) of the three-dimensional network structure body. Apparent density (g/cm 3) = W/(10 x 10 x height of test piece/10)
[0050] (8) Fiber Diameter of Three-dimensional Network Structure Body From the three-dimensional network structure body, a test piece having a size of "10 cm x 10 cm x thickness of three-dimensional network structure body" is collected. From the resulting test piece, filaments at 10 places are each sampled with a length of about 5 mm. The fiber diameter is measured for the sampled filaments using an optical microscope adjusted to the appropriate magnification and focused on the measurement point, and the average of the values at the 10 places is designated as the fiber diameter (mm) of the three-dimensional network structure body.
[0051] [Example 1] (1) Manufacture of Thermoplastic Polyester-based elastomer As a thermoplastic polyester-based elastomer, dimethyl terephthalate (DMT), 1,4-butanediol (1,4-BD), and polytetramethylene glycol (PTMG: average molecular weight of 1000) were charged together with a small amount of a catalyst, and transesterification was performed through a usual method. Then, the mixture was subjected to polycondensation while the temperature was raised under reduced pressure and pelletized to thereby manufacture a polyether ester block copolymer elastomer. In this case, the product was manufactured by a conventional method in which a method of lowering a thermal history until pelletization after polymerization through a polycondensation reaction was not employed. Monomer compositional features, a melting point, an acid value, and reduced viscosity of the resulting thermoplastic polyester-based elastomer (A-1) are shown in Table 1.
[0052] [Table 1]
Hard segment Soft segment Amount of Resin property Resin Number- soft Acid Glycol Naverage segment Melting Acid Reduced name component compone nt molecule (parts by point value viscosity r weight mass) (°C) (meqlkg) (dl/g) I_ A-1I DTM 1,4 BD PTMG 1000 43 190 39 1.89
[0053] (2) Manufacture of Resin Composition Constituting Three-dimensional Network Fibrous Structure Body Into 99.49% by mass of the thermoplastic polyester-based elastomer (A-1), 0.01% by mass of fine powder of borosilicate glass (manufactured by Ishizuka Glass Co., Ltd., E74527), and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. Then, the mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition that serves as a raw material for a three-dimensional network fibrous structure body. The main compositional features of the borosilicate glass used in the experiment are as follows. B 2 0 3 : 61 mol0 %, SiO 2 : 23 mol%, alkali metal oxide:16 mol%
[0054] (3) Manufacture of Three-dimensional Network Structure Body A nozzle was provided having orifices that are zigzag-arranged at a pitch between holes of 8 mm and have an outer diameter of 5.0 mm and a hollow-forming cross section of a triple bridge, on a nozzle effective face of 1,120 mm in the width direction and 34.5 mm in width in the thickness direction. When the thermoplastic polyester-based elastomer (A-1) was used as a base resin, a resin composition obtained by adding 0.01% by mass of the borosilicate glass to the base resin was discharged to downward from a nozzle at a spinning temperature of 2400C and a speed of 1.5 g/min in terms of discharge amount per hole using the nozzle. Then, it passed through a cooling space with an ambient temperature of 25 to 35°C, cooling air was not blown, and cooling water was arranged at a position 23 cm below the nozzle face. Endless nets that were formed of stainless steel having a width of 150 cm were disposed parallel at an interval of 25 mm in opening width to form a pair of take-up conveyors so as to be partially exposed over a water surface. The discharged filaments in a molten state were curled and loops were formed by fusing the contacting parts on the conveyor nets over the water surface to form a three-dimensional network structure body. The three dimensional network structure body in the molten state was sandwiched at both surfaces by the take-up conveyors, and drawn into cooling water at a speed of 0.9 m per minute, thereby solidified and flattened at both surfaces. Subsequently, it was cut into a predetermined size and dried/heat-treated with hot air at 105°C for 30 minutes to obtain a three-dimensional network structure body. The properties of the obtained three-dimensional network structure body are shown in Table 3. The obtained three dimensional network structure body had reduced viscosity retention of 70% after heat treatment and was excellent in hydrolysis resistance.
[0055] Note that the following two methods of reducing the thermal history during melt extrusion were not used. (a) Shear amount per discharge (Q/N, unit: cm3/rev) of no less than 3 and no more than 200 Q: Amount of the resin discharged from the nozzle per minute (cm 3/min) N: Screw rotation speed for producing Q (rev/min) (b) Pass-through time (V/Q, unit: min) in the pipe of no less than 1 and no more than 30 V: Total volume of resin melted and extruded by the extruder until it is discharged from the nozzle via the pipe after leaving the extruder (cm 3 )
Q: Amount of the resin discharged from the nozzle per minute (cm 3/min)
[0056] [Example 2] Into 99.40% by mass of the thermoplastic polyester-based elastomer (A-1), 0.10% by mass of the same fine powder of borosilicate glass as in Example 1, and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. Then, the mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 3. The obtained three dimensional network structure body had a reduced viscosity retention of 79% after heat treatment and was excellent in hydrolysis resistance.
[0057] [Example 3] Into 99.25% by mass of the thermoplastic polyester-based elastomer (A-1), 0.25% by mass of the same fine powder of borosilicate glass as in Example 1, and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. Then, the mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 3. The obtained three dimensional network structure body had a reduced viscosity retention of 87% after heat treatment and was excellent in hydrolysis resistance.
[0058] [Example 4] Into 99.00% by mass of the thermoplastic polyester-based elastomer (A-1), 0.50% by mass of the same fine powder of borosilicate glass as in Example 1, and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. Then, the mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 3. The obtained three dimensional network structure body had a reduced viscosity retention of 89% after heat treatment and was excellent in hydrolysis resistance.
[0059] [Example 5] Into 98.50% by mass of the thermoplastic polyester-based elastomer (A-1), 1.00% by mass of the same fine powder of borosilicate glass as in Example 1, and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 3. The obtained three dimensional network structure body had a reduced viscosity retention after heat treatment of 90% and was excellent in hydrolysis resistance.
[0060] [Comparative Example 1] Into 99.50% by mass of the thermoplastic polyester-based elastomer (A-1), 0.25% by mass of each of the phenol-based antioxidant, and the phosphorus-based antioxidant was mixed. Then, the mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three dimensional network fibrous structure body. The obtained resin composition was used in the same manner as in Example 1 to obtain a three-dimensional network structure body. The properties of the obtained three-dimensional network structure body are shown in Table 3. Since the obtained three-dimensional network structure body did not contain borosilicate glass, it had a reduced viscosity retention of 62% after heat treatment and was inferior in hydrolysis resistance.
[0061] [Comparative Example 2] (1) Manufacture of Thermoplastic Elastomer
As a thermoplastic polyester-based elastomer, dimethyl terephthalate (DMT) and 1,4-butanediol (1,4-BD) were charged together with a small amount of a catalyst, transesterification was performed through a usual method, polytetramethylene glycol (PTMG) was then added, and then subjected to polycondensation while the temperature was raised and the pressure was reduced, so that a polyether ester block copolymer elastomer was generated. Next, 1% of an antioxidant was added thereto, and the mixture was mixed and kneaded employing a method of lowering the thermal history after polymerization compared to a conventional method. Subsequently, it was pelletized and dried in a vacuum at 50°C for 48 hours to obtain a thermoplastic elastomer (A-2). Monomer compositional features, a melting point, an acid value, and reduced viscosity of the thermoplastic polyester-based elastomer (A-2) are shown in Table 2. The thermoplastic polyester-based elastomer (A-2) had a lower acid value than the thermoplastic polyester-based elastomer (A-1).
[0062] [Table 2]
Hard segment Soft segment Amount Resin property Resin Number- of soft name Acid Glycol average segment Melting Acid Reduced component component Component molecular (parts by point value viscosity weight mass) (°C) (meqlkg) (dl/g) I_ A-2 DTM 1,4 BD PTMG 1000 43 192 19 1.86
[0063] (2) Manufacture of Three-dimensional Network Structure Body A nozzle was provided having orifices that are zigzag-arranged at a pitch between holes of 8 mm and shaped to have an outer diameter of 5.0 mm and a hollow forming cross section of a triple bridge, on a nozzle effective face of 1,120 mm in the width direction and 64 mm in width in the thickness direction. In Comparative Example 2, the method of reducing the thermal history during melt extrusion at spinning, as described in Example 1, was used. The resin composition of the thermoplastic polyester-based elastomer was discharged to downward from a nozzle at a melting temperature of 240°C and a speed of 3.2 g/min in terms of discharge amount per hole (Q) under the following conditions using the nozzle. The screw rotation speed (N) was 70 rpm, the shear amount per discharge (Q/N) was 48.7 cm3/rev, and the pass-through time in the pipe was 1 minute. Cooling water was arranged at a position 33 cm below the nozzle face. Endless nets made of stainless steel having a width of 150 cm were disposed parallel at an interval of 50 mm in opening width to form a pair of take-up conveyors so as to be partially exposed over a water surface. The discharged filaments in a molten state were curled and loops were formed by fusing the contacting parts on the conveyor nets over the water surface to form a three-dimensional network structure. The network in the molten state was sandwiched at both surfaces by the take-up conveyors and drawn into cooling water at a speed of 2.0 m/min, thereby solidified, flattened at both surfaces of the thickness direction, then cut into a predetermined size, and dried/heat-treated with hot air at 110°C for 15 minutes to obtain a three-dimensional network structure body. The properties of the obtained three-dimensional network structure body containing the thermoplastic polyester-based elastomeric resin are shown in Table 3. The obtained three-dimensional network structure body had a reduced viscosity retention of 62% after heat treatment and was inferior in hydrolysis resistance.
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[0065] [Example 6] Into 9 9 .4 9 7 % by mass of the thermoplastic polyester-based elastomer (A-1), 0.003% by mass of the same fine powder of borosilicate glass as in Example 1 and 0.250% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 68% after heat treatment and was excellent in hydrolysis resistance.
[0066] [Example 7] Into 99.494% by mass of the thermoplastic polyester-based elastomer (A-1), 0.006% by mass of the same fine powder of borosilicate glass as in Example 1 and 0.250% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 69% after heat treatment and was excellent in hydrolysis resistance.
[0067] [Example 8] Into 99.40% by mass of the thermoplastic polyester-based elastomer (A-1), 0.10% by mass of fine powder of borosilicate glass (manufactured by Toagosei Co., Ltd., VZ100), and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 82% after heat treatment and was excellent in hydrolysis resistance.
[0068] [Example 9] Into 99.00% by mass of the thermoplastic polyester-based elastomer (A-1), 0.50% by mass of the same fine powder of borosilicate glass as in Example 8, and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 86% after heat treatment and was excellent in hydrolysis resistance.
[0069] [Example 10] Into 99.00% by mass of the thermoplastic polyester-based elastomer (A-1), 0.50% by mass of fine powder of borosilicate glass (manufactured by Nippon Frit, EHO151U40), and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 81% after heat treatment and was excellent in hydrolysis resistance.
[0070] [Example 11] Into 98.50% by mass of the thermoplastic polyester-based elastomer (A-1), 1.00% by mass of the same fine powder of borosilicate glass as in Example 10 and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 83% after heat treatment and was excellent in hydrolysis resistance.
[0071] [Example 12] Into 79.50% by mass of the thermoplastic polyester-based elastomer (A-1), 20.00% by mass of the same fine powder of borosilicate glass as in Example 1, and 0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. The obtained three dimensional network structure body had a reduced viscosity retention of 97% after heat treatment and was excellent in hydrolysis resistance.
[0072] [Example 13] Into 77.30% by mass of the thermoplastic polyester-based elastomer (A-1), 22.20% by mass of the same fine powder of borosilicate glass as in Example 1, and
0.25% by mass of each of the phenol-based antioxidant and the phosphorus-based antioxidant were mixed. The mixture was melt-extruded with a twin-screw extruder, cooled, pelletized, and dried to obtain a resin composition of a three-dimensional network fibrous structure body. A three-dimensional network structure body was obtained using the obtained resin composition in the same manner as in Example 1. The properties of the obtained three-dimensional network structure body are shown in Table 4. Although the obtained three-dimensional network structure body had a reduced viscosity retention of 97% after heat treatment and was excellent in hydrolysis resistance, the three dimensional network structure body gave a strong sticky feeling as a texture when touched.
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a)0
x 0 -a31 2
[0074] The three-dimensional network structure body of the present invention has excellent hydrolysis resistance and is not easily degraded by moisture in the air when used for a long period of time, thus making it suitable for long-term use in cushioning materials that are used for office chairs; furniture; sofas; beddings such as beds; seats for vehicles such as those for trains, automobiles, two-wheeled vehicles, child seats, and buggies; floor mats; and mats for impact absorption such as members for prevention of collision and nipping.
[0075] In the present specification and claims, the term 'comprising' and its derivatives including 'comprises' and 'comprise' is used to indicate the presence of the stated integers but does not preclude the presence of other unspecified integers.
Claims (2)
1. A three-dimensional network structure body comprising a resin composition of a thermoplastic polyester-based elastomer and having a three dimensional random loop-bonded structure that is formed of a continuous filament, wherein the resin composition contains borosilicate glass, the borosilicate glass has a mole fraction of the amount of boron atoms B (mol) to the amount of silicon atoms Si (mol) (B/Si) of 0.3 to 20, an amount of the borosilicate glass added is in the range of 0.01 to 20% by mass based on 100% by mass of the resin composition, and the three-dimensional network structure body has a boron content of no less than 15 ppm on a mass basis with respect to the three-dimensional network structure body.
2. The three-dimensional network structure body according to claim 1, wherein the borosilicate glass contains B 2 0 3 , Si0 2 , and an alkali metal oxide.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020077438 | 2020-04-24 | ||
| JP2020-077438 | 2020-04-24 | ||
| JP2021058055A JP2021175839A (en) | 2020-04-24 | 2021-03-30 | Three-dimensional net-like structure |
| JP2021-058055 | 2021-03-30 | ||
| PCT/JP2021/014394 WO2021215226A1 (en) | 2020-04-24 | 2021-04-02 | Three dimensional network structure body |
Publications (2)
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| AU2021260324A1 AU2021260324A1 (en) | 2022-12-15 |
| AU2021260324B2 true AU2021260324B2 (en) | 2024-02-08 |
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| AU2021260324A Active AU2021260324B2 (en) | 2020-04-24 | 2021-04-02 | Three dimensional network structure body |
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| KR (1) | KR20230002908A (en) |
| CN (1) | CN115427623A (en) |
| AU (1) | AU2021260324B2 (en) |
| TW (1) | TWI823079B (en) |
| WO (1) | WO2021215226A1 (en) |
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| CN114535867B (en) * | 2022-02-23 | 2022-09-20 | 哈尔滨焊接研究院有限公司 | Active agent for titanium alloy laser wire filling surfacing cladding and preparation method and application thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2921638B2 (en) | 1993-02-26 | 1999-07-19 | 東洋紡績株式会社 | Cushion net structure and manufacturing method |
| JPH08118533A (en) * | 1994-10-24 | 1996-05-14 | Asahi Glass Co Ltd | Resin molded object having multilayered structure |
| JPH10218641A (en) * | 1997-01-31 | 1998-08-18 | Nippon Glass Fiber Co Ltd | Antimicrobial and antifungal glass and resin composition containing the same glass |
| JP3152630B2 (en) * | 1997-04-28 | 2001-04-03 | イビデン株式会社 | Antibacterial and antifungal decorative board |
| JP2002194184A (en) * | 2000-12-26 | 2002-07-10 | Daicel Chem Ind Ltd | Polyester resin composition excellent in molding stability and molding |
| US20030216500A1 (en) * | 2002-04-29 | 2003-11-20 | Mckenna James Michael | Hydrolysis resistant polyester elastomer compositions and related articles and methods |
| JP2004050688A (en) * | 2002-07-22 | 2004-02-19 | Nippon Steel Chem Co Ltd | Laminate having nonwoven fabric layer |
| JP2004202844A (en) * | 2002-12-25 | 2004-07-22 | Toyobo Co Ltd | Thermoplastic polyester elastomer laminate excellent in weatherability |
| DE102004011520A1 (en) * | 2004-03-08 | 2005-10-06 | Schott Ag | Antimicrobial refractive index adapted phosphate glass |
| DE102006055478A1 (en) * | 2006-11-24 | 2008-05-29 | Bayer Materialscience Ag | Toughened filled polycarbonate compositions |
| DE102012004357B4 (en) * | 2012-03-07 | 2016-04-07 | Trovotech Gmbh | Flame retardant composition for thermoplastic polymers consisting of porous, amorphous glass powder and melamine cyanurate, their use as well as moldings, fibers and films finished therewith |
| JP5569641B1 (en) * | 2013-10-28 | 2014-08-13 | 東洋紡株式会社 | Elastic network structure with excellent quietness and lightness |
| CN108138409B (en) | 2015-10-16 | 2021-01-12 | 东洋纺株式会社 | Net-shaped structure having excellent hydrolysis resistance and method for producing same |
| US20200141029A1 (en) * | 2017-11-15 | 2020-05-07 | Primaloft, Inc. | Reduced density synthetic fiber utilizing hollow microcapsules |
| KR102243795B1 (en) * | 2018-09-28 | 2021-04-23 | 코아 가라스 가부시키가이샤 | Antimicrobial fiber and method for producing antimicrobial fiber |
| CN110655877A (en) * | 2019-11-15 | 2020-01-07 | 东莞市瑞年塑胶科技有限公司 | Dampproof, mildewproof, insect-proof and antibacterial self-adhesive wall sticker and preparation method thereof |
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2021
- 2021-04-02 WO PCT/JP2021/014394 patent/WO2021215226A1/en active Application Filing
- 2021-04-02 CN CN202180029891.1A patent/CN115427623A/en active Pending
- 2021-04-02 AU AU2021260324A patent/AU2021260324B2/en active Active
- 2021-04-02 KR KR1020227040610A patent/KR20230002908A/en unknown
- 2021-04-23 TW TW110114618A patent/TWI823079B/en active
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| CN115427623A (en) | 2022-12-02 |
| WO2021215226A1 (en) | 2021-10-28 |
| TWI823079B (en) | 2023-11-21 |
| KR20230002908A (en) | 2023-01-05 |
| TW202146721A (en) | 2021-12-16 |
| AU2021260324A1 (en) | 2022-12-15 |
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