WO2013073425A1 - プレス成型用不織布及びその製造方法並びに成型体の製造方法 - Google Patents
プレス成型用不織布及びその製造方法並びに成型体の製造方法 Download PDFInfo
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- WO2013073425A1 WO2013073425A1 PCT/JP2012/078801 JP2012078801W WO2013073425A1 WO 2013073425 A1 WO2013073425 A1 WO 2013073425A1 JP 2012078801 W JP2012078801 W JP 2012078801W WO 2013073425 A1 WO2013073425 A1 WO 2013073425A1
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- nonwoven fabric
- polylactic acid
- fibers
- kenaf
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4266—Natural fibres not provided for in group D04H1/425
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/48—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
- D04H1/485—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation in combination with weld-bonding
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/55—Polyesters
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- 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/558—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in combination with mechanical or physical treatments other than embossing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/043—PGA, i.e. polyglycolic acid or polyglycolide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0809—Fabrics
- B29K2105/0818—Fleece
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/697—Containing at least two chemically different strand or fiber materials
- Y10T442/698—Containing polymeric and natural strand or fiber materials
Definitions
- the present invention relates to a nonwoven fabric for performing press molding, a method for producing the same, and a method for producing a molded body using the nonwoven fabric.
- Patent Document 1 For the purpose of reducing deforestation, hot-press molding of lignocellulose short fibers and thermosetting resins obtained from oil palm, coconut palm, and kenaf A fiberboard has been proposed (Patent Document 1). Further, for the purpose of further reducing the environmental load, a fiber-based board has been proposed in which plant-derived polylactic acid resin and natural fibers are mixed and heated and pressurized to form the entire apparent density within a specific range. (Patent Document 2). Furthermore, as an improved invention of the invention of Patent Document 2, a wood molded body is disclosed in which an inorganic filler is further added to polylactic acid fibers and natural fibers in order to shorten the molding time (Patent Document 3).
- the manufacturing method of a molded object is the press solid molding method which heat-processes a nonwoven fabric and compresses using a metal mold
- wrinkles are generated in the molded body at the portion where the mold stops, which is the corner of the molded body.
- the molded body is thinned at that portion, and as a result, see-through and cracks occur.
- JP 2003-260704 A (Claims 1, 2 and 3) (US Pat. No. 6,197,414) JP 2004-130796 A (Claim 1, paragraphs 0006, 0023, 0024) (US Patent Application Publication No. 2004/096623) Japanese Patent Laying-Open No. 2005-262559 (Claim 1, paragraph 0007) (European Patent Application Publication No. 1726418)
- the present invention is intended to solve the problems related to press moldability in a three-dimensional molded body using a nonwoven fabric containing polylactic acid fibers and natural fibers.
- the first problem is the molding speed.
- the polylactic acid fiber mixed with talc used in Patent Document 3 has a cooling crystallization temperature of 99 ° C.
- it is necessary to cool the molded body after molding to 99 ° C. or less, and there is a problem that the cooling time is long.
- the second problem is the occurrence of wrinkles at the corners of the molded body corresponding to the rising part of the die diaphragm.
- the wrinkles at the corners of the rising parts are due to the low mold followability of the nonwoven fabric during fiber-based board molding, and the elongation of the nonwoven fabric when molded at a molding temperature of 200 ° C. has been a problem.
- the third problem is the occurrence of see-through and cracks in the molded product corresponding to the rising part of the deep drawing of the mold.
- the see-through part and cracks are caused by thinning of the molded body because the tensile strength of the nonwoven fabric is low when pulled by a mold, and optimization of the tensile properties of the nonwoven fabric was a problem. .
- the present invention has the following configuration.
- a nonwoven fabric comprising polylactic acid fibers and natural fibers, wherein the polylactic acid fibers have a temperature drop crystallization temperature of 120 ° C. or higher, the nonwoven fabric has a tensile strength of 20 N / cm 2 or higher, and is tensile in a 200 ° C. atmosphere.
- a non-woven fabric for press molding wherein the nonwoven fabric having an elongation of 30% has a tensile stress of 80 N / cm 2 or less.
- a polylactic acid fiber having a cooling crystallization temperature of 120 ° C. or more and a dry heat shrinkage of 5% or less and a natural fiber having a tensile strength of 1.0 cN / dtex or more are mixed, and then the total needle density is 30
- a method for producing a non-woven fabric for press molding characterized by performing needle punching at a rate of up to 200 pieces / cm 2 .
- a high-strength three-dimensional molded body using a nonwoven fabric containing polylactic acid fibers and natural fibers can be molded in a short time, and wrinkles, see-through, and cracks can be formed in the molded body corresponding to the rising portion of the die drawing. It is possible to obtain a material that is difficult to generate.
- FIG. 1A is a partially broken perspective view of a male mold when a molded body is produced
- FIG. 1B is a male mold of FIG. 1A and a female mold of FIG. 1C
- FIG. 1 (c) is a partially broken perspective view of a female mold when a molded body is manufactured
- 2 (a) is a plan view of the female mold shown in FIG. 1 (c)
- FIG. 2 (b) is a front view of the female mold
- FIG. 2 (c) is a right side view of the female mold. (The left side is symmetrical with the right side).
- FIG. 3 is a plan view showing a thickness measurement part (a circle with hatching) of the molded body.
- FIG. 4 is a plan view showing sampling positions (rectangles with diagonal lines) of test pieces for measuring the density and bending strength of the molded body.
- the polylactic acid fiber used in the present invention is a polymer having — (O—CHCH 3 —CO) — as a main repeating unit, and is obtained by polymerizing lactic acid or its oligomer. Since lactic acid has two types of optical isomers, D-lactic acid and L-lactic acid, the polymer is also composed of poly (D-lactic acid) consisting only of D isomer and poly (L-lactic acid) consisting only of L isomer and There is polylactic acid consisting of both. The optical purity of D-lactic acid or L-lactic acid in polylactic acid is lowered, the crystallinity is lowered and the melting point is lowered.
- the optical purity is preferably 90% or more in order to improve heat resistance.
- a more preferable optical purity is 93% or more, and a most preferable optical purity is 97% or more.
- the optical purity has a strong correlation with the melting point.
- the optical purity is about 90%, the melting point is about 150 ° C., the optical purity is 93%, the melting point is about 160 ° C., the optical purity is 97%, and the melting point is about 170 ° C. It becomes.
- the melting point of polylactic acid is preferably 200 ° C. or less, more preferably 190 ° C. or less, and most preferably 180 ° C. or less.
- a polymerization method to polylactic acid resin used for polylactic acid fiber direct dehydration condensation method in which lactic acid is dehydrated and condensed as it is in the presence of an organic solvent and a catalyst, lactide, aromatic polyester and / or aliphatic polyester are used. Examples thereof include a ring-opening copolymerization and transesterification reaction in the presence of a ring-opening polymerization catalyst, and an indirect polymerization method in which lactic acid is once dehydrated to form a cyclic dimer and then subjected to ring-opening polymerization.
- the weight average molecular weight of the polylactic acid fiber is preferably 80,000 or more from the viewpoint of heat resistance and moldability, more preferably 100,000 or more, and further preferably 120,000 or more.
- the polylactic acid fiber has a weight average molecular weight of preferably 350,000 or less, more preferably 300,000 or less, and even more preferably 250,000 or less.
- these low molecular weight residues are a cause of causing fouling of heaters used in stretching and false twisting processes. Become. Further, in order to promote the hydrolyzability of the polylactic acid fiber and reduce the durability, these low molecular weight residues are preferably 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.2% by mass. % Or less.
- the polylactic acid fiber is preferably partially or entirely blocked from the COOH end group terminal of the molecular chain. By blocking the COOH end group end of a part of the molecular chain of polylactic acid, heat resistance and hydrolysis resistance can be improved.
- the polylactic acid fiber preferably has a COOH end group concentration in the range of 1 to 20 equivalents / ton. More preferably, it is in the range of 1 to 10 equivalent / ton.
- the reason for setting the COOH end group concentration of the polylactic acid fiber to 20 equivalent / ton or less is that it is possible to improve the durability of the polylactic acid fiber that is susceptible to degradation due to hydrolysis during storage or transportation by sea. It can be mentioned. Moreover, when it is 10 equivalent / ton or less, it is further excellent in durability and can be applied to more severe applications. Further, when the COOH end group concentration is less than 1 equivalent / ton, it is very difficult to produce staple fibers.
- the polylactic acid fiber preferably has an epoxy residual value of 0.1 to 0.5 equivalent / kg. By doing so, it is suitable for longer-term storage and more excellent in durability when used as a fiber structure, and is useful for expanding the range of use of polylactic acid fibers.
- the epoxy residual value indicates the amount of the epoxy compound remaining in the polylactic acid fiber, and the unreacted epoxy compound reacts newly in the process where the polylactic acid fiber is hydrolyzed by storage and processing. By reacting with the COOH end group in the lactic acid fiber, there is an effect of further suppressing hydrolysis of polylactic acid.
- the epoxy residual value in the polylactic acid fiber is less than 0.1 equivalent / kg, the amount of epoxy compound remaining in the polylactic acid fiber is small, so when the polylactic acid fiber begins to hydrolyze, This is not preferable because the COOH end groups of the poly (lactic acid) increase at an accelerated rate and the high elongation of the polylactic acid fiber decreases. Further, if it is more than 0.5 equivalent / kg, the amount of the epoxy compound in the polylactic acid fiber is increased, the spinnability is deteriorated, and the epoxy compound in the polylactic acid fiber is bleed, which is preferable in use. Absent.
- the amount of the epoxy compound to be added, the amount of the epoxy compound that reacts with the COOH terminal of the polylactic acid fiber, and the number of epoxy groups in one molecule of the epoxy compound are adjusted. Can be done.
- a base chip obtained by adding 10 to 20% by mass of an epoxy compound to a virgin chip of polylactic acid fiber is used as a first step.
- a master chip is prepared by kneading at °C, and the reaction is further advanced by kneading the virgin tip and the master chip at 220 to 240 ° C. in a spinning extruder.
- reaction of the COOH terminal of a polylactic acid fiber and an epoxy compound can be advanced, and an epoxy residual value can be adjusted to a predetermined range.
- the addition amount of the epoxy compound is preferably 1 to 5% by mass based on the polylactic acid fiber.
- the epoxy compound is tetrakis (oxiranylmethyl) 7,8-dimethyl-1,7,8,14-tetradecanetetracarboxylate, 7-oxabicyclo [4.
- Diglycidyl heptane-3,4-dicarboxylate and triglycidyl isocyanurate are preferable, and triglycidyl isocyanurate is particularly preferable as the monomer because of its high reactivity and excellent handleability.
- Triglycidyl isocyanurate is a powder having a melting point of about 100 ° C., and is easy to handle.
- triglycidyl isocyanurate When triglycidyl isocyanurate is melted and mixed with polylactic acid, triglycidyl isocyanurate is an epoxy having three or more functions in polylactic acid. A structure in which the compound is finely dispersed can be obtained, the spots of the melt viscosity and molecular weight of the resin can be reduced, and the polylactic acid fiber used in the present invention can be stably produced. Furthermore, since triglycidyl isocyanurate is excellent in the crystallinity of the compound itself, it is possible to suppress fuming due to scattering of the epoxy compound, particularly in the production of a melt-formed product using the polylactic acid fiber used in the present invention. This is preferable.
- the polylactic acid fiber needs to have a cooling crystallization temperature of 120 ° C. or higher.
- a temperature-falling crystallization temperature of 120 ° C or higher.
- crystallization of polylactic acid starts at a high temperature in press solid molding, so the crystallization speed is fast and even in a short press cycle (less than 10 seconds) High crystallinity can be maintained. That is, since the temperature-falling crystallization temperature is 120 ° C. or higher, it is possible to shorten the press time at the time of three-dimensional molding that affects the bending strength of the molded body, and it becomes possible to mold with high productivity.
- the temperature-falling crystallization temperature is more preferably 125 ° C. or higher, and further preferably 130 ° C. or higher.
- polylactic acid fibers are not crystallized at lower temperatures when crystal nucleating agents are not used, and a high strength molding with a bending strength of 20 N / mm 2 or more is achieved by cooling a heat-treated 200 ° C. nonwoven fabric to about 50 ° C. You can get a body. In this case, a solid molding time of about 15 seconds is required, and if it is less than 15 seconds, a molded body with low bending strength is obtained.
- the temperature-falling crystallization temperature is 99 ° C.
- the heat-treated 200 ° C. non-woven fabric is cooled to 99 ° C. to have a bending strength of 20 N / mm 2 or more.
- a molded article with high strength can be obtained.
- a solid molding time is required for about 10 seconds, and if it is less than 10 seconds, a molded body with low bending strength is obtained.
- the temperature-falling crystallization temperature can be increased to 120 ° C. or higher, and the heat-treated 200 ° C. non-woven fabric is cooled to 120 ° C. to have a bending strength of 20 N / mm 2.
- the above-mentioned high strength molded product can be obtained.
- the three-dimensional molding time may be about 8 seconds, which can be shortened by about 2 seconds compared to the case where talc is used.
- This polylactic acid fiber having a temperature-falling crystallization temperature of 120 ° C. or higher can be achieved by using an organic or inorganic crystal nucleating agent.
- carbon black which is an inorganic crystal nucleating agent, is preferable because the crystal nuclei of polylactic acid can be formed in a short time and the temperature-falling crystallization temperature can be raised to 120 ° C. or higher. The reason for this seems to be that the particle size is very small. Therefore, the particle size of the carbon black is preferably 50 nm or less, more preferably 40 nm or less, and still more preferably 30 nm or less.
- the amount of the crystal nucleating agent added to the polylactic acid fiber is preferably 0.01% by mass or more, and preferably 0.1% by mass or more as the lower value of the addition amount from the viewpoint of moldability and production cost. More preferably, it is more preferably 0.5% by mass or more.
- the upper value of the amount of the crystal nucleating agent added relative to the polylactic acid fiber is preferably 10.0% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.
- the polylactic acid fiber may contain particles, flame retardants, plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants such as ethylenebissteasanamide, etc. in addition to the crystal nucleating agent.
- cross-sectional shape of the polylactic acid fiber a round cross-section, a hollow cross-section, a porous hollow cross-section, a multileaf cross-section such as a trilobal cross section (triangular cross section, Y cross section, T cross section, etc.), flat cross section, W cross section, X cross section, etc. It is possible.
- the tensile strength of the polylactic acid fiber measured according to the method A is preferably 0.5 cN / dtex or more.
- the carding passability is remarkably deteriorated. More preferably, it is 1.0 cN / dtex or more, More preferably, it is 2.0 cN / dtex or more.
- the tensile elongation of the polylactic acid fiber is preferably 60% or more.
- the nonwoven fabric can be easily stretched and the followability of the nonwoven fabric to the mold becomes high, so the nonwoven fabric is not torn and the quality of the molded body is good.
- the tensile elongation of the polylactic acid fiber is more preferably 65% or more, and further preferably 70% or more.
- the dry heat shrinkage of the polylactic acid fiber measured according to b) is preferably 5% or less.
- the dry heat shrinkage rate is 5% or less, the dimensional stability of the molded body is increased. If the dry heat shrinkage is too high, wrinkles are generated during press solid molding of the nonwoven fabric, and the quality of the molded body may be lowered.
- the polylactic acid fiber preferably has crimps.
- the number of crimps is preferably 6 to 20 peaks / 25 mm, more preferably 8 to 15 peaks / 25 mm.
- the crimping degree is preferably 10 to 50%, more preferably 15 to 30%.
- the fineness of the polylactic acid fiber measured according to JIS L 1015 (1999) 8.5.1 A method is preferably 0.5 to 100 dtex.
- the fineness is less than 0.5 dtex, the carding passability is remarkably deteriorated, and it becomes difficult to obtain a spun yarn or a nonwoven fabric.
- it exceeds 100 dtex, the fiber dispersibility in the nonwoven fabric production process is lowered. More preferably, it is 1.0 to 10 dtex, and still more preferably 3.0 to 7.0 dtex.
- the fiber length of the polylactic acid fiber measured according to the method A is preferably 5 to 150 mm.
- the fiber length of the polylactic acid fiber is more preferably 10 to 100 mm, still more preferably 30 to 70 mm.
- a spinning oil containing a smoothing agent is applied to the polylactic acid fiber.
- the slipperiness of the polylactic acid fiber is improved, and the processability of carding, such as spinning and drawing, is improved.
- the crimped spots of the obtained fiber itself can be reduced, the quality of fluff and the like can be improved, and the fiber opening property and the dispersibility of the fiber in the fiber structure can be improved.
- the smoothing agent include fatty acid esters, polyhydric alcohol esters, ether esters, polyethers, silicones, and mineral oils. These smoothing agents may be used as a single component, or a plurality of components may be mixed and used.
- the amount of the oil agent to be attached is preferably 0.1 to 2.0% by mass, more preferably 0.2 to 0.7% by mass with respect to the polylactic acid fiber. By setting it within the range, the process passability during carding can be improved.
- the oil agent is an emulsifier, an antistatic agent, an ionic surfactant, a bundling agent, a rust preventive agent that emulsifies the oil agent in water to lower the viscosity and improve adhesion to the yarn and permeability. It is also preferable to add a preservative, an antioxidant and the like.
- Polylactic acid fiber can be produced by a known method such as a method of melt spinning a polylactic acid resin.
- the yarn made of the melted polylactic acid resin is cooled, provided with an oil agent, and taken off.
- the take-up speed is preferably 400 to 2000 m / min.
- the undrawn yarn of polylactic acid fiber is drawn and drawn.
- the drawing is preferably performed so that the total fineness of the tow after drawing becomes 50,000 to 1,000,000 dtex.
- the drawing of the polylactic acid fiber is preferably performed by liquid bath drawing using hot water at 60 to 100 ° C. in order to obtain a uniform tow.
- the draw ratio for drawing the polylactic acid fiber is preferably 1.5 to 6 times. By doing so, polylactic acid fibers having appropriate strength can be obtained.
- crimping is preferably applied to the drawn yarn.
- the crimping method include a stuffing box method, an indentation heating gear method, and a high-speed air injection indentation method.
- the polylactic acid fiber is preferably subjected to relaxation heat treatment in a tow state after crimping. By doing so, crimps can be maintained and polylactic acid fibers having a low dry heat shrinkage rate can be produced. It is preferable to set the temperature in the relaxation heat treatment to 100 to 170 ° C. because the dry heat shrinkage of the polylactic acid fiber becomes 5% or less.
- the temperature in the relaxation heat treatment is more preferably 120 to 165 ° C, still more preferably 140 to 160 ° C. Thereafter, the polylactic acid fiber can be cut into a desired fiber length by a cutting device such as a rotary cutter.
- Natural fiber examples include wood pulp, bagasse, wheat straw, reed, papyrus, bamboo, pulp, cotton, kenaf, roselle, asa, flax, ramie, jute, hemp, sisal, Manila asa, palm, banana and the like. These may be used alone, but preferably contain one or more fibers selected from these. In particular, kenaf fiber has excellent strength among natural fibers. Kenaf fibers have a relatively long fiber length. Kenaf is an annual grass that grows very fast in the tropics and temperate regions, and belongs to herbs that can be easily cultivated.
- the natural fiber of the present invention preferably contains kenaf fiber.
- the ratio in the natural fiber is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 90% by mass or more.
- Kenaf fiber is cut into kenaf stalks, then subjected to a reading process, and cut to the desired fiber length with a guillotine cutter.
- Reding treatment is a method of peeling the core portion and bast fiber portion of kenaf.
- the kenaf stem can be easily peeled off by fermentation with bacteria.
- Fermentation methods include a method of leaving on the ground and fermenting with moisture in the air, and a method of immersing in water of rivers and swamps and fermenting. This fermentation causes an unpleasant odor in the kenaf fiber.
- As a countermeasure against odor when fermenting in water, it is preferable because odor can be reduced by fermentation in a clean river.
- the odor can be further reduced by placing the kenaf fiber in an aqueous sodium hydroxide solution at 100 ° C. and treating it for 20 minutes.
- the sodium hydroxide aqueous solution preferably has a sodium hydroxide concentration of 10% or less, more preferably 5% or less, and still more preferably 2% or less. By doing so, an odor component can be removed while maintaining the strength of the kenaf fiber.
- the kenaf fiber is treated in a swamp that is dirty and does not flow, there is a risk of generating a strong unpleasant odor.
- the natural fiber such as kenaf fiber is 1-methoxy-2-propylacetate (C) in the odor amount measured by (2) Method for measuring the odor amount of natural fiber such as kenaf fiber (see paragraph 0081).
- 6 H 12 O 3 ), ethanol, 2-methoxy-acetate (C 5 H 10 O 3 ), and formaldehyde are each preferably 2 ⁇ g / kg or less. More preferably, it is 1 ⁇ g / kg or less, more preferably 0.5 ⁇ g / kg or less.
- acetic acid, trimethylbenzene, and acetaldehyde are each preferably 10 ⁇ g / kg or less. More preferably, it is 5 ⁇ g / kg or less, more preferably 3 ⁇ g / kg or less.
- the natural fiber such as kenaf fiber has a tensile strength measured by (2) Tensile strength / tensile elongation measuring method of natural fiber such as kenaf fiber (see paragraph 0079) in the below-mentioned Examples of 1.0 cN / dtex or more. Preferably there is.
- a non-woven fabric containing natural fibers such as kenaf fibers having a tensile strength of 1.0 cN / dtex or more a molded body having high bending strength is obtained. More preferably, the natural fiber has a tensile strength of 1.5 cN / dtex or more, and more preferably 2.0 cN / dtex or more.
- the natural fiber such as kenaf fiber has a fiber length of 150 mm or less as measured by the fiber length measurement method (see paragraph 0077) of natural fiber such as kenaf fiber in Examples described later. If the average fiber length is too long, it becomes difficult to uniformly disperse natural fibers such as kenaf fibers and polylactic acid fibers in the manufacturing process of the nonwoven fabric. As a result, productivity decreases and the strength of the nonwoven fabric and the molded body becomes non-uniform, and the strength may partially decrease.
- the average fiber length of natural fibers is more preferably 120 mm or less, and still more preferably 100 mm or less.
- the natural fiber such as kenaf fiber preferably has a fiber diameter of 200 ⁇ m or less as measured by the fiber diameter measurement method (see paragraph 0078) of natural fiber such as kenaf fiber in Examples described later. Since the fiber diameter is 200 ⁇ m or less, the dispersibility of natural fibers and polylactic acid fibers is improved in the nonwoven fabric production process, and a uniform nonwoven fabric can be produced. More preferably, the fiber diameter of the natural fiber is 150 ⁇ m or less, and more preferably 100 ⁇ m.
- the natural fiber such as kenaf fiber is composed of 5 or more voids derived from the conduit measured by the method for measuring the number of voids of natural fiber such as kenaf fiber (see paragraph 0082) in Examples described later. It is preferable. If the number of voids derived from the conduit in the kenaf fiber is less than 5, the tensile strength is low, which may adversely affect the properties of the nonwoven fabric and the molded product. The number of voids is more preferably 10 or more, and still more preferably 20 or more.
- the natural fiber such as kenaf fiber preferably has a moisture content of 20% by mass or less as measured by the method for measuring the moisture content of natural fiber such as kenaf fiber (see paragraph 0080) in Examples described later. If the water content is more than 20% by mass, water vapor is generated during hot press molding and may burst when the press is released, damaging the fiber board. The water content is more preferably 15% by mass or less, and still more preferably 10% by mass or less.
- the nonwoven fabric used in the present invention can be produced by blending, opening, and interlacing polylactic acid fibers and natural fibers such as kenaf fibers.
- polylactic acid fiber and natural fiber are mixed with an opener.
- the obtained product is opened by a carding method or an airlaid method to form a web.
- a plurality of the obtained products are laminated. And this laminated body is put together and the fibers are entangled by the needle punch method or the like to obtain a non-woven fabric having a high density.
- Kenaf fibers have a low tensile elongation, fiber diameters vary, and there are nodes and the like.
- the needle density of the needle punched nonwoven fabric is preferably 30 to 200 needles / cm 2 in total. More preferably, it is 40 to 150 / cm 2 , and still more preferably 50 to 100 / cm 2 .
- an excessive needle punch with needle density exceeding 200 needles / cm 2 is performed on a nonwoven fabric, natural fibers such as kenaf fibers are destroyed by needles of the needle punch, the length of natural fibers such as kenaf fibers is shortened, and the fiber length is 45 mm or more.
- the natural fiber such as kenaf fiber is less than 30% by mass, and the entanglement between the polylactic acid fiber and the natural fiber such as kenaf fiber tends to decrease. Further, when the needle density is less than 30 / cm 2, the entanglement of natural fibers such as polylactic acid fibers and kenaf fibers is weakened, the tensile strength of the nonwoven fabric is lowered, and the strength of the molded body using the nonwoven fabric is also lowered. Tend.
- the needle density of this nonwoven fabric is the actual number of nonwoven fabrics hit by the needles of the needle punch device, and can be set by the number of needles of the needle punch device and the moving speed of the nonwoven fabric.
- the nonwoven fabric needs to have a tensile strength of 20 N / cm 2 or more measured in (3) Tensile strength / tensile elongation measurement method (see paragraph 0088) of the nonwoven fabric in Examples described later. More preferably, it is 50 N / cm ⁇ 2 > or more, More preferably, it is 100 N / cm ⁇ 2 > or more.
- the tensile strength is in the above-described range, a molded body without wrinkles, see-through, and cracks can be manufactured at the rising portion of the mold during the press three-dimensional molding of the nonwoven fabric without being tangled between fibers.
- the nonwoven fabric having a tensile strength of 20 N / cm 2 or more for example, in the fiber length frequency distribution (histogram) of natural fibers such as kenaf fibers in the nonwoven fabric, natural fibers such as kenaf fibers having a fiber length of 45 mm or more are 30% or more. This is preferable because it can be achieved.
- the strength and entanglement of natural fibers such as kenaf fibers are particularly important compared to the physical properties of polylactic acid fibers. By doing so, the entanglement between the fibers becomes strong.
- the fiber length frequency distribution of natural fibers such as kenaf fibers is more preferably 40% or more when the fiber length is 45 mm or more, and even more preferably 50% or more when the fiber length is 45 mm or more.
- the fabric weight of a nonwoven fabric is 450 g / m ⁇ 2 > or more. If the basis weight of the non-woven fabric is less than 450 g / m 2 , the thickness of the die will be reduced at the rising edge of the die during press solid molding, thereby causing see-through and cracking. More preferably, the basis weight of the nonwoven fabric is 700 g / m 2 or more, and more preferably 1000 g / m 2 or more.
- the tensile elongation measured by (3) Tensile strength / tensile elongation measuring method (see paragraph 0088) of the nonwoven fabric in Examples described later is 30% or more.
- the tensile elongation of the nonwoven fabric is 30% or more, the followability of the nonwoven fabric to the mold at the rising portion of the mold drawing during press three-dimensional molding is enhanced, and the molded body is free from wrinkles, see-through, and cracks.
- the nonwoven fabric has a tensile elongation of 40% or more, more preferably 50% or more.
- the nonwoven fabric has a tensile stress of 80 N / cm 2 or less at a tensile elongation of 30% in a 200 ° C. atmosphere measured by (3) Tensile strength / tensile elongation measurement method (see paragraph 0088) of the nonwoven fabric in Examples described later. It is necessary to be. More preferably, the tensile stress at a tensile elongation of 30% in an atmosphere of 200 ° C. is 60 N / cm 2 or less, more preferably 50 N / cm 2 or less.
- the tensile stress at a tensile elongation of 30% in an atmosphere of 200 ° C. specified in the present invention assumes the molding of the rising portion of the die drawing at the time of press solid molding of a nonwoven fabric.
- the nonwoven fabric follows the corner of the rising part of the die drawing without resistance, and the wrinkle is not formed at the corner of the rising part.
- the body can be manufactured.
- a nonwoven fabric having a tensile stress of 80 N / cm 2 or less at a tensile elongation of 30% in an atmosphere of 200 ° C. is preferable because the weight per unit area is 3000 g / m 2 or less.
- the nonwoven fabric By setting the basis weight of the nonwoven fabric to 3000 g / m 2 or less, the nonwoven fabric becomes a flexible nonwoven fabric that follows the corner of the rising portion of the die diaphragm. Since the nonwoven fabric having a basis weight of more than 3000 g / m 2 is difficult to stretch, a large amount of the nonwoven fabric is gathered at the corner of the rising portion of the die drawing and wrinkles are generated.
- the basis weight of the nonwoven fabric is more preferably 2500 g / m 2 or less, and still more preferably 2000 g / m 2 or less.
- the air permeability of the nonwoven fabric is preferably 30 cc / cm 2 / sec or more.
- the air permeability of the nonwoven fabric is more preferably 40 cc / cm 2 / sec or more, and still more preferably the air permeability is 50 cc / cm 2 / sec or more.
- the thickness of the nonwoven fabric is preferably 1 mm or more, more preferably 2 mm or more, more preferably 5 mm or more, and more preferably 300 mm or less, more preferably 200 mm or less, and even more preferably 50 mm or less. Even more preferred.
- the processability in the nonwoven fabric manufacturing process is good, and the molded body using the nonwoven fabric has bending strength, It will be excellent in quality.
- the nonwoven fabric preferably has a mass ratio of 20 to 60 to 80 to 40 of natural fibers such as polylactic acid fibers and kenaf fibers.
- natural fibers such as polylactic acid fibers and kenaf fibers.
- the ratio of the polylactic acid fiber and the natural fiber such as kenaf fiber is more preferably 25 to 55 to 75 to 45, and further preferably 30 to 50 to 70 to 50 in terms of mass ratio.
- the non-woven fabric used was (1) 1-methoxy-2-propylacetate (C 6 H 12 O 3 ), ethanol, 2 in the odor amount measured by (3) Method for measuring odor amount of non-woven fabric (see paragraph 0090).
- -Methoxy-acetate (C 5 H 10 O 3 ) and formaldehyde are each preferably 2 ⁇ g / kg or less. More preferably, it is 1 ⁇ g / kg or less, more preferably 0.5 ⁇ g / kg or less.
- acetic acid, trimethylbenzene, and acetaldehyde are each preferably 10 ⁇ g / kg or less. More preferably, it is 5 ⁇ g / kg or less, more preferably 3 ⁇ g / kg or less.
- the molded body of the present invention is obtained by press molding the above-mentioned nonwoven fabric. Unlike injection molding and extrusion molding, press molding can efficiently obtain a relatively large molded body such as 1 m square. Since a non-woven fabric is used as a material, a part or all of the molded body is usually plate-shaped.
- Examples of the molding method of the molded body are as follows. First, the nonwoven fabric is cut and laminated so as to achieve the target weight. The laminated nonwoven fabric is subjected to a hot press and a cooling press to produce a flat plate-like preboard. Thereafter, the preboard is heat-treated and three-dimensionally molded using a mold. As molding conditions, molding in the following range is preferable because bending strength is increased.
- Hot press conditions platen temperature 150 to 220 ° C., pressure 10 to 5000 kN / m 2 , press time 5 to 240 seconds.
- Cold press conditions platen temperature 10 ° C. to 40 ° C., pressure 10 to 5000 kN / m 2 , press time 5 to 240 seconds.
- Heat treatment conditions Heat until the internal temperature of the preboard reaches 150-220 ° C.
- Three-dimensional molding conditions mold temperature 10 to 40 ° C., pressure 10 to 5000 kN / m 2 , press time 5 to 240 seconds.
- the nonwoven fabric is cut and laminated so as to have a target basis weight.
- the laminated nonwoven fabric is heat-treated and three-dimensionally molded using a mold. This method is preferable because the number of steps required for molding can be reduced.
- As the molding conditions it is preferable to perform molding within the following range because the bending strength is increased.
- Heat treatment conditions Heat until the internal temperature of the non-woven fabric reaches 170 to 220 ° C.
- Three-dimensional molding conditions mold temperature 10 to 40 ° C., pressure 10 to 5000 kN / m 2 , press time 5 to 240 seconds.
- a nonwoven fabric does not need to be laminated
- a roll press machine, a flat plate press machine or the like can be used as the pressing method.
- a hot press machine that presses with a pair of upper and lower hot press surface plates is preferable because a sufficient hot press time can be secured.
- heat treatment method hot air, far-infrared heat, and microwave heat can be used.
- far-infrared heat and microwave heat are preferable because they can give heat to the inside of the nonwoven fabric in a short time.
- the three-dimensional molding is preferably performed by three-dimensional press molding using a cooling press machine equipped with a general-purpose cooling means such as air or water and attached with a mold.
- the press time (the time from the start of pressurization to the release) of the preboard or nonwoven fabric after the heat treatment is preferably 8 seconds or less, more preferably 7.5 seconds or less, and even more preferably 7 seconds or less. By doing so, the molding time can be shortened and the production cost can be reduced.
- the density of the obtained molded body is preferably 0.4 to 1.2 g / cm 3 . Since the density is 0.4 to 1.2 g / cm 3 , the bending strength of the molded body can be increased. When the density is less than 0.4 g / cm 3, the strength required for automobile interior materials and building materials is insufficient. A density exceeding 1.2 g / cm 3 is not preferable because lightness is lost.
- the density of the molded body is more preferably 0.5 to 1.1 g / cm 3 , and still more preferably 0.6 to 1.0 g / cm 3 .
- a molded body having a bending strength of less than 10 N / mm 2 has a low strength and is difficult to apply to automobile interior materials and building materials.
- the molded body is preferably 3 or less (there is an obvious odor but no unpleasant odor) in the numerical value determined by the after-mentioned Example (4) odor sensory test method (see paragraph 0096) of the molded body. More preferably, it is 2 or less (there is odor but no unpleasant odor), and more preferably 1 (no odor).
- This is made possible by molding the nonwoven fabric of the present invention under the above heat treatment conditions. In particular, when the upper limit of the heat treatment condition exceeds 220 ° C., natural fibers such as kenaf fibers in the nonwoven fabric are burnt, and a strong unpleasant odor is generated from the molded body.
- Fiber length Measured according to JIS L 1015 (1999) 8.4.1 A method. Weigh 800 mg of sample, create a staple diagram, equally divide the staple diagram into 50 fiber length groups, measure the boundary and fiber length of each segment, and determine the average fiber length of 49 at both ends In addition, the average fiber length (mm) was calculated by dividing by 50, and the average value of 2 times was defined as the fiber length.
- Tensile strength (cN / dtex) SD / F0
- SD maximum load (cN)
- F0 single yarn fineness (dtex) of the sample
- Tensile elongation (%) (E1-E2) / (L + E1) ⁇ 100
- E1 Looseness (mm)
- E2 Elongation at maximum load (mm)
- L Grazing interval (mm).
- Dry heat shrinkage (%) ((L ⁇ L ′) / L) ⁇ 100
- L Distance between grips when initial load before 150 ° C treatment is applied (mm)
- L ' Distance between grips when initial load is applied after 150 ° C treatment (mm)
- E. Molecular weight Polylactic acid is dissolved in chloroform to obtain a measurement solution, which is measured by gel permeation chromatography (GPC) under conditions of a column temperature of 40 ° C. and a flow rate of 1 ml / min.
- the number average molecular weight (Mn) and weight in terms of polystyrene Average molecular weight (Mw) was determined. The number of measurements was 5, and the arithmetic average value was calculated.
- the particle size is SALD-7100 manufactured by Shimadzu Corporation.
- the median diameter d50 of laser diffraction method (distribution standard is number, 50% cumulative particle size where the number of particles on the large diameter side is equal to the number of particles on the small diameter side. Measure the diameter). The number of tests was five, and the arithmetic average value was taken as the particle size.
- Epoxy residual value It measured according to the epoxy equivalent of JISK7236 (2001) epoxy resin.
- the sample was taken in a beaker, dissolved in 20 ml of chloroform, dissolved, 40 ml of acetic acid and 10 ml of tetraethylammonium bromide solution were added, and potentiometric titration was performed with a 0.1 mol / liter perchloric acid acetic acid solution. Thereafter, in order to correct the 0.1 mol / liter perchloric acid acetic acid solution consumption by the sample, only chloroform and acetic acid were added to the sample, the titrated value was subtracted, and the epoxy residual value was calculated by a method of performing correction.
- COOH end group concentration A weighed sample was dissolved in o-cresol, and an appropriate amount of dichloromethane was added, followed by titration with a 0.02 N KOH methanol solution. At this time, an oligomer such as lactide, which is a cyclic dimer of lactic acid, is hydrolyzed to generate a COOH group terminal, so that all of the COOH group terminal of the polymer, the monomer-derived COOH group terminal, and the oligomer-derived COOH group terminal are combined. The COOH group terminal concentration is determined. This concentration was defined as the COOH end group concentration.
- the number of crimps was measured according to JIS L 1015 (1999) 8.12.1. A dividing line is made in the same manner as the tensile strength / tensile elongation of JIS L 1015 (1999) 8.7.1 (however, the spatial distance is 25 mm), and several pieces in which the crimp is not impaired. One sample collected from each part was loosened by 25 ⁇ 5% with respect to the spatial distance, and both ends were fixed with an adhesive.
- the sample is attached to the grip of the crimping tester one by one, and after cutting the piece of paper, the distance between the grips when the initial load (0.18 mN x number of displayed tex) is applied to the sample (space distance: mm)
- the number of crimps at that time was counted to obtain the number of crimps per 25 mm length, and the arithmetic average value of 20 times was defined as the number of crimps.
- Natural fibers such as kenaf fiber Fiber length 100 natural fibers such as kenaf fiber length were randomly collected from 1 kg of natural fibers such as kenaf fiber. At the time of sampling, natural fibers such as kenaf fibers with broken or broken pieces were not used as test pieces. The collected natural fibers such as kenaf fibers were pasted on a backing sheet with a double-sided tape affixed straight with an appropriate force, the fiber length was measured to 1 mm with calipers, and the arithmetic average value of 100 fibers was defined as the fiber length.
- Fiber diameter The fiber diameter of natural fibers such as kenaf fibers was randomly selected from 1 kg of natural fibers such as kenaf fibers, and the cross-sectional diameter (diameter of circumscribed circle) was measured with a magnifier using a scanning electron microscope. The arithmetic average value of 60 fibers was taken as the fiber diameter. The fiber diameter was measured with an accuracy of 0.1 ⁇ m.
- test pieces are collected from natural fibers such as kenaf fiber. Each test piece was placed in a 600 milliliter Duran bottle, sealed, and allowed to stand for 24 hours in a standard state of 20 ° C. and a relative humidity of 65%. After leaving, 2 L of the atmosphere in the Duran bottle was sampled into the collection tube while sending high purity nitrogen gas into the Duran bottle. Aldehydes (acetaldehyde, formaldehyde) were eluted with 5 ml of acetonitrile using a collection tube (DNPH SILICA sampler), and the extract was concentrated 10 times by nitrogen purge.
- DNPH SILICA sampler a collection tube
- Odor amount of aldehydes [component amount in extract ( ⁇ g / ml) ⁇ extract amount (ml) ⁇ aldehyde molecular weight ⁇ 1000] / [concentration magnification ⁇ (aldehyde molecular weight + 180) / sample amount ( g)]
- VOC volatile organic compound
- the number of voids The cross section of natural fibers such as kenaf fibers was observed with an SEM (scanning electron microscope), and the number of voids derived from the conduits was counted. The number of voids of 10 natural fibers such as kenaf fiber was counted, and the number of voids was divided by 10 to obtain the arithmetic average value per one as the number of voids.
- the frequency distribution was divided into fiber lengths of less than 45 mm, fiber lengths of 45 mm or more and less than 65 mm, 65 mm or more and less than 85 mm, and 85 mm or more, the respective numbers were counted, and the fiber length ratio was calculated by the following formula.
- the basis weight was measured according to JIS L 1906 (2000) 5.2. Three test pieces each having a size of 200 mm ⁇ 250 mm were taken from different parts of the sample, allowed to stand for 24 hours in a standard state at a temperature of 20 ° C. and a relative humidity of 65%, weighed each mass (g), and an arithmetic average value thereof. Was expressed in terms of mass per 1 m 2 (g / m 2 ).
- Thickness Three test pieces with a size of 200 mm x 250 mm were collected from different parts of the sample and left for 24 hours in a standard state at a temperature of 20 ° C and a relative humidity of 65%. The thickness (mm) was measured to 0.01 mm with a measuring instrument (TECLOCK type SM-123), and the arithmetic average value was defined as the thickness.
- the suction fan was adjusted so that the inclination type barometer showed a pressure of 125 Pa by an adjusting resistor, and from the pressure indicated by the vertical type barometer and the type of air hole used, The amount of air passing through the test piece was obtained from the table attached to the tester, and the arithmetic average value for the five test pieces was defined as the air permeability.
- test pieces each having a size of 50 mm ⁇ 200 mm were collected from the nonwoven fabric in the vertical direction and the horizontal direction. Each test piece was allowed to stand for 48 hours in a standard state at a temperature of 20 ° C. and a relative humidity of 65%, and then the test piece was attached to a tensile tester at a spacing of 100 mm. A load was applied at a tensile speed of 100 mm / min until the test piece was cut, the strength at the maximum load was measured, and the arithmetic average value of 5 times was calculated for each of the vertical and horizontal directions using the following formulas. .
- G Tensile stress with a tensile elongation of 30% in an atmosphere of 200 ° C.
- Five test pieces each having a size of 50 mm ⁇ 200 mm were taken from the nonwoven fabric in the vertical direction and the horizontal direction.
- a heating furnace is attached to the tensile tester, and the test piece is placed in a tensile tester with a holding interval of 100 mm and left for 1 min in a state where the test piece is placed in a 200 ° C. atmosphere, and then the test piece is cut at a tensile speed of 100 mm / min.
- Odor amount Two test pieces of 22 g were collected from the nonwoven fabric. The collected test piece was measured for the odor amount in the same manner as in (2) Method for measuring odor amount of natural fiber such as kenaf fiber (see paragraph 0081).
- Molded body weight (g / m 2 ) nonwoven fabric weight (g / m 2 )
- Thickness is measured at the three points shown in Fig. 3 (see circles with diagonal lines in Fig. 3) after the molded body is left for 24 hours in a standard state at a temperature of 20 ° C and a relative humidity of 65%.
- the thickness (mm) of the body was measured to 0.1 mm with a measuring instrument (type LA-2 manufactured by PEACOCK), and the average value of three points was taken as the thickness.
- Density Density was measured according to JIS A 5905 (2003) 6.3. 4 (see the hatched rectangle in FIG. 4), from the molded body 3 in each of the vertical direction (vertically elongated rectangle with diagonal lines) and the horizontal direction (horizontal rectangle with diagonal lines). Three test pieces each having a width of 50 mm and a length of 150 mm were collected. After each test piece is left for 24 hours in a standard condition of a temperature of 20 ° C. and a relative humidity of 65%, the width, length and thickness of the test piece are measured, and the average value of three pieces is obtained for each, and the width of the test piece is determined. The volume (v) was determined from the average values of length and thickness.
- D. Formability As for formability, the appearance of the rising portion of the molded body molded by the following molding method was evaluated.
- a. Molding method The nonwoven fabric 1 matched with the target density is heated to a nonwoven fabric internal temperature of 200 ° C. with a far-infrared heater, and then set to a temperature of 30 ° C.
- the male mold 1 shown in FIG. 1 (a) and shown in FIG. 1 (c) A mold comprising the female mold 2 was subjected to a cooling press at a pressure of 3000 kN / m 2 for 8 seconds to produce a molded body 3 having a thickness of 5 mm or less as shown in FIG. b.
- the bending strength was measured according to JIS A 5905: 2003 6.6. 4 (see the hatched rectangle in FIG. 4), from the molded body 3 in each of the vertical direction (vertically elongated rectangle with diagonal lines) and the horizontal direction (horizontal rectangle with diagonal lines). Three test pieces each having a width of 50 mm and a length of 150 mm were collected. After leaving each test piece for 48 hours in a standard condition of a temperature of 20 ° C. and a relative humidity of 65%, the test piece was placed in a bending strength test apparatus with a span (L) of 100 mm, and the test piece was placed at an intermediate position of the span.
- L span
- Bending strength (N / mm 2 ) [3 ⁇ maximum load (N) ⁇ L (mm)] / [2 x width (mm) x thickness 2 (mm)]
- Judgment A Bending strength is 20 N / mm 2 or more (both vertical and horizontal) (excellent)
- Example 1 A polylactic acid chip (melting point 170 ° C., weight average molecular weight 11.3 ⁇ 10 4 ), 1% by mass of carbon black having a median diameter d50 of 20 nm as a crystal nucleating agent, and triglycidyl isocyanurate (Nissan Chemical) as a hydrolysis inhibitor 2% by mass of “TEPIC” (registered trademark; the same applies hereinafter) manufactured by Kogyo Co., Ltd. was charged into a spinning machine hopper, melt-spun at an spinning temperature of 230 ° C. with an extruder-type spinning machine, and the spinning yarn was cooled. After the oil agent was applied and converged, it was taken up at 1000 m / min to obtain an undrawn yarn.
- TEPIC registered trademark; the same applies hereinafter
- the resulting undrawn yarn is converged to 800,000 dtex, drawn 4.0 times in a 90 ° C. liquid bath, mechanically crimped with a stuffer box, heated at 145 ° C. for 10 minutes, was applied by a spray method so as to be 0.5% by weight with respect to the fiber, and cut to 51 mm to obtain a short polylactic acid fiber having a single particle fineness of 6.6 dtex. There was no yarn breakage or fluffing in the spinning and drawing processes, and the raw cotton could be obtained stably.
- the obtained polylactic acid short fiber has a tensile strength of 2.1 cN / dtex, a tensile elongation of 72%, a crimp number of 10.2 ridges / 25 mm, a crimp of 14%, and a dry heat shrinkage of 1.2%.
- the temperature drop crystallization temperature was 127 ° C. and the crystallization rate was fast, and the epoxy residual value was 0.18 equivalent / kg.
- Kenaf fiber was prepared by reading the stalk of kenaf in a river, collecting bast fiber, and cutting it with a guillotine cutter.
- the obtained kenaf fiber had a fiber length of 119 mm, a fiber diameter of 58 ⁇ m, 41 voids derived from the conduit, a moisture content of 17% by mass, and a tensile strength of 2.0 cN / dtex.
- the odor amount of kenaf fiber is 0.3 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.9 ⁇ g / kg for ethanol, 2-methoxy-acetate, 0.3 ⁇ g / kg for acetic acid, and 1.1 ⁇ g for trimethylbenzene.
- acetaldehyde was 4.2 ⁇ g / kg, and formaldehyde was not detected.
- the polylactic acid short fiber and the kenaf fiber were mixed using a roller card at a mass ratio of 30:70, and opened to produce a web.
- needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 529 g / m 2 and a thickness of 3.4 mm.
- Its non-woven fabric a longitudinal direction of the tensile strength 98 N / cm 2, the transverse direction of the tensile strength 56N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 14N / cm 2, the transverse direction tensile stress was 10N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in the nonwoven fabric was 127 ° C., and the crystallization rate was fast.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 86%, and the entanglement between polylactic acid fibers and kenaf fibers was a very strong structure.
- the odor amount of the nonwoven fabric was 0.3 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.9 ⁇ g / kg for ethanol, 2-methoxy-acetate, 2.7 ⁇ g / kg for acetic acid, and 1.8 ⁇ g / kg for trimethylbenzene. kg, acetaldehyde was 5.2 ⁇ g / kg, and formaldehyde was not detected.
- one nonwoven fabric matched with the target density shown in Table 1 was heated to a nonwoven fabric internal temperature of 200 ° C. with a far infrared heater. Then, a cooling press was performed for 8 seconds at a pressure of 3000 kN / m 2 in a mold set at a temperature of 30 ° C. (see FIGS. 1A and 1C), and the density was 0.76 g / cm 3 and the thickness was A 0.7 mm three-dimensional molded body was prepared. The molded body was transparent at the rising portion, had no cracks, and had no wrinkles at the corners.
- Example 2 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a mass ratio of 50:50, and opened to produce a web. Next, needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 556 g / m 2 and a thickness of 3.6 mm.
- a longitudinal direction of the tensile strength 128N / cm 2 the transverse direction of the tensile strength 84N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 19N / cm 2, the transverse direction tensile stress was 16N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of the kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 87%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- the odor amount of the nonwoven fabric was 0.3 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.9 ⁇ g / kg for ethanol, 2-methoxy-acetate, 2.4 ⁇ g / kg for acetic acid, and 1.5 ⁇ g / kg for trimethylbenzene.
- kg, acetaldehyde was 4.1 ⁇ g / kg, and formaldehyde was not detected.
- a molded body having a density of 0.70 g / cm 3 and a thickness of 0.8 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 24N / mm 2, bending strength of the transverse direction was as high as 22N / mm 2.
- the determination of the odor sensory test of the molded product was 2, and there was odor but no unpleasant odor.
- Example 3 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a mass ratio of 30:70, and opened to produce a web. Next, needle punching is performed under the conditions of 80 first punches / cm 2 , 80 second punches / cm 2 , and a total needle density of 160 needles / cm 2 , which are entangled to have a basis weight of 514 g / m 2 and a thickness of 3.4 mm. A non-woven fabric was obtained.
- a longitudinal direction of the tensile strength 58N / cm 2 the transverse direction of the tensile strength 34N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 9N / cm 2, the transverse direction tensile stress was 8N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 57%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a strong structure.
- a molded body having a density of 0.73 g / cm 3 and a thickness of 0.7 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed and had no cracks at the rising portion, but was transparent, and the corner of the rising portion was free from wrinkles.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 17N / mm 2, the transverse direction of the bending strength was as high as 15N / mm 2.
- Example 4 A nonwoven fabric having a basis weight of 1012 g / m 2 and a thickness of 6.1 mm was obtained using the same polylactic acid short fibers and kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1. Its non-woven fabric, a longitudinal direction of the tensile strength 131N / cm 2, the transverse direction of the tensile strength 107N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 32N / cm 2, the transverse direction tensile stress was 21N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 91%, and the entanglement between polylactic acid fibers and kenaf fibers was a very strong structure.
- a molded body having a density of 0.72 g / cm 3 and a thickness of 1.4 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- the cooling press time of the mold was as short as 8 seconds, the bending strength in the vertical direction was 20 N / mm 2 and the bending strength in the horizontal direction was as high as 23 N / mm 2 .
- Example 5 A nonwoven fabric having a basis weight of 1584 g / m 2 and a thickness of 8.2 mm was obtained using the same polylactic acid short fibers and kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1.
- the non-woven fabric has a vertical tensile strength of 157 N / cm 2 , a horizontal tensile strength of 110 N / cm 2 , a tensile stress in the vertical direction with a tensile elongation of 30% at 200 ° C., and a horizontal tensile stress of 56 N / cm 2 .
- tensile stress was 17N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 94%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- the odor amount of the nonwoven fabric is 0.3 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.9 ⁇ g / kg for ethanol, 2-methoxy-acetate, 2.9 ⁇ g / kg for acetic acid, and 1.8 ⁇ g / kg for trimethylbenzene. kg, acetaldehyde was 5.1 ⁇ g / kg, and formaldehyde was not detected.
- a molded body having a density of 0.75 g / cm 3 and a thickness of 2.1 mm was formed under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- the bending strength in the longitudinal direction 27N / mm 2 was as high as 29N / mm 2.
- the determination of the odor sensory test of the molded body was 3, and there was an obvious odor but no unpleasant odor.
- Example 6 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a mass ratio of 50:50, and opened to produce a web. Next, needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 1615 g / m 2 and a thickness of 8.2 mm.
- a longitudinal direction of the tensile strength 175 N / cm 2 the transverse direction of the tensile strength 107N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 44N / cm 2, the transverse direction tensile stress was 15N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 92%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- the odor amount of the nonwoven fabric was 0.3 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.9 ⁇ g / kg for ethanol, 2-methoxy-acetate, 2.2 ⁇ g / kg for acetic acid, 1.5 ⁇ g / kg for trimethylbenzene.
- kg, acetaldehyde was 3.9 ⁇ g / kg, and formaldehyde was not detected.
- a molded body having a density of 0.73 g / cm 3 and a thickness of 2.2 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 26N / mm 2, bending strength of the transverse direction was as high as 27N / mm 2.
- the determination of the odor sensory test of the molded body was 3, and there was an obvious odor but no unpleasant odor.
- Example 7 As a kenaf fiber, a kenaf stalk was read-processed in the river, bast fiber was extract
- the obtained kenaf fiber had a fiber length of 142 mm, a fiber diameter of 40 ⁇ m, 28 voids derived from the conduit, a moisture content of 16 mass%, and a tensile strength of 1.5 cN / dtex.
- the odor amount of kenaf fiber is 0.1 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.4 ⁇ g / kg for ethanol, 2-methoxy-acetate, 0.2 ⁇ g / kg for acetic acid, and 0.9 ⁇ g for trimethylbenzene.
- / Kg, acetaldehyde was 1.8 ⁇ g / kg, and formaldehyde was not detected.
- a nonwoven fabric having a basis weight of 1571 g / m 2 and a thickness of 10.4 mm was obtained using the same polylactic acid short fiber and the kenaf fiber as in Example 1 under the same nonwoven fabric processing conditions as in Example 1. Its non-woven fabric, a longitudinal direction of the tensile strength 61N / cm 2, the transverse direction of the tensile strength 33N / cm 2, 200 tensile elongation of 30% in the longitudinal direction of the tensile stress at °C atmosphere 10 N / cm 2, the transverse direction tensile stress was 5N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 68%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a strong structure.
- the odor amount of the nonwoven fabric was 0.2 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.4 ⁇ g / kg for ethanol, 2-methoxy-acetate, 1.5 ⁇ g / kg for acetic acid, and 1.1 ⁇ g / kg for trimethylbenzene. kg, acetaldehyde was 2.4 ⁇ g / kg, and formaldehyde was not detected.
- a molded body having a density of 0.71 g / cm 3 and a thickness of 2.2 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 23N / mm 2, bending strength of the transverse direction was as high as 19N / mm 2.
- the determination of the odor sensory test of the molded body was 1, and there was no odor.
- Example 8 The same polylactic acid short fiber and kenaf fiber as in Example 1 were obtained under the same nonwoven fabric processing conditions as in Example 1 to obtain a nonwoven fabric having a basis weight of 1982 g / m 2 and a thickness of 13.1 mm. Its non-woven fabric, a longitudinal direction of the tensile strength 193 n / cm 2, the transverse direction of the tensile strength 157N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 63N / cm 2, the transverse direction tensile stress was 27N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 95%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- a molded body having a density of 0.73 g / cm 3 and a thickness of 2.7 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 25 N / mm 2, bending strength of the transverse direction was as high as 26N / mm 2.
- Example 9 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a weight ratio of 30:70, opened, and a web was produced. Next, needle punching is performed under the conditions of 50 first punches / cm 2 , 50 second punches / cm 2 , and a total needle density of 100 needles / cm 2 , which are entangled to have a basis weight of 2538 g / m 2 and a thickness of 13.8 mm. A non-woven fabric was obtained.
- the nonwoven fabric has a vertical tensile strength of 281 N / cm 2 , a horizontal tensile strength of 237 N / cm 2 , a tensile stress in the vertical direction of 30% tensile elongation at 200 ° C. in the vertical direction of 78 N / cm 2 ,
- the tensile stress was / 53 N / cm 2 and the air permeability was as low as 26 cc / cm 2 / sec.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 96%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- a molded body having a density of 1.21 g / cm 3 and a thickness of 2.1 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, had no see-through and cracks at the rising portion, and the corner of the rising portion had small wrinkles with a step of less than 0.5 mm.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 55N / mm 2, bending strength of the transverse direction was as high as 48N / mm 2.
- a kenaf stalk was read in a swamp, a bast fiber was collected, and cut with a guillotine cutter to prepare a kenaf fiber.
- the obtained kenaf fiber had a fiber length of 184 mm, a fiber diameter of 93 ⁇ m, 30 voids derived from the conduit, a moisture content of 13 mass%, and a tensile strength of 0.9 cN / dtex.
- the odor amount of kenaf fiber is 0.4 ⁇ g / kg for 1-methoxy-2-propyl acetate, 1.8 ⁇ g / kg for ethanol, 2-methoxy-acetate, 3.7 ⁇ g / kg for acetic acid, and 2.2 ⁇ g for trimethylbenzene.
- / Kg, acetaldehyde was 5.8 ⁇ g / kg, and formaldehyde was not detected.
- a nonwoven fabric having a basis weight of 530 g / m 2 and a thickness of 3.0 mm was obtained using the same polylactic acid short fiber and the kenaf fiber as in Example 1 under the same nonwoven fabric processing conditions as in Example 1. Its non-woven fabric, a longitudinal direction of the tensile strength 81N / cm 2, the transverse direction of the tensile strength 35N / cm 2, 200 tensile elongation of 30% in the longitudinal direction of the tensile stress at °C atmosphere 12N / cm 2, the transverse direction tensile stress was 7N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 52%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a strong structure.
- the odor amount of the nonwoven fabric is 0.5 ⁇ g / kg for 1-methoxy-2-propyl acetate, 2.1 ⁇ g / kg for ethanol, 2-methoxy-acetate, 4.9 ⁇ g / kg for acetic acid, and 2.7 ⁇ g / kg for trimethylbenzene. kg, acetaldehyde was 6.8 ⁇ g / kg, and formaldehyde was not detected.
- a molded body having a density of 0.76 g / cm 3 and a thickness of 0.7 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed and had no cracks at the rising portion, but was transparent, and the corner of the rising portion was free from wrinkles.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 28N / mm 2, bending strength of the transverse direction was as high as 26N / mm 2.
- the determination of the odor sensory test of the molded product was 4, which had an unpleasant odor.
- Example 11 Polylactic acid chip (melting point 170 ° C., weight average molecular weight 10.8 ⁇ 10 4 ), 1% by mass of carbon black having a median diameter d50 of 20 nm as a crystal nucleating agent, and triglycidyl isocyanurate (Nissan Chemical) as a hydrolysis inhibitor “TEPIC” manufactured by Kogyo Co., Ltd.) was charged into a spinning machine hopper, melt-spun at an extruder-type spinning machine at a spinning temperature of 230 ° C., this spinning yarn was cooled, and an oil was added to converge. Then, it was taken up at 1000 m / min to obtain an undrawn yarn.
- the obtained undrawn yarn is converged to 800,000 dtex, drawn 4.0 times in a 90 ° C. liquid bath, mechanically crimped with a stuffer box, heated at 90 ° C. for 10 minutes, was applied by a spray method so as to be 0.5% by weight with respect to the fiber, and cut to 51 mm to obtain a short polylactic acid fiber having a single particle fineness of 6.6 dtex. There was no yarn breakage or fluffing in the spinning and drawing processes, and the raw cotton could be obtained stably.
- the obtained polylactic acid short fiber has a tensile strength of 2.3 cN / dtex, a tensile elongation of 56%, a crimp number of 10.8 ridges / 25 mm, a crimp of 12%, and a dry heat shrinkage of 7.5%.
- the temperature drop crystallization temperature was 127 ° C. and the crystallization rate was fast.
- a nonwoven fabric having a basis weight of 1534 g / m 2 and a thickness of 8.1 mm was obtained using the polylactic acid short fibers and the same kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1.
- the nonwoven fabric has a vertical tensile strength of 166 N / cm 2 , a horizontal tensile strength of 114 N / cm 2 , a tensile stress in the vertical direction of 30% tensile elongation at 200 ° C. in the horizontal direction, 59 N / cm 2 , tensile stress was 23N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 92%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- a molded body having a density of 0.73 g / cm 3 and a thickness of 2.1 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, had no see-through and cracks at the rising portion, and had small wrinkles with a step of less than 0.5 mm at the corner of the rising portion.
- the mold cooling press time was as short as 8 seconds, the bending strength in the vertical direction was as high as 22 N / mm 2 and the bending strength in the horizontal direction was as high as 23 N / mm 2 .
- Example 12 A polylactic acid chip (melting point 170 ° C., weight average molecular weight 11.3 ⁇ 10 4 ), 1% by mass of carbon black having a median diameter d50 of 20 nm as a crystal nucleating agent, and triglycidyl isocyanurate (Nissan Chemical) as a hydrolysis inhibitor "TEPIC” manufactured by Kogyo Co., Ltd.) was charged into a spinning machine hopper, melt-spun at an extruder type spinning machine at a spinning temperature of 230 ° C, the spinning yarn was cooled, and an oil agent was applied. Then, the yarn was taken up at 1000 m / min to obtain an undrawn yarn.
- triglycidyl isocyanurate Nasan Chemical
- the resulting undrawn yarn is converged to 800,000 dtex, drawn 4.0 times in a 90 ° C. liquid bath, mechanically crimped with a stuffer box, heated at 145 ° C. for 10 minutes, was applied by a spray method so as to be 0.5% by weight with respect to the fiber, and cut to 51 mm to obtain a short polylactic acid fiber having a single particle fineness of 6.6 dtex. There was no yarn breakage or fluffing in the spinning and drawing processes, and the raw cotton could be obtained stably.
- the obtained polylactic acid short fiber has a tensile strength of 2.2 cN / dtex, a tensile elongation of 71%, a crimp number of 10.5 peaks / 25 mm, a crimp of 13%, and a dry heat shrinkage of 1.4%.
- the crystallization temperature was 127 ° C. and the crystallization rate was fast, and the epoxy residual value was 0.04 equivalent / kg.
- a nonwoven fabric having a basis weight of 516 g / m 2 and a thickness of 3.5 mm was obtained using the polylactic acid short fibers and the same kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1. Its non-woven fabric, a longitudinal direction of the tensile strength 74N / cm 2, the transverse direction of the tensile strength 44N / cm 2, 200 tensile elongation of 30% in the longitudinal direction of the tensile stress at °C atmosphere 10 N / cm 2, the transverse direction tensile stress was 8N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC. The fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 89%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- a molded body having a density of 0.74 g / cm 3 and a thickness of 0.7 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed and had no cracks at the rising portion, but was transparent, and the corner of the rising portion was free from wrinkles.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 18N / mm 2, bending strength of the transverse direction was 13N / mm 2.
- Example 13 Polylactic acid chip (melting point 170 ° C., weight average molecular weight 11.3 ⁇ 10 4 ), 1% by mass of carbon black having a median diameter d50 of 10 nm as a crystal nucleating agent, and triglycidyl isocyanurate (Nissan Chemical) as a hydrolysis inhibitor “TEPIC” manufactured by Kogyo Co., Ltd.) was charged into a spinning machine hopper, melt-spun at an extruder-type spinning machine at a spinning temperature of 230 ° C., this spinning yarn was cooled, and an oil was added to converge. Then, it was taken up at 1000 m / min to obtain an undrawn yarn.
- the resulting undrawn yarn is converged to 800,000 dtex, drawn 4.0 times in a 90 ° C. liquid bath, mechanically crimped with a stuffer box, heated at 145 ° C. for 10 minutes, was applied by a spray method so as to be 0.5% by weight with respect to the fiber, and cut to 51 mm to obtain a short polylactic acid fiber having a single particle fineness of 6.6 dtex. There was no yarn breakage or fluffing in the spinning and drawing processes, and the raw cotton could be obtained stably.
- the obtained polylactic acid short fiber has a tensile strength of 2.0 cN / dtex, a tensile elongation of 70%, a crimp number of 10.9 ridges / 25 mm, a crimp of 13%, and a dry heat shrinkage ratio of 1.1%.
- the crystallization temperature was 138 ° C. and the crystallization rate was fast, and the epoxy residual value was 0.18 equivalent / kg.
- a nonwoven fabric having a basis weight of 1534 g / m 2 and a thickness of 8.1 mm was obtained using the polylactic acid short fibers and the same kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1.
- the nonwoven fabric has a vertical tensile strength of 154 N / cm 2 , a horizontal tensile strength of 108 N / cm 2 , a tensile stress in the vertical direction with a tensile elongation of 30% in an atmosphere of 200 ° C. of 51 N / cm 2 , tensile stress was 18N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in the nonwoven fabric was 138 ° C., and the crystallization rate was fast.
- the fiber length frequency distribution of the kenaf fiber having a fiber length of 45 mm or more in the nonwoven fabric was 95%, and the entanglement between the polylactic acid fiber and the kenaf fiber was a very strong structure.
- the odor amount of the nonwoven fabric was 0.3 ⁇ g / kg for 1-methoxy-2-propyl acetate, 0.9 ⁇ g / kg for ethanol, 2-methoxy-acetate, 2.5 ⁇ g / kg for acetic acid, and 1.4 ⁇ g / kg for trimethylbenzene. kg, acetaldehyde was 4.0 ⁇ g / kg, and formaldehyde was not detected.
- one nonwoven fabric matched with the target density shown in Table 1 was heated to a nonwoven fabric internal temperature of 200 ° C. with a far infrared heater. Thereafter, a cooling press was performed for 7 seconds at a pressure of 3,000 kN / m 2 with a mold set at a temperature of 30 ° C. (see FIGS. 1A and 1C), and the density was 0.72 g / cm 3 .
- a three-dimensional molded body having a thickness of 2.1 mm was produced. The molded body was transparent at the rising portion, had no cracks, and had no wrinkles at the corners.
- Example 14 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a mass ratio of 20:80, and opened to produce a web. Next, needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 563 g / m 2 and a thickness of 3.5 mm.
- a longitudinal direction of the tensile strength 52N / cm 2 a longitudinal direction of the tensile strength 52N / cm 2
- the transverse direction of the tensile strength 31N / cm 2 200 tensile elongation of 30% in the longitudinal direction of the tensile stress at °C atmosphere 12N / cm 2
- the transverse direction tensile stress was 8N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 90%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- a molded body having a density of 0.70 g / cm 3 and a thickness of 0.8 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed and had no cracks at the rising portion, but was transparent, and the corner of the rising portion was free from wrinkles.
- the cooling press time of the mold was as short as 8 seconds
- the bending strength in the vertical direction was 19 N / mm 2
- the bending strength in the horizontal direction was as high as 16 N / mm 2 .
- Example 15 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a mass ratio of 60:40, and opened to produce a web. Next, needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 580 g / m 2 and a thickness of 3.6 mm.
- the nonwoven fabric has a vertical tensile strength of 149 N / cm 2 , a horizontal tensile strength of 98 N / cm 2 , a vertical tensile stress of 24 N / cm 2 with a tensile elongation of 30% at 200 ° C., and a horizontal direction tensile stress was 18N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 95%, and the entanglement between polylactic acid fibers and kenaf fibers was a very strong structure.
- a molded body having a density of 0.73 g / cm 3 and a thickness of 0.8 mm was created under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising portion, had no cracks, and had no wrinkles on the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 26N / mm 2, the transverse direction of the bending strength was as high as 25 N / mm 2.
- the determination of the odor sensory test of the molded product was 2, and there was odor but no unpleasant odor.
- Example 16 As jute fibers, jute stalks were read in swamps, bast fibers were collected, and cut with a guillotine cutter to produce jute fibers.
- the obtained jute fiber had a fiber length of 123 mm, a fiber diameter of 43 ⁇ m, 38 voids derived from the conduit, a moisture content of 15% by mass, and a tensile strength of 1.7 cN / dtex.
- a nonwoven fabric having a basis weight of 1513 g / m 2 and a thickness of 8.2 mm was obtained using the same polylactic acid short fibers and the jute fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1.
- the non-woven fabric has a vertical tensile strength of 151 N / cm 2 , a horizontal tensile strength of 110 N / cm 2 , a tensile strength in the vertical direction of 30% tensile elongation at 200 ° C. in an atmosphere of 54 N / cm 2 , tensile stress was 23N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 88%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a strong structure.
- a molded body having a density of 0.72 g / cm 3 and a thickness of 2.1 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 26N / mm 2, bending strength of the transverse direction was as high as 28N / mm 2.
- Example 17 The same polylactic acid fiber and kenaf fiber as in Example 1 were mixed using airlaid at a mass ratio of 30:70, opened, and a web was produced. Next, needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 1542 g / m 2 and a thickness of 8.3 mm.
- the nonwoven fabric has a vertical tensile strength of 163 N / cm 2 , a horizontal tensile strength of 117 N / cm 2 , a tensile stress in the vertical direction of 30% tensile elongation at 200 ° C.
- tensile stress was 19N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 95%, and the entanglement between polylactic acid fibers and kenaf fibers was a very strong structure.
- a molded body having a density of 0.73 g / cm 3 and a thickness of 2.1 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, was transparent at the rising part, had no cracks, and had no wrinkles at the corners.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 30 N / mm 2, bending strength of the transverse direction was as high as 29N / mm 2.
- Example 1 Polylactic acid chip (melting point 170 ° C., weight average molecular weight 10.6 ⁇ 10 4 ), median diameter d50 as crystal nucleating agent 1% by mass of 200 ⁇ 10 3 nm talc, and triglycidyl isocyanurate as hydrolysis inhibitor (Nissan Chemical Co., Ltd. “TEPIC”) 2 mass% was used to obtain a polylactic acid short fiber having a single particle fineness of 6.6 dtex and a fiber length of 51 mm in the same manner as in Example 1. There was no yarn breakage or fluffing in the spinning and drawing processes, and the raw cotton could be obtained stably.
- TEPIC triglycidyl isocyanurate
- the obtained polylactic acid short fiber has a tensile strength of 2.1 cN / dtex, a tensile elongation of 69%, a crimp number of 11.6 ridges / 25 mm, a crimp of 13%, and a dry heat shrinkage of 1.4%.
- the temperature-falling crystallization temperature was 99 ° C., which was a slow crystallization rate.
- a nonwoven fabric having a basis weight of 1571 g / m 2 and a thickness of 10.6 mm was obtained using the polylactic acid short fibers and the same kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1. Its non-woven fabric, a longitudinal direction of the tensile strength 149N / cm 2, tensile strength in the transverse direction is 117N / cm 2, 200 °C tensile elongation of 30% in the longitudinal direction of the tensile stress in the atmosphere 51N / cm 2, the transverse direction tensile stress was 18N / cm 2.
- the temperature-falling crystallization temperature of the polylactic acid fiber in the nonwoven fabric was 99 ° C., which was a slow crystallization rate.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 70%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a very strong structure.
- a molded body having a density of 0.75 g / cm 3 and a thickness of 2.1 mm was produced under the same molding conditions as in Example 1.
- the molded body had a low molding speed, but was transparent to the rising portion, free from cracks, and without wrinkles at the corners.
- the mold cooling press time is as short as 8 seconds, polylactic acid (PLA) cannot be crystallized, the bending strength in the vertical direction is as low as 12 N / mm 2 , and the bending strength in the horizontal direction is as low as 8 N / mm 2 Met.
- Example 1 using a polylactic acid chip (melting point 170 ° C., weight average molecular weight 12.8 ⁇ 10 4 ) and 2% by mass of triglycidyl isocyanurate (“TEPIC” manufactured by Nissan Chemical Industries, Ltd.) as a hydrolysis inhibitor
- TEPIC triglycidyl isocyanurate
- the resulting polylactic acid short fiber has a tensile strength of 2.3 cN / dtex, a tensile elongation of 71%, a crimp number of 11.8 ridges / 25 mm, a crimp of 15%, and a dry heat shrinkage of 1.5%. However, the temperature-falling crystallization temperature was not detected.
- a nonwoven fabric having a basis weight of 1542 g / m 2 and a thickness of 10.1 mm was obtained using the polylactic acid short fibers and the same kenaf fibers as in Example 1 under the same nonwoven fabric processing conditions as in Example 1. Its non-woven fabric, a longitudinal direction of the tensile strength 168n / cm 2, the transverse direction of the tensile strength 102N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 58N / cm 2, the transverse direction tensile stress was 16N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was not detected. In addition, the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 64%, and the entanglement between polylactic acid fibers and kenaf fibers was a strong structure.
- a molded body having a density of 0.70 g / cm 3 and a thickness of 2.2 mm was produced under the same molding conditions as in Example 1.
- the molded body had a low molding speed, but was transparent to the rising portion, free from cracks, and without wrinkles at the corners. Also, since the mold cooling press time is as short as 8 seconds, polylactic acid (PLA) cannot be crystallized, and the bending strength in the vertical direction is as low as 9 N / mm 2 and the bending strength in the horizontal direction is as low as 7 N / mm 2. Met.
- PLA polylactic acid
- Example 3 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a weight ratio of 30:70, opened, and a web was produced. Next, needle punching is performed under the conditions of 80 first punch / cm 2 , second punch 80 / cm 2 , third punch 80 / cm 2 , total needle density 240 / cm 2 , and entangled with a basis weight of 521 g / A nonwoven fabric with m 2 and a thickness of 3.4 mm was obtained.
- the nonwoven fabric has a vertical tensile strength of 14 N / cm 2 , a horizontal tensile strength of 9 N / cm 2 , a tensile stress of 2 N / cm 2 in a vertical direction with a tensile elongation of 30% in an atmosphere of 200 ° C.
- Tensile stress was 1 N / cm 2 , and many kenaf fibers dropped out from the nonwoven fabric.
- the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 8%, and the entanglement between the polylactic acid fibers and the kenaf fibers was weak.
- a molded body having a density of 0.65 g / cm 3 and a thickness of 0.8 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, but cracks occurred at the rising portion, and the corner of the rising portion was free from wrinkles.
- the cooling press time of the mold was as short as 8 seconds, the bending strength in the vertical direction was 5 N / mm 2 , and the bending strength in the horizontal direction was 3 N / mm 2 and the strength was low.
- Example 4 A nonwoven fabric having a basis weight of 428 g / m 2 and a thickness of 2.9 mm was obtained using the same polylactic acid short fiber and kenaf fiber as in Example 10 under the same nonwoven fabric processing conditions as in Example 10. Its non-woven fabric, a longitudinal direction of the tensile strength 45N / cm 2, the transverse direction of the tensile strength 18N / cm 2, 200 tensile elongation of 30% in the longitudinal direction of the tensile stress at °C atmosphere 4N / cm 2, the transverse direction tensile stress was 3N / cm 2. Moreover, the temperature-falling crystallization temperature of the polylactic acid fiber in a nonwoven fabric was 127 degreeC. The fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 42%, and the entanglement between the polylactic acid fibers and the kenaf fibers was a strong structure.
- a molded body having a density of 0.71 g / cm 3 and a thickness of 0.6 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, but cracks occurred at the rising portion, and the corner of the rising portion was free from wrinkles.
- cooling press time of the mold and the shorter 8 seconds the bending strength in the longitudinal direction 18N / mm 2, the transverse direction of the bending strength was as high as 15N / mm 2.
- Example 5 The same polylactic acid short fiber and kenaf fiber as in Example 1 were obtained under the same nonwoven fabric processing conditions as in Example 1 to obtain a nonwoven fabric having a basis weight of 3428 g / m 2 and a thickness of 14.0 mm. Its non-woven fabric, a longitudinal direction of the tensile strength 378N / cm 2, the transverse direction of the tensile strength 341N / cm 2, 200 of the tensile elongation of 30% in the longitudinal direction at °C atmosphere tensile stress 93N / cm 2, the transverse direction The tensile stress was 84 N / cm 2 and the air permeability was as low as 21 cc / cm 2 / sec.
- the temperature-falling crystallization temperature of the polylactic acid short fiber in the nonwoven fabric was 127 ° C.
- the fiber length frequency distribution of kenaf fibers having a fiber length of 45 mm or more in the nonwoven fabric was 97%, and the entanglement between polylactic acid fibers and kenaf fibers was a very strong structure.
- a molded body having a density of 0.69 g / cm 3 and a thickness of 5.0 mm was produced under the same molding conditions as in Example 1.
- the molding body had a high molding speed, there was no see-through or crack at the rising portion, and the corner of the rising portion had wrinkles with a step of 0.5 mm or more.
- the cooling press time of the mold was as short as 8 seconds, the bending strength in the vertical direction was as high as 22 N / mm 2 and the bending strength in the horizontal direction was as high as 20 N / mm 2 .
- Example 6 The same polylactic acid short fiber and kenaf fiber as in Example 1 were blended using a roller card at a mass ratio of 10:90, opened, and a web was produced. Next, needle punching was performed under the condition of a needle density of 60 / cm 2 and entangled to obtain a nonwoven fabric having a basis weight of 524 g / m 2 and a thickness of 3.5 mm.
- a molded body having a density of 0.66 g / cm 3 and a thickness of 0.8 mm was produced under the same molding conditions as in Example 1.
- the molded body had a high molding speed, but cracks occurred at the rising portion, and the corner of the rising portion was free from wrinkles.
- the mold cooling press time was as short as 8 seconds, the bending strength in the vertical direction was 13 N / mm 2 , and the bending strength in the horizontal direction was 9 N / mm 2 , which was low.
- the nonwoven fabric of the present invention is useful as a press-molded product, and can be used for, for example, automobile parts, electrical / electronic parts, building materials, civil engineering materials, furniture members, and gaming machine materials.
- Automobile parts can be applied particularly to ceiling materials for interior materials, package trays, backboards in front seats and rear seats, door trims, pillars, and the like.
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Abstract
Description
また、更に環境負荷の低減を目的に、植物由来のポリ乳酸樹脂及び天然繊維を混在させて加熱、加圧し、全体の見かけ密度を特定範囲とするように成形した繊維系ボードが提案されている(特許文献2)。
更に、特許文献2の発明の改良発明として、成型時間を短縮するために、ポリ乳酸繊維および天然繊維に、さらに無機フィラーを添加した木質成形体が開示されている(特許文献3)。
また、成型体の製造方法は、不織布を熱処理し、金型を用いて圧縮するプレス立体成型方法が一般的である。しかしながら、金型の絞りの立ち上がり部位であって、成型体の角となるに部分において、成型体にシワが発生する問題があった。
更に、金型の深い絞りの立ち上がり部位では、その部位において成型体が薄肉化し、結果として透けや亀裂が発生する問題があった。
第1の課題は、成型速度である。特許文献3で用いられているタルクを混合したポリ乳酸繊維は、降温結晶化温度が99℃である。自動車内装材や建築材料などに用いる成型体の強度を保持するためには、成型後の成型体を99℃以下まで冷却する必要があり、冷却時間が長いという課題があった。
(1)ポリ乳酸繊維と天然繊維とを含む不織布であって、ポリ乳酸繊維の降温結晶化温度が120℃以上であり、不織布の引張強度が20N/cm2以上であり、200℃雰囲気における引張伸度30%の不織布の引張応力が80N/cm2以下であることを特徴とするプレス成型用不織布。
(2)前記不織布が、目付450~3000g/m2であることを特徴とする前記(1)に記載のプレス成型用不織布。
(3)前記不織布の中の天然繊維において、繊維長45mm以上の天然繊維の割合が30%以上であることを特徴とする前記(1)または(2)に記載のプレス成型用不織布。
(4)前記ポリ乳酸繊維がカーボンブラックを含んでいることを特徴とする前記(1)ないし(3)のいずれかに記載のプレス成型用不織布。
(5)前記ポリ乳酸繊維の乾熱収縮率が5%以下であることを特徴とする前記(1)ないし(4)のいずれかに記載のプレス成型用不織布。
(6)前記天然繊維の引張強度が1.0cN/dtex以上であることを特徴とする前記(1)ないし(5)のいずれかに記載のプレス成型用不織布。
(7)前記天然繊維が、ケナフ繊維であることを特徴とする前記(1)ないし(6)のいずれかに記載のプレス成型用不織布。
(8)降温結晶化温度が120℃以上で、乾熱収縮率5%以下のポリ乳酸繊維と、引張強度が1.0cN/dtex以上の天然繊維を混合し、その後、合計の針密度が30~200本/cm2でニードルパンチを行うことを特徴とするプレス成型用不織布の製造方法。
(9)前記(1)ないし(7)のいずれかに記載のプレス成型用不織布をプレス成型することを特徴とする成型体の製造方法。
(10)プレス成型が冷却手段を備えた金型を用いるものであって、冷却手段を備えた金型での成型時間が8秒以下であることを特徴とする前記(9)に記載の成型体の製造方法。
(11)混合される天然繊維がケナフ繊維であることを特徴とする前記(9)または(10)に記載の成型体の製造方法。
[ポリ乳酸繊維]
本発明に用いられるポリ乳酸繊維は、-(O-CHCH3-CO)-を主要な繰り返し単位とするポリマーであり、乳酸やそのオリゴマーを重合したものをいう。乳酸にはD-乳酸とL-乳酸の2種類の光学異性体が存在するため、その重合体もD体のみからなるポリ(D-乳酸)とL体のみからなるポリ(L-乳酸)および両者からなるポリ乳酸がある。ポリ乳酸中のD-乳酸、あるいはL-乳酸の光学純度は、低くなるとともに結晶性が低下し、融点が低下してくる。そのため、耐熱性を高めるために光学純度は90%以上であることが好ましい。より好ましい光学純度は93%以上、最も好ましい光学純度は97%以上である。なお、光学純度は前記した様に融点と強い相関が認められ、光学純度90%程度で融点が約150℃、光学純度93%で融点が約160℃、光学純度97%で融点が約170℃となる。また、成型性の観点よりポリ乳酸の融点は200℃以下であることが好ましく、より好ましくは190℃以下、最も好ましくは180℃以下である。
本発明に用いられる天然繊維としては、木材パルプ、バガス、ムギワラ、アシ、パピルス、タケ、パルプ、木綿、ケナフ、ローゼル、アサ、アマ、ラミー、ジュート、ヘンプ、サイザルアサ、マニラアサ、ヤシ、バナナ等があり、これらを単独で用いても良いがこれらの中のから選ばれる1種以上の繊維が含まれていることが好ましい。特に、ケナフ繊維は、天然繊維の中でも優れた強度を有している。また、ケナフ繊維は比較的繊維長が長い。ケナフは一年草であって熱帯地方及び温帯地方での成長が極めて早く、容易に栽培できる草本類に属する。ケナフの靭皮にはセルロースが60質量%以上と高い含有率で存在しており、かつ高い強度を有しており、安価である。そこでケナフ靭皮から採取されるケナフ繊維を用いることが好ましい。したがって、本発明の天然繊維はケナフ繊維を含有することが好ましい。ケナフ繊維を含有する場合、天然繊維における割合は、30質量%以上が好ましく、50質量%以上がより好ましく、さらに90質量%以上が一層好ましい。
本発明に用いられる不織布は、ポリ乳酸繊維とケナフ繊維等の天然繊維とを混綿、そして開繊し、そして交絡させることにより作成することができる。まず、ポリ乳酸繊維と天然繊維をオープナーにかけて混綿する。得られたものを、カーディング法又はエアレイド法にて開繊し、ウェブ化する。さらに得られたものを複数積層する。そして、この積層体をまとめてニードルパンチ法などにより繊維間相互を交絡させて密度が高くなった不織布を得る。ケナフ繊維は、引張伸度が低く、繊維径がバラバラで、節などが存在する。そのため、オープナーからカーディング又はエアレイド、そしてニードルパンチを行う不織布化加工工程を通過することで、繊維が千切れ易く、繊維長が短くなる。特にニードルパンチの条件が大きく寄与する。ニードルパンチされた不織布の針密度は、合計で30~200本/cm2が好ましい。より好ましくは、40~150本/cm2、更に好ましくは50~100本/cm2である。不織布に針密度が200本/cm2を超える過度のニードルパンチを行うと、ケナフ繊維等の天然繊維がニードルパンチの針に破壊され、ケナフ繊維等の天然繊維長が短くなり、繊維長45mm以上のケナフ繊維等の天然繊維が30質量%未満となり、ポリ乳酸繊維とケナフ繊維等の天然繊維の交絡が低下する傾向にある。また、針密度が30本/cm2未満の場合も、ポリ乳酸繊維とケナフ繊維等の天然繊維の交絡が弱くなり、不織布の引張強度が低下、更にそれを用いた成型体の強度も低下する傾向がある。この不織布の針密度は、不織布がニードルパンチ機器の針に打たれた実本数であり、ニードルパンチ機器の針本数と不織布の移動速度により設定することができる。
本発明の成型体は、上記の不織布をプレス成型して得られる。プレス成型は、射出成型や押出し成型とは違い、例えば1m角などの比較的大きな成型体を効率的に得ることができる。素材として不織布を使用することから、通常は成型体の一部または全部が板状となる。
・冷プレス条件:定盤温度10℃~40℃、圧力10~5000kN/m2、プレス時間5~240秒間。
・熱処理条件 :プレボードの内部温度150~220℃となるまで加熱する。
・立体成型条件:金型温度10~40℃、圧力10~5000kN/m2、プレス時間5~240秒。
・熱処理条件:不織布の内部温度が170~220℃となるまで加熱する。
・立体成型条件:金型温度10~40℃、圧力10~5000kN/m2、プレス時間5~240秒間。
プレス方法は、ロールプレス機、平板プレス機などを使用することができる。成型体の強度を高めるためには、上下一対の熱プレス定盤にてプレスする熱プレス機が、十分な熱プレス時間を確保できるため好ましい。
(1)ポリ乳酸繊維
A.繊度
JIS L 1015(1999)8.5.1 A法に準じて測定した。試料若干量を金ぐしで平行に引きそろえ、これを切断台上に置いたラシャ紙の上に載せ、適度の力でまっすぐに張ったままゲージ板を圧縮し、安全かみそりで30mmの長さに切断し、繊維を数えて300本を一組とし、その質量を量り、見かけ繊度を求めた。見かけ繊度から、次の式によって正量繊度を求め、算術平均値を繊度とした。
正量繊度(dtex)=D′×(100+Rc)/(100+Re)
ここに、D′:見かけ繊度(dtex)、Rc:公定水分率(%)、Re:平衡水分率(%)。
JIS L 1015(1999)8.4.1 A法に準じて測定した。試料を800mg量り取り、ステープルダイヤグラムを作成し、ステープルダイヤグラムを50の繊維長群に等分し、各区分の境界及び両端の繊維長を測定し、両端繊維長の平均に49の境界繊維長を加えて50で除して平均繊維長(mm)を算出し、2回の平均値を繊維長とした。
JIS L 1015(1999)8.7.1に準じて測定した。引張速度20mm/min、つかみ間隔20mmで試験し、次の式により引張強度と引張伸度を求めた。試験回数は10回とし、その算術平均値を算出した。
引張強度(cN/dtex)=SD/F0
ここに、SD:最大荷重(cN)、F0:試料の単糸繊度(dtex)
引張伸度(%)=(E1-E2)/(L+E1)×100
ここに、E1:緩み(mm)、E2:最大荷重時の伸び(mm)、L :つかみ間隔(mm)。
JIS L 1015(1999)8.15.b)に準じて測定した。JIS L 1015(1999)8.7.1の引張強度・引張伸度と同様の方法にて区分線を作り(ただし、空間距離は25mmとした)、初荷重をかけたときの距離(mm)を読んだ。試料を装置から取り出し、150℃の乾燥機中につり下げ、30分間放置後取り出し、室温まで冷却後、再び装置に取り付け、初荷重をかけたときのつかみ間の距離を読み、次の式によって乾熱収縮率を測定した。
乾熱収縮率(%)=((L-L’)/L)×100
L:150℃処理前の初荷重をかけたときのつかみ間の距離(mm)
L’:150℃処理後の初荷重をかけたときのつかみ間の距離(mm)
ポリ乳酸をクロロホルムに溶解させて測定溶液とし、ゲルパーミエーションクロマトグラフィー(GPC)でカラム温度40℃、流量1ミリリットル/minの条件にて測定し、ポリスチレン換算で数平均分子量(Mn)、重量平均分子量(Mw)を求めた。測定数は5回とし、その算術平均値を算出した。
粒子径は、島津製作所製SALD-7100を用い、レーザー回折法のメディアン径d50(分布基準は個数であり、大径側の粒子数と小径側の粒子数が等しくなる累積50%の粒径を測定)を測定した。試験回数は5回とし、その算術平均値を粒子径とした。
島津製作所社製示差走査熱量計DSC-60型を用い、試料2.0mgを昇温速度10℃/min、目標温度250℃、ホールド時間5分間、その後、降温速度10℃/min、目標温度30℃にて測定した。得た融解吸熱曲線(昇温時)の極値の温度を融点(℃)、結晶化発熱曲線(降温時)の極値の温度を降温結晶化温度(℃)とした。試験回数は5回とし、その算術平均値を算出した。
JIS K7236(2001)エポキシ樹脂のエポキシ当量に準じて測定した。試料をビーカーにとり、クロロホルム20mlを加え、溶解し、酢酸40mlおよび臭化テトラエチルアンモニウム酢酸溶液10mlを加え、0.1mol/リットル過塩素酸酢酸溶液で電位差滴定を行った。その後、試料による0.1mol/リットル過塩素酸酢酸溶液消費量を補正するため、試料にクロロホルムと酢酸のみを加え、滴定した値を差し引きし、補正を行う方法によりエポキシ残価を算出した。
秤量した試料をo-クレゾールに溶解し、ジクロロメタンを適量添加した後、0.02規定のKOHメタノール溶液で滴定した。この時、乳酸の環状2量体であるラクチド等のオリゴマーは加水分解され、COOH基末端を生じるため、ポリマーのCOOH基末端およびモノマー由来のCOOH基末端、オリゴマー由来のCOOH基末端の全てを合計したCOOH基末端濃度が求められる。この濃度をCOOH末端基濃度とした。
JIS L 1015(1999)8.12.1に準じて測定した。JIS L 1015(1999)8.7.1の引張強度・引張伸度と同様の方法にて区分線を作り(ただし、空間距離は25mmとした)、これに捲縮が損なわれていない数個の部分から採取した試料を1本ずつ、空間距離に対して25±5%の緩みをもたせて、両端を接着剤ではり付け固着させた。この試料を1本ずつ、捲縮試験機のつかみに取り付け、紙片を切断した後、試料に初荷重(0.18mN×表示テックス数)をかけたときのつかみ間の距離(空間距離:mm)を読み、そのときの捲縮数を数えて、25mm長当たりの捲縮数を求め、20回の算術平均値を捲縮数とした。
JIS L 1015(1999)8.12.2に準じて測定した。試料に初荷重(0.18mN×表示テックス数)かけたときの長さと、これに荷重(4.41mN×表示テックス数)をかけたときの長さを測り、次式によって捲縮度を算出した。
Cp={(b-a)/b}×100
Cp:捲縮度(%)
a:初荷重をかけたときの長さ(mm)
b:4.41mN×表示テックス数をかけたときの長さ(mm)
A.繊維長
ケナフ繊維長等の天然繊維は、ケナフ繊維等の天然繊維1kgの中よりランダムで100本採取した。採取する際に、折れ・千切れなどのあるケナフ繊維等の天然繊維は試験片としなかった。採取したケナフ繊維等の天然繊維を両面テープを貼り付けた台紙に、適度の力でまっすぐに貼り付け、ノギスにて繊維長を1mmまで測定し、100本の算術平均値を繊維長とした。
ケナフ繊維等の天然繊維の繊維径はケナフ繊維等の天然繊維1kgの中よりランダムで60本の繊維を採り、走査電子顕微鏡による拡大鏡によってその断面径(外接円の直径)を測定し、60本の算術平均値を繊維径とした。繊維径は0.1μmの精度で測定した。
ケナフ繊維等の天然繊維を標準状態(20℃、相対湿度65%)で48hr放置した後、そのケナフ繊維等の天然繊維から繊維量600dtex(繊維の折れや切れがない部分を使用)を10点採取し、10本の繊維束を得た(繊維長75mmの場合4.5mgを採取した)。各繊維束の両端を2つの厚紙を用いて、厚紙間が10mmになるように両面テープにて貼り付けた。そして、繊維束の厚紙部分を引張試験機のチャックにつかみ間隔10mmで取付けた。引張試験機にて引張速度10mm/minで、繊維束が切断するまで荷重を加え、次式によって10回の算術平均値を算出した。
引張強度(cN/dtex)=[最大荷重時の引張強さ(cN)]/[繊維量600dtex]
引張伸度(%)=[最大荷重時の伸び(mm)]/[つかみ間隔10(mm)]。
試験繊維は、1kgのケナフ繊維等の天然繊維の中から繊維10gを3点採取し、そのケナフ繊維等の天然繊維を秤量瓶に入れた。標準状態(20℃、相対湿度65%)で48hr放置した後、初期重量を電子天秤にて測定した。その後、105℃で48hr乾燥処理して(これを絶対乾燥状態という)、重量を測定し、次式によって含水率を算出した。放置および乾燥処理の際は秤量瓶の蓋を取って処理を行った。
含水率(%)=[初期質量(g)-絶対乾燥状態の質量(g)]/
[絶対乾燥状態の質量(g)]×100
ケナフ繊維等の天然繊維から22gの試験片を2個採取する。各試験片を600ミリリットルのデュラン瓶に入れ、密閉し、20℃、相対湿度65%の標準状態にて24時間放置した。放置後、上記デュラン瓶内に高純度窒素ガスを送りながら、デュラン瓶内の雰囲気を捕集管に2L採気した。
アルデヒド類(アセトアルデヒド、ホルムアルデヒド)は、捕集管(DNPH SILICAサンプラー)を用いてアセトニトリル5mlで溶出、抽出液を窒素パージにて10倍濃縮した。その試験液をGC/MS(ガスクロマトグラフィーを直結した質量分析計)に導入して分析を行い、下記の式にて臭気量を算出した。
アルデヒド類の臭気量(μg/kg)=[抽出液中の成分量(μg/ml)×抽出液量(ml)×アルデヒド分子量×1000]/[濃縮倍率×(アルデヒド分子量+180)/サンプル量(g)]
VOC(揮発性有機化合物)は、捕集管(カーボントラップ400)より捕集成分を加熱脱離し、脱離成分をGC/MSに導入、分析を行い、下記の式にて臭気量を算出した。
VOCの臭気量(μg/kg)=成分量(ng)/サンプル量(g)。
ケナフ繊維等の天然繊維の断面をSEM(走査型電子顕微鏡)にて観察し、導管に由来する空隙数を数えた。ケナフ繊維等の天然繊維10本の空隙数を数え、その空隙数を10で除して1本当たりの算術平均値を空隙数とした。
A.混率
試料の異なる箇所から、50mm×50mmの大きさの正方形の試験片を5枚採取した。標準状態(20℃、相対湿度65%)で48hr放置した後、初期重量を電子天秤にて測定した。その試験片をクロロホルムに浸漬させ、ポリ乳酸繊維を全て溶かした。その後、標準状態(20℃、相対湿度65%)で48hr放置し、放置後の重量を測定し、下記式にて混率を求めた。
ポリ乳酸繊維混率(%)=[初期重量-放置後の質量]/初期重量×100
ケナフ等の天然繊維混率(%)=[100-ポリ乳酸繊維混率]。
ポリ乳酸繊維とケナフ繊維等の天然繊維とを含む不織布から200mm×200mmの大きさの正方形状のものを採取し、その中よりランダムでケナフ繊維等の天然繊維を100点採取した。採取する際に、折れ・千切れなどのあるケナフ繊維等の天然繊維は試験片としなかった。採取したケナフ繊維等の天然繊維を両面テープを貼り付けた台紙に、適度の力でまっすぐに貼り付け、ノギスにて繊維長を1mmまで測定した。度数分布は、繊維長45mm未満、繊維長45mm以上65mm未満、65mm以上85mm未満、85mm以上に分け、それぞれの本数を数え、下記の式により繊維長の割合を計算した。
繊維長45mm未満のケナフ繊維等の天然繊維(%)=(繊維長45mm未満のケナフ繊維等の天然繊維の本数/100)×100
繊維長45mm以上65mm未満のケナフ繊維等の天然繊維(%)=(繊維長45mm以上65mm未満のケナフ繊維等の天然繊維の本数/100)×100
繊維長65mm以上85mm未満のケナフ繊維等の天然繊維(%)=(繊維長65mm以上85mm未満のケナフ繊維等の天然繊維の本数/100)×100
繊維長85mm以上のケナフ繊維等の天然繊維(%)=(繊維長85mm以上のケナフ繊維等の天然繊維の本数/100)×100
繊維長45mm以上のケナフ繊維等の天然繊維(%)=(100-繊維長45mm未満のケナフ繊維等の天然繊維(%))。
目付はJIS L 1906(2000)5.2に準じて測定した。試料の異なる箇所から200mm×250mmの大きさの試験片を3枚採取し、温度20℃、相対湿度65%の標準状態にて24hr放置後、それぞれの質量(g)を量り、その算術平均値を1m2当たりの質量(g/m2)で表し、目付とした。
試料の異なる箇所から200mm×250mmの大きさの試験片を3枚採取し、温度20℃、相対湿度65%の標準状態にて24hr放置後、それぞれの中央と4隅の5点の厚さ(mm)を測定器(TECLOCK type SM-123)にて0.01mmまで測定し、その算術平均値を厚さとした。
JIS L 1096(1999)8.27.1 A法(フラジール形法)に準じて測定した。試料の異なる箇所から200mm×250mmの大きさの試験片を5枚採取し、フラジール形試験機を用い、円筒の一端(吸気側)に試験片を取り付けた。試験片の取り付けに際し、円筒の上に試験片を置き、試験片上から吸気部分を塞がないように均等に約98N(10kgf)の荷重を加え試験片の取り付け部におけるエアーの漏れを防止した。試験片を取り付けた後、加減抵抗器によって傾斜形気圧計が125Paの圧力を示すように吸込みファンを調整し、そのときの垂直形気圧計の示す圧力と、使用した空気孔の種類とから、試験機に付属の表によって試験片を通過する空気量を求め、5枚の試験片についての算術平均値を通気度とした。
不織布から50mm×200mmの大きさの試験片をタテ方向、ヨコ方向それぞれ5枚採取した。各試験片を温度20℃、相対湿度65%の標準状態にて48hr放置後、試験片を引張試験機につかみ間隔100mmで取付けた。引張速度100mm/minで、試験片が切断するまで荷重を加え、最大荷重時の強さを測定し、下記式にて、タテ方向とヨコ方向のそれぞれについて、5回の算術平均値を算出した。
引張強度(N/cm2)=[最大荷重時の引張強さ(N)]/[5(cm)×厚さ(cm)]
引張伸度(%)=[最大荷重時の伸び(mm)]/[つかみ間隔100(mm)]
不織布から50mm×200mmの大きさの試験片をタテ方向、ヨコ方向それぞれ5枚採取した。引張試験機に加熱炉を取り付け、試験片を当該加熱炉により200℃雰囲気下においた状態で、引張試験機につかみ間隔100mmで取付け1min放置後、引張速度100mm/minで、試験片が切断するまで荷重を加え、最大荷重時の強度を測定し、引張伸度30%の際の試験片の引張強さを求め、下記式にて引張応力を算出した。
200℃雰囲気における引張伸度30%の引張応力(N/cm2)
=[伸率30%時の引張強さ(N)]/[5(cm)×厚さ(cm)]
不織布から22gの試験片を2枚採取した。採取した試験片を前述の実施例の(2)ケナフ繊維等の天然繊維の臭気量測定方法(段落0081参照)と同様に臭気量を測定した。
A.目付
目付は不織布の目付と同じと仮定し、下記式にて算出した。
成型体の目付(g/m2)=不織布の目付(g/m2)
厚さは、成型体を温度20℃、相対湿度65%の標準状態にて24hr放置後、図3に記載の3点の部位で(図3の斜線を付した丸印参照)、成型体の厚さ(mm)を測定器(PEACOCK社製のtype LA-2)にて0.1mmまで測定し、3点の平均値を厚さとした。
密度はJIS A 5905(2003)6.3に準じて測定した。図4に記載の部位で(図4の斜線を付した長方形参照)、成型体3から、タテ方向(斜線を付した縦長の長方形)およびヨコ方向(斜線を付した横長の長方形)のそれぞれについて、幅50mm、長さ150mmの試験片を3枚ずつ採取した。各試験片を温度20℃、相対湿度65%の標準状態にて24hr放置後、試験片の幅、長さ及び厚さを測定し、それぞれについて3枚の平均値を求め、その試験片の幅、長さ及び厚さの平均値から体積(v)を求めた。次に、質量(g)を測定し、次式によって、密度を算出した。厚さ、幅及び長さは0.1mm、質量は0.01gの精度まで測定し、密度は0.01g/cm3単位まで次式によって算出した。1枚の試験片ごとに密度を求めた上で、3枚の試験片の平均値を求め、この平均値を密度とした。
密度(g/cm3)=m/v
ここに、m:質量(g)
v:体積(cm3)。
成型性は下記の成型方法により成型した成型体の立ち上がり部位の外観を評価した。
a.成型方法
目的密度に合わせた不織布を遠赤外線ヒーターにて不織布内部温度200℃まで加熱、その後、温度30℃に設定した、図1(a)に示す雄金型1と図1(c)に示す雌金型2からなる金型にて、圧力3000kN/m2で冷却プレスを8秒間行い、図1(b)に示すような厚さ5mm以下の成型体3を作成した。
b.成型体の立ち上がり部位の角のシワ
成型体の立ち上がり部位の角のシワの判定は、次のように行った。
A:成型体の立ち上がり部位の角にシワがない(優)
B:成型体の立ち上がり部位の角に、段差0.5mm未満のシワがある(良)
C:成型体の立ち上がり部位の角に、段差0.5mm以上のシワがある(不良)
c.成型体の立ち上がり部位の透け、亀裂
成型体の立ち上がり部位の透け、亀裂の判定は、次のように行った。
A:成型体の立ち上がり部位に透けや亀裂がない(優)
B:成型体の立ち上がり部位に亀裂はないが、透けがある(良)
C:成型体の立ち上がり部位に亀裂がある(不良)
曲げ強度はJIS A 5905:2003 6.6に準じて測定した。図4に記載の部位で(図4の斜線を付した長方形参照)、成型体3から、タテ方向(斜線を付した縦長の長方形)およびヨコ方向(斜線を付した横長の長方形)のそれぞれについて、幅50mm、長さ150mmの試験片を3枚ずつ採取した。各試験片を温度20℃、相対湿度65%の標準状態にて48時間放置後、曲げ強さ試験装置に、スパン(L)100mmとして試験片を設置し、スパンの中間位置にて試験片の表面から50mm/minの速度で荷重を加え、その最大荷重を測定し、次式によって曲げ強度を求め、3枚の平均値を曲げ強度とした。
曲げ強度(N/mm2)=[3×最大荷重(N)×L(mm)]/
[2×幅(mm)×厚さ2(mm)]
判定
A:曲げ強度が20N/mm2以上(タテ、ヨコ両方)(優)
B:曲げ強度が10N/mm2以上(タテ、ヨコ両方)(良)
C:曲げ強度が10N/mm2未満(タテ、ヨコ両方)(不良)
成型体より幅50mm、長さ100mmの大きさの試験片を5枚ずつ採取した。試験片を2リットルのガラス瓶に1枚ずつ入れ、蓋をした。ガラス瓶を乾燥機(90℃)に入れ、1時間加熱した。その後、乾燥機から取り出し、室温まで冷却した。ガラス瓶の入口に鼻を近づけ、蓋を開け、臭いを嗅ぎ、判定は下記の通り行った。臭気官能試験者は5人にて行い、各人が5枚の試験片の臭いを嗅ぎ、25枚についての5人の平均値を求めた。
1.無臭
2.臭気はあるが、不快臭なし
3.明らかな臭気はあるが、不快臭なし
4.不快臭あり
5.強烈な不快臭あり
ポリ乳酸チップ(融点170℃、重量平均分子量11.3×104)と、結晶核剤としてのメディアン径d50が20nmのカーボンブラック1質量%と、加水分解抑制剤としてトリグリシジルイソシアヌレート(日産化学工業株式会社製「TEPIC」(登録商標。以下同じ。))2質量%を紡糸機ホッパーに仕込み、エクストルーダー型紡糸機にて、紡糸温度230℃にて溶融紡糸し、この紡糸糸条を冷却させ、油剤を付与して収束した後、1000m/分で引き取り、未延伸糸を得た。
実施例1と同じのポリ乳酸短繊維とケナフ繊維とを50対50の質量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次に針密度60本/cm2の条件にてニードルパンチを行い、交絡させて、目付556g/m2、厚さ3.6mmの不織布を得た。その不織布は、タテ方向の引張強度が128N/cm2、ヨコ方向の引張強度が84N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が19N/cm2、ヨコ方向の引張応力が16N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は87%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。不織布の臭気量は1-メトキシ-2-プロピルアセテートが0.3μg/kg、エタノール,2-メトキシ-,アセテートが0.9μg/kg、酢酸が2.4μg/kg、トリメチルベンゼンが1.5μg/kg、アセトアルデヒドが4.1μg/kg、ホルムアルデヒドは検出されなかった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを30対70の質量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次にファーストパンチ80本/cm2、セカンドパンチ80本/cm2、合計針密度160本/cm2の条件にてニードルパンチを行い、交絡させて、目付514g/m2、厚さ3.4mmの不織布を得た。その不織布は、タテ方向の引張強度が58N/cm2、ヨコ方向の引張強度が34N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が9N/cm2、ヨコ方向の引張応力が8N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は57%であり、ポリ乳酸繊維とケナフ繊維の交絡は強固な構造であった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを実施例1と同様の不織布加工条件にて目付1012g/m2、厚さ6.1mmの不織布を得た。その不織布は、タテ方向の引張強度が131N/cm2、ヨコ方向の引張強度が107N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が32N/cm2、ヨコ方向の引張応力が21N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを実施例1と同様の不織布加工条件にて目付1584g/m2、厚さ8.2mmの不織布を得た。その不織布は、タテ方向の引張強度が157N/cm2、ヨコ方向の引張強度が110N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が56N/cm2、ヨコ方向の引張応力が17N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は94%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。不織布の臭気量は1-メトキシ-2-プロピルアセテートが0.3μg/kg、エタノール,2-メトキシ-,アセテートが0.9μg/kg、酢酸が2.9μg/kg、トリメチルベンゼンが1.8μg/kg、アセトアルデヒドが5.1μg/kg、ホルムアルデヒドは検出されなかった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを50対50の質量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次に針密度60本/cm2の条件にてニードルパンチを行い、交絡させて、目付1615g/m2、厚さ8.2mmの不織布を得た。その不織布は、タテ方向の引張強度が175N/cm2、ヨコ方向の引張強度が107N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が44N/cm2、ヨコ方向の引張応力が15N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は92%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。不織布の臭気量は1-メトキシ-2-プロピルアセテートが0.3μg/kg、エタノール,2-メトキシ-,アセテートが0.9μg/kg、酢酸が2.2μg/kg、トリメチルベンゼンが1.5μg/kg、アセトアルデヒドが3.9μg/kg、ホルムアルデヒドは検出されなかった。
ケナフ繊維として、ケナフの茎を河川にてレッディング処理し靭皮繊維を採取し、ギロチンカッターにて切断することによりケナフ繊維を作製した。その後、100℃の10%水酸化ナトリウム水溶液にてケナフ繊維を20分間処理した。得られたケナフ繊維は、繊維長142mm、繊維径40μm、導管に由来する空隙が28個、含水率が16質量%、引張強度が1.5cN/dtexであった。ケナフ繊維の臭気量は1-メトキシ-2-プロピルアセテートが0.1μg/kg、エタノール,2-メトキシ-,アセテートが0.4μg/kg、酢酸が0.2μg/kg、トリメチルベンゼンが0.9μg/kg、アセトアルデヒドが1.8μg/kg、ホルムアルデヒドは検出されなかった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを実施例1と同様の不織布加工条件にて目付1982g/m2、厚さ13.1mmの不織布を得た。その不織布は、タテ方向の引張強度が193N/cm2、ヨコ方向の引張強度が157N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が63N/cm2、ヨコ方向の引張応力が27N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを30対70の重量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次にファーストパンチ50本/cm2、セカンドパンチ50本/cm2、合計針密度100本/cm2の条件にてニードルパンチを行い、交絡させて、目付2538g/m2、厚さ13.8mmの不織布を得た。その不織布は、タテ方向の引張強度が281N/cm2、ヨコ方向の引張強度が237N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が78N/cm2、ヨコ方向の引張応力が/53N/cm2であり、通気度26cc/cm2/secと低いものであった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は96%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。
ケナフ繊維として、ケナフの茎を沼にてレッディング処理し靭皮繊維を採取し、ギロチンカッターにて切断することによりケナフ繊維を作製した。得られたケナフ繊維は、繊維長184mm、繊維径93μm、導管に由来する空隙が30個、含水率が13質量%、引張強度が0.9cN/dtexであった。ケナフ繊維の臭気量は1-メトキシ-2-プロピルアセテートが0.4μg/kg、エタノール,2-メトキシ-,アセテートが1.8μg/kg、酢酸が3.7μg/kg、トリメチルベンゼンが2.2μg/kg、アセトアルデヒドが5.8μg/kg、ホルムアルデヒドは検出されなかった。
ポリ乳酸チップ(融点170℃、重量平均分子量10.8×104)と、結晶核剤としてのメディアン径d50が20nmのカーボンブラック1質量%と、加水分解抑制剤としてトリグリシジルイソシアヌレート(日産化学工業株式会社製「TEPIC」)2質量%を紡糸機ホッパーに仕込み、エクストルーダー型紡糸機にて、紡糸温度230℃にて溶融紡糸し、この紡糸糸条を冷却させ、油剤を付与して収束した後、1000m/分で引き取り、未延伸糸を得た。
ポリ乳酸チップ(融点170℃、重量平均分子量11.3×104)と、結晶核剤としてのメディアン径d50が20nmのカーボンブラック1質量%と、加水分解抑制剤としてトリグリシジルイソシアヌレート(日産化学工業株式会社製「TEPIC」)0.5質量%を紡糸機ホッパーに仕込み、エクストルーダー型紡糸機にて、紡糸温度230℃にて溶融紡糸し、この紡糸糸条を冷却させ、油剤を付与して収束した後、1000m/分で引き取り、未延伸糸を得た。
ポリ乳酸チップ(融点170℃、重量平均分子量11.3×104)と、結晶核剤としてのメディアン径d50が10nmのカーボンブラック1質量%と、加水分解抑制剤としてトリグリシジルイソシアヌレート(日産化学工業株式会社製「TEPIC」)2質量%を紡糸機ホッパーに仕込み、エクストルーダー型紡糸機にて、紡糸温度230℃にて溶融紡糸し、この紡糸糸条を冷却させ、油剤を付与して収束した後、1000m/分で引き取り、未延伸糸を得た。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを20対80の質量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次に針密度60本/cm2の条件にてニードルパンチを行い、交絡させて、目付563g/m2、厚さ3.5mmの不織布を得た。その不織布は、タテ方向の引張強度が52N/cm2、ヨコ方向の引張強度が31N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が12N/cm2、ヨコ方向の引張応力が8N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は90%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを60対40の質量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次に針密度60本/cm2の条件にてニードルパンチを行い、交絡させて、目付580g/m2、厚さ3.6mmの不織布を得た。その不織布は、タテ方向の引張強度が149N/cm2、ヨコ方向の引張強度が98N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が24N/cm2、ヨコ方向の引張応力が18N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は95%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。
ジュート繊維として、ジュートの茎を沼にてレッディング処理し靭皮繊維を採取し、ギロチンカッターにて切断することによりジュート繊維を作製した。得られたジュート繊維は、繊維長123mm、繊維径43μm、導管に由来する空隙が38個、含水率が15質量%、引張強度が1.7cN/dtexであった。
実施例1と同じポリ乳酸繊維とケナフ繊維とを30対70の質量比でエアレイドを用いて混綿し、開繊し、ウェブを作製した。次に針密度60本/cm2の条件にてニードルパンチを行い、交絡させて、目付1542g/m2、厚さ8.3mmの不織布を得た。その不織布は、タテ方向の引張強度が163N/cm2、ヨコ方向の引張強度が117N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が52N/cm2、ヨコ方向の引張応力が19N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は95%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。
ポリ乳酸チップ(融点170℃、重量平均分子量10.6×104)と、結晶核剤としてのメディアン径d50が200×103nmのタルク1質量%と、加水分解抑制剤としてトリグリシジルイソシアヌレート(日産化学工業株式会社製「TEPIC」)2質量%を用いて実施例1と同様の方法で、単子繊度6.6dtex、繊維長51mmのポリ乳酸短繊維を得た。紡糸、延伸工程で糸切れや毛羽の発生もなく、安定して原綿を得ることができた。得られたポリ乳酸短繊維は引張強度2.1cN/dtex、引張伸度69%、捲縮数11.6山/25mm、捲縮度13%、乾熱収縮率1.4%と十分実用性のある力学特性であるが、降温結晶化温度は99℃と結晶化速度の遅いものであった。
ポリ乳酸チップ(融点170℃、重量平均分子量12.8×104)と、加水分解抑制剤としてトリグリシジルイソシアヌレート(日産化学工業株式会社製「TEPIC」)2質量%を用いて実施例1と同様の方法で、単子繊度6.6dtex、繊維長51mmのポリ乳酸短繊維を得た。紡糸、延伸工程で糸切れや毛羽の発生もなく、安定して原綿を得ることができた。得られたポリ乳酸短繊維は引張強度2.3cN/dtex、引張伸度71%、捲縮数11.8山/25mm、捲縮度15%、乾熱収縮率1.5%と十分実用性のある力学特性であるが、降温結晶化温度は検出されなかった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを30対70の重量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次にファーストパンチ80本/cm2、セカンドパンチ80本/cm2、サードパンチ80本/cm2、合計針密度240本/cm2の条件にてニードルパンチを行い、交絡させて、目付521g/m2、厚さ3.4mmの不織布を得た。その不織布は、タテ方向の引張強度が14N/cm2、ヨコ方向の引張強度が9N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が2N/cm2、ヨコ方向の引張応力が1N/cm2であり、不織布中からケナフ繊維の脱落が多く発生した。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は8%であり、ポリ乳酸繊維とケナフ繊維の交絡は弱い構造であった。
実施例10と同じポリ乳酸短繊維とケナフ繊維とを、実施例10と同様の不織布加工条件にて目付428g/m2、厚さ2.9mmの不織布を得た。その不織布は、タテ方向の引張強度が45N/cm2、ヨコ方向の引張強度が18N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が4N/cm2、ヨコ方向の引張応力が3N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は42%であり、ポリ乳酸繊維とケナフ繊維の交絡は強固な構造であった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを、実施例1と同様の不織布加工条件にて目付3428g/m2、厚さ14.0mmの不織布を得た。その不織布は、タテ方向の引張強度が378N/cm2、ヨコ方向の引張強度が341N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が93N/cm2、ヨコ方向の引張応力が84N/cm2であり、通気度は21cc/cm2/secと低いものであった。また、不織布中のポリ乳酸短繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は97%であり、ポリ乳酸繊維とケナフ繊維の交絡は非常に強固な構造であった。
実施例1と同じポリ乳酸短繊維とケナフ繊維とを10対90の質量比でローラーカードを用いて混綿し、開繊し、ウェブを作製した。次に針密度60本/cm2の条件にてニードルパンチを行い、交絡させて、目付524g/m2、厚さ3.5mmの不織布を得た。その不織布は、タテ方向の引張強度が32N/cm2、ヨコ方向の引張強度が17N/cm2、200℃雰囲気における引張伸度30%のタテ方向の引張応力が6N/cm2、ヨコ方向の引張応力が4N/cm2であった。また、不織布中のポリ乳酸繊維の降温結晶化温度は127℃であった。また、不織布中の繊維長45mm以上のケナフ繊維の繊維長度数分布は86%であったが、ポリ乳酸繊維とケナフ繊維の交絡は弱いものであった。
2 雌金型
3 成型体
Claims (11)
- ポリ乳酸繊維と天然繊維とを含む不織布であって、ポリ乳酸繊維の降温結晶化温度が120℃以上であり、不織布の引張強度が20N/cm2以上であり、200℃雰囲気における引張伸度30%の不織布の引張応力が80N/cm2以下であることを特徴とするプレス成型用不織布。
- 前記不織布が、目付450~3000g/m2であることを特徴とする請求項1に記載のプレス成型用不織布。
- 前記不織布中の天然繊維において、繊維長45mm以上の天然繊維の割合が30%以上であることを特徴とする請求項1又は2のいずれかに記載のプレス成型用不織布。
- 前記ポリ乳酸繊維がカーボンブラックを含んでいることを特徴とする請求項1~3のいずれかに記載のプレス成型用不織布。
- 前記ポリ乳酸繊維の乾熱収縮率が5%以下であることを特徴とする請求項1~4のいずれかに記載のプレス成型用不織布。
- 前記天然繊維の引張強度が1.0cN/dtex以上であることを特徴とする請求項1~5のいずれかに記載のプレス成型用不織布。
- 前記天然繊維が、ケナフ繊維であることを特徴とする請求項1~6に記載のプレス成型用不織布。
- 降温結晶化温度が120℃以上で乾熱収縮率5%以下のポリ乳酸繊維と、引張強度が1.0cN/dtex以上の天然繊維を混合し、その後、合計の針密度が30~200本/cm2でニードルパンチを行うことを特徴とするプレス成型用不織布の製造方法。
- 請求項1~7いずれかに記載のプレス成型用不織布をプレス成型することを特徴とする成型体の製造方法。
- プレス成型が冷却手段を備えた金型を用いるものであって、冷却手段を備えた金型での成型時間が8秒以下であることを特徴とする請求項9記載の成型体の製造方法。
- 混合される天然繊維がケナフ繊維であることを特徴とする請求項9または10に記載の成型体の製造方法。
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EP12849313.7A EP2781636B1 (en) | 2011-11-14 | 2012-11-07 | Nonwoven fabric for press molding, method for producing same, and method for producing molded article |
JP2012551818A JP6011343B2 (ja) | 2011-11-14 | 2012-11-07 | プレス成型用不織布及びその製造方法並びに成型体の製造方法 |
CN201280055502.3A CN103946433B (zh) | 2011-11-14 | 2012-11-07 | 加压成型用无纺布及其制造方法以及成型体的制造方法 |
KR20147008101A KR20140095463A (ko) | 2011-11-14 | 2012-11-07 | 프레스 성형용 부직포와 그 제조 방법 및 성형체의 제조 방법 |
US14/357,946 US20140300024A1 (en) | 2011-11-14 | 2012-11-07 | Nonwoven fabric for press molding, method for producing the same, and method for producing molded product |
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WO2017094850A1 (ja) * | 2015-12-02 | 2017-06-08 | 王子ホールディングス株式会社 | 繊維強化プラスチック成形体用シート、繊維強化プラスチック成形体用プリプレスシート及び成形体 |
JP2020523489A (ja) * | 2017-06-15 | 2020-08-06 | ジーピーシーピー アイピー ホールディングス エルエルシー | バイオ系繊維と熱接着されている洗濯可能な植物系基材 |
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US10933597B2 (en) * | 2015-12-25 | 2021-03-02 | Teijin Limited | Press-molding material including discontinuous reinforcing fibers and thermoplastic resin as matrix, shaped product thereof, and manufacturing method for same |
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JPWO2013073425A1 (ja) | 2015-04-02 |
CN103946433B (zh) | 2016-04-27 |
EP2781636B1 (en) | 2016-06-08 |
CN103946433A (zh) | 2014-07-23 |
US20140300024A1 (en) | 2014-10-09 |
EP2781636A4 (en) | 2015-07-08 |
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JP6011343B2 (ja) | 2016-10-19 |
KR20140095463A (ko) | 2014-08-01 |
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