WO2006001439A1 - スパンボンド不織布 - Google Patents
スパンボンド不織布 Download PDFInfo
- Publication number
- WO2006001439A1 WO2006001439A1 PCT/JP2005/011796 JP2005011796W WO2006001439A1 WO 2006001439 A1 WO2006001439 A1 WO 2006001439A1 JP 2005011796 W JP2005011796 W JP 2005011796W WO 2006001439 A1 WO2006001439 A1 WO 2006001439A1
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- WO
- WIPO (PCT)
- Prior art keywords
- nonwoven fabric
- elongation
- melting point
- fabric
- aromatic polyester
- Prior art date
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Classifications
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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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
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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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
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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]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
Definitions
- the present invention relates to a polyester spunbond nonwoven fabric having a low modulus and excellent extensibility, and more specifically, an automobile interior having excellent molding processability and followability and excellent dimensional stability after molding.
- the present invention relates to a polyester spunbond nonwoven fabric suitable for a backing material.
- Sarasuko relates to a polyester spunbond nonwoven fabric that is ideal for backing fabric for door trims.
- Knitted fabrics such as knitted fabrics and tricots, woven fabrics such as gold widths, and non-woven fabrics such as spunbond and short fiber nonwoven fabrics are widely used as backing fabrics for automobile interior materials.
- automotive interior materials in recent years, not only design but also a high-quality feel has been demanded, and therefore skin softness is strongly required.
- the stretchability and followability of the backing fabric will greatly affect the finish of the skin, i.e., the appearance, via the cushion layer. It's getting higher.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-113569
- nonwoven fabrics having a low modulus and excellent extensibility are disclosed.
- Molding force Automotive interior materials such as door trims that are particularly excellent in moldability and followability and excellent in dimensional stability after molding A non-woven fabric suitable for the backing fabric is obtained.
- the present invention has been made against the background of the problems of the prior art, has a low modulus, maintains a high extensibility, is particularly excellent in molding processability and followability, and has a dimensional stability after molding.
- the spunbonded nonwoven fabric of the present invention has a low modulus, maintains high extensibility, is excellent in molding processability and followability, and is excellent in dimensional stability after molding.
- a polyester spunbond nonwoven fabric suitable for the fabric can be provided at a low cost. More specifically, the spunbonded nonwoven fabric of the present invention has high crystallinity, good thermal stability, slightly low modulus, polybutylene terephthalate or polytrimethylene terephthalate as a main component, and thermoformability. In order to improve, by setting the heat distortion temperature low, it has excellent low modulus, maintains high extensibility, and is particularly excellent in moldability and followability. Even a car interior material backing base fabric with excellent dimensional stability can be provided at a low cost as a polyester spunbond nonwoven fabric particularly suitable for door trims that are greatly deformed.
- the aromatic polyester is a polyester of an aromatic dicarboxylic acid such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polybutylene naphthalate, polycyclohexylene dimethyl terephthalate, and diol. I prefer that.
- the other materials Since it is combined with other materials used as automotive interior materials, it is not preferable that the other materials have a melting point at a temperature at which the other materials do not deteriorate. Also, when the composite fluid is deformed and flowed at a temperature that is too low, the heat resistance requirement is not satisfied, which is not preferable.
- the most preferred embodiment of the present invention is a polyester having a melting point (hereinafter abbreviated as Tm) of 220 ° C to 250 ° C that has good thermoformability and can also maintain heat resistance. Can be mentioned.
- PBT polybutylene terephthalate
- PBN polybutylene naphthalate
- the melting point (hereinafter abbreviated as Tm2) of the aromatic copolyester used in the present invention is 150 ° C to
- Tml—20 ° C. is preferable. If the Tm2 is less than 150 ° C, the heat resistance of the non-woven fabric is poor, and if it is less than (Tml-20 ° C), it is difficult to improve the adhesion between the fibers. It is particularly preferably 155 ° C to (Tml-30 ° C), more preferably 160 ° C to (Tml-40 ° C).
- the aromatic copolymer polyester in the present invention refers to a polyester obtained by copolymerizing the aromatic polyester exemplified above with another third component.
- the acid component is a copolymer of a third component such as isophthalic acid, adipic acid, sebacic acid, or daltaric acid
- the diol component is a diol component such as diethylene glycol, neopentyl glycol, butanediol or ethylene glycol.
- Polymerized polyester can be mentioned. If these copolymer components are used, it is possible to obtain a polyester spunbonded nonwoven fabric having flexibility and having a strong bonding force for the following reasons.
- the reason why the above-mentioned copolymer aromatic polyester having the melting point Tm2 is contained in the aromatic polyester having the melting point Tml is as follows. That is, the force that passes through the spinning orifice in a state in which the copolymerized aromatic polyester is well dispersed in the matrix of the melted aromatic polyester. At the contact interface in the molten state before spinning, the copolymerized polyester and the aromatic polyester As the copolymerization progresses, the copolymerization is completed and dispersed in the matrix in a relatively short time with a small addition amount. Next, when a large shear force is applied to the spinning orifice, it is presumed that the copolymer having a low melt viscosity is ejected to the wall surface of the orifice to form a seascore structure.
- aromatic polyester and copolymerized aromatic polyester are resin blends (two or more kinds of polymers are added as resins, mixed in an etastruder, melt extruded, and spun).
- the copolymerized polyester and the aromatic polyester may be copolymerized from before the resin is added in advance by kneading or the like.
- the melting point and the flow start temperature which are the average characteristics of the resin constituting the fiber, are only slightly lowered. In other words, it exhibits a habit that hardly impairs the characteristics of the aromatic polyester, which is the main component.
- the content of the aromatic copolyester capable of exhibiting such an effect is 1 to 15% by weight. Below 1%, almost no effect is observed. When the content exceeds 15% by weight, the characteristics of the aromatic polyester, which is the main component, are slightly degraded. This is not desirable because
- the melting point and flow start temperature of the copolymerized polyester are lowered. Since the heat resistance (flow start temperature and melting point are high !, better! /,) And shape formation (flow start temperature should be lower than the temperature of the intended use + 20 ° C or higher) at the same time, the flow start temperature is The temperature is preferably 140 ° C to 240 ° C, more preferably 160 ° C to 230 ° C, and most preferably 190 ° C to 220 ° C. In the present invention, the flow start temperature can be replaced by the endothermic start temperature measured with a differential scanning calorimeter. Below 140 ° C, the heat resistance is poor, which is not preferable.
- Exceeding 240 ° C is not preferable because the setability at the time of molding deteriorates.
- the non-woven fabric of the present invention is a non-woven fabric composed of a continuous fiber composed of the above-mentioned polyester cable, wherein the non-woven fabric has a load at 5% elongation of 1.2 NZ50 mm or less per gZm 2 basis weight. It is preferable that it is a nonwoven fabric.
- the nonwoven fabric of the present invention is a member that is required to have sufficient strength even with a low basis weight, and is composed of long fibers. Short fiber nonwoven fabrics have a problem that they cannot provide sufficient strength with a low basis weight. Since the long fiber nonwoven fabric of the present invention is a span bond nonwoven fabric, sufficient strength can be imparted even with a low basis weight.
- the spunbonded nonwoven fabric of the present invention preferably has an elongation in the machine and transverse directions of 20% or more and 100% or less. If the elongation is less than 20%, when used as a backing base fabric, it is difficult to stretch, so the followability to the mold shape is inferior, and the desired shape may not be obtained or may be damaged. If the elongation exceeds 100%, the uniform reinforcing function of the backing fabric may be reduced, and the shape may be sag.
- the preferred elongation is 25% to 80%, more preferably 30% to 60%.
- the spunbonded nonwoven fabric of the present invention preferably has a load force at 5% elongation of 1 ⁇ 2 Zm2 per unit weight of 1.2 N / 50 mm or less and a low initial resistance at the time of elongation to ensure followability to the mold shape. Good. When the initial resistance to stretching is large, the followability to the mold shape is poor and the finished shape is poor. Moreover, since it may be damaged, it is not preferable.
- the preferred range is 1. ON / 50 mm to 0.4 NZ50 mm, more preferably 0.8 N / 50 mm to 0.4 NZ50 mm.
- the fineness of the single fiber constituting the spunbonded nonwoven fabric of the present invention is not particularly limited, In order to efficiently provide flexibility, a reinforcing function, and a shielding function, the backing fabric for automobile interior materials is preferably 15 dtex or less, more preferably ldtex to 8 dtex.
- the bonding form of the fibers constituting the spunbonded nonwoven fabric of the present invention is not particularly limited, but embossing force is appropriate for thin materials that require strength. When embossing is required for dot addition and surface smoothing, plane processing is preferred. If a thick and bulky material is required, the needle punch force is appropriate.
- the thickness of the spunbonded nonwoven fabric of the present invention is not particularly limited, but it is desirable to select the optimum thickness for the site of use.
- the sheet backing material is preferably 0.2 mm to 0.5 mm in view of wear resistance and shape followability.
- 0.3mn is required to maintain the molded oil shielding function and reinforcement function! ⁇ Lmm is preferred.
- ceiling materials the importance of adhesion to the ceiling is important, so 0. lmn! ⁇ 0.3 mm is preferred. Trunk interior materials need sound insulation and vibration absorption functions, so 3mn! ⁇ 5mm is preferred.
- Intrinsic viscosity 1.20 or more, 1.80 or less of (hereinafter abbreviated as PBT) polybutylene terephthalate and polyethylene terephthalate with a diol, for example, in 30 mole 0/0 copolymerized melting point of 180 ° C an aromatic polyester (PET copolymer)
- PBT polybutylene terephthalate
- PET copolymer an aromatic polyester
- the mixture be vacuum-dried while being mixed and used for spinning with a water content of at least 0.003% by weight or less.
- a preferable moisture content in the present invention is 0.002% by weight or less.
- melt spinning is performed by a conventional method.
- the spinning temperature is recommended to be 15 ° C to 40 ° C higher than the melting point of polybutylene terephthalate.
- a temperature of preferably 25 ° C to 35 ° C is recommended.
- Orifice force When discharging molten polymer, in the present invention, a hole diameter that can set a high shear rate is recommended.
- the discharge amount is preferably set to an optimum amount that achieves a desired fineness according to the structure formation with a high shear rate and the take-up speed.
- the preferred fineness force Sldtex to 8 dtex so that if the take-up speed is 4000 mZ, the discharge amount per single hole is preferably 0.4 gZ to 3.2 gZ.
- the required number of nozzles can be set as many as small nozzles in multiple rows, or a single nozzle with multiple rows of holes can be used. Yes.
- the discharged molten filament is thinned while being cooled and taken off.
- a web is formed by picking up with an ejector that has an aspirator function and shaking it onto a transport net to open and laminate the fiber array in a random state.
- the fiber may be delayed and recovered within the elastic recovery limit, and the mechanical properties may deteriorate.
- Specific examples include a method of fixing by pinching with a take-off net and a method of fixing using a pressing roller.
- the amount of fiber to be shaken off is adjusted according to the take-up net speed so as to obtain a desired basis weight.
- MD net traveling direction
- MD net traveling direction
- the laminated web is embossed in a continuous or non-continuous manner.
- the emboss shape select the best dot shape, density, or plain shape according to the required functions of the desired nonwoven fabric surface.
- the embossing force temperature is 180 ° C to 220 ° C for PBT, and the linear pressure is 20 kNZn! ⁇ 200kNZm is appropriate.
- the embossed spunbond nonwoven fabric of the present invention obtained by force can be provided as it is as a base fabric for various automobile interior materials.
- the nonwoven fabric of the present invention when used for door trim applications, it is particularly preferred that it has the following constitution. That is, the present invention comprises (A) 80 mol% or more of an aromatic polyester unit, and the endothermic start temperature of the endothermic peak showing the melting point in the temperature rising process in the differential scanning calorimeter is 160 ° C. to 260 ° C. in also the nonwoven continuous fibers force which is C, at 120 ° C the heating of the nonwoven fabric, 100% elongation at least 40% less, spunbond is 0.
- composition of the fibers constituting the nonwoven fabric of the present invention the aromatic polyester unit containing 80 mol 0/0 or more, in the Atsushi Nobori process in a differential scanning calorimeter, an endothermic onset temperature of an endothermic peak showing the melting point
- it may be a non-woven fabric with continuous fiber strength of 160 ° C or higher! /.
- the aromatic polyester unit referred to in the present invention is a polyester of aromatic dicarboxylic acid and diol such as ethylene terephthalate, ethylene naphthalate, trimethylene terephthalate, trimethylene naphthalate, butylene terephthalate, butylene naphthalate, cyclohexylene dimethyl terephthalate, etc. Use units.
- the present invention it is preferable to contain at least 80 mol% or more of an aromatic polyester unit serving as a skeleton that retains heat resistance. If it is less than 80 mol%, the heat resistance is poor, which is not preferable.
- the content is preferably 90 mol%, and most preferably 100 mol%.
- the other material since it is combined with another material used as an automobile interior material, it is preferable that the other material has a melting point at a temperature at which the other material does not deteriorate. Is not preferable. In addition, when deforming and flowing at a temperature that is too low for compounding, it does not satisfy the heat resistance requirement, which is not preferable.
- an aromatic polyester having a melting point (hereinafter abbreviated as Tm) of 220 ° C to 250 ° C having a good thermoformability and heat resistance, and having a slightly low modulus
- Tm melting point
- PTT Polytrimethylene terephthalate
- PTN Polytrimethylene naphthalate
- PBT Polybutylene terephthalate
- PBN polybutylene naphthalate
- the nonwoven fabric has a continuous fiber force with an endothermic start temperature of 160 ° C to 260 ° C of an endothermic peak indicating a melting point in the temperature rising process in the differential scanning calorimeter. If the endothermic temperature is less than 160 ° C, sagging or peeling due to plastic deformation may occur, which is not preferable. If it exceeds 260 ° C, the setability during molding may be poor. Moreover, since it is necessary to perform the heat treatment at the time of forming the nonwoven fabric in the nonwoven fabric manufacturing process at a high temperature, there may be a problem in that it is disadvantageous in terms of energy saving.
- the preferred endothermic endothermic temperature of the present invention is 170 ° C to 220 ° C, more preferably 180 ° C to 210 ° C.
- the melting start temperature can be lowered by preferably setting the temperature to 220 ° C to 250 ° C. Since it can be lowered, it is advantageous in terms of energy saving.
- the other third component can be copolymerized to give a slightly low modulus of Tm of 220 to 250 ° C. of the high melting point aromatic polyester.
- the acid component is a copolymer of a third component such as isophthalic acid, adipic acid, sebacic acid, and dartaric acid
- the diol component is diethylene glycol, neopentyl glycol, butane.
- Examples include polyesters obtained by copolymerizing diol components such as diol Z ethylene glycol.
- copolymerization may be performed when the copolymerized aromatic polyester or aliphatic polyester is mixed and melted.
- the non-woven fabric of the present invention is a non-woven fabric composed of the above-described polyester fiber, and when the non-woven fabric is heated at 120 ° C, the elongation is 40% or more and 100% or less, and 5%.
- a spunbonded nonwoven fabric characterized by a load force of 1 ⁇ 2 / m 2 per unit weight is preferably 0.2 N / 50 mm or less.
- the main purpose of the nonwoven fabric of the present invention is to propose a nonwoven fabric useful as a backing base fabric such as a door trim.
- the usual method is to inject molten resin from the back side of the skin material, cushion material, adhesive film Z nonwoven fabric laminate, and injection molding. At this time, the back base fabric needs to be molded by injecting the molten resin while deforming along the shape and preventing damage to the cushion material and the skin due to the molten resin by the molten resin.
- the elongation can be achieved by limiting the elongation at 120 ° C heating and the load at 5% elongation. That is, in the present invention, the nonwoven fabric is heated at 120 ° C. in the longitudinal direction and the transverse direction. It is preferable that the elongation in the vertical direction and the horizontal direction at the time of 5% elongation is 0.2 NZ50 mm or less per 2 basis weight.
- the elongation at heating at 120 ° C is less than 40%, it does not conform to the shape of the mold, and the back base fabric may be torn or floated, resulting in wrinkling. If it exceeds 100%, sagging, sagging, and wrinkles are likely to occur, which is not preferable. Also, undesirable 120 ° if it exceeds 5% elongation load strength 1 ⁇ 2Zm per w 2 0. 2NZ50mm during the time C heating is hardly along the die shape, since elongation generates a floating even 40% or more easily .
- the preferred elongation of the present invention is 45% to 90%, more preferably 50% to 80%.
- the preferred load per unit weight gZm 2 at 5% elongation of the present invention is from 0.10 NZ50 mm to 0.001 N Z50 mm, more preferably from 0.05 N / 50 mm to 0.005 NZ50 mm.
- the dense layer prevents leakage of the press-fit molten resin from the nonwoven fabric side to the surface layer and cushion layer of the resin, and the dense layer improves the formability by helping the diffusion of the press-fit molten resin into the mold. Can do.
- the dense layer is a spunbond nonwoven fabric having an apparent density of 0.5 lg / cm 3 using a flat cross-sectional yarn of 0.5 dtex, and the coarse layer is a deformed shape of 3.4 dtex.
- Examples thereof include a spunbond nonwoven fabric in which a spunbond nonwoven fabric having an apparent density of 0.05 gZcm 3 using a cross-sectional yarn is entangled with a water jet.
- Basis weight of each layer are not particularly limited, for example, with the eyes of the dense layer 20g / m 2 ⁇ 80g / m 2 , density layer is 50g / m 2 ⁇ : L00g / m 2 is preferred.
- the fiber fineness is not particularly limited, but 0.5 to 3 dtex is preferable for the dense layer, and ldtex to 10 dte X for the dense layer.
- the fineness of the single fiber constituting the spunbonded nonwoven fabric of the present invention is not particularly limited, but for use as a backing base fabric for automobile interior materials, flexibility and a reinforcing function or a shielding function are efficiently imparted. Therefore, it is preferably 15 dtex or less, more preferably 0.5 dtex to 8 dtex.
- the cross-sectional shape of the single fiber constituting the spunbonded nonwoven fabric of the present invention can be a round cross-section or an irregular cross-section, and is not particularly limited. In order to efficiently provide a shielding function, a flat cross-section is recommended. When bulkiness is required, a hollow cross section or irregular cross section can be recommended.
- the bonding form of the fibers constituting the spunbonded nonwoven fabric of the present invention is not particularly limited, but in order to prevent the penetration of the molten resin, a dense structure is preferred, for example, embossing is appropriate. When embossing is required for dot processing and surface smoothing, plane processing is preferred. When a thick and bulky material is required, the needle punching force is appropriate.
- the thickness of the spunbonded nonwoven fabric of the present invention is not particularly limited, but it is desirable to select the optimum thickness for the site of use. For example, for door trims, 0.3mn! ⁇ Lmm is preferred. For ceiling materials, adhesion to the ceiling is important, so 0. lmn! ⁇ 0.3 mm is preferred.
- the interior material of the trunk is preferably 3mm to 5mm because it requires sound insulation and vibration absorption functions!
- the basis weight of the spunbonded nonwoven fabric of the present invention is not particularly limited, but it is desirable to select an optimal one at the site of use.
- 30 g / m 2 to: LOOg / m 2 is preferable in order to maintain a molded resin shielding function and a reinforcing function.
- adhesion to the ceiling is important, so 15 g / m 2 to 30 g / m 2 is preferable.
- the trunk interior material needs sound insulation and vibration absorption function, so 100g / m 2 to 300g / m 2 is preferred.
- Intrinsic viscosity 1 20-1. 80 polybutylene terephthalate (hereinafter abbreviated as PBT), or polytrimethylene terephthalate with a intrinsic viscosity of 0.8 to 1.6, copolymerized with polyethylene terephthalate, for example, 30 mol% It is recommended that the aromatic polyester with a melting point of 180 ° C (PET copolymer) be vacuum-dried while being mixed and used for spinning with a moisture content of at most 0.003% by weight. A preferable moisture content in the present invention is 0.002% by weight or less. If the drying process is omitted and moisture is removed from the vent at the spinning stage, a method of removing moisture at high vacuum immediately before and immediately after melting by an extruder is recommended.
- melt spinning is performed by a conventional method.
- the spinning temperature is recommended to be 15 ° C to 40 ° C higher than the melting point of polybutylene terephthalate.
- a temperature of preferably 25 ° C to 35 ° C is recommended.
- Orifice force When discharging molten polymer, in the present invention, a hole diameter that can set a high shear rate is recommended. It is particularly preferable to increase the shear rate because a pseudo seascore structure can be formed.
- the preferred shear rate is 500Z to 5000Z seconds, more preferred It is preferably 1500Z seconds to 4000Z seconds. If the shear rate exceeds 10000 Z seconds, abnormal flow occurs and the strength of the fiber decreases, which is not preferable.
- the discharge amount is preferably set to an optimum amount that achieves a desired fineness according to the structure formation with a high shear rate and the take-up speed.
- the discharge amount per single hole is preferably 0.2 gZ to 3.2 gZ.
- the required number of nozzles to be ejected may be set as many as small nozzles in multiple rows, or a single nozzle having multiple rows of holes may be used.
- the molten filaments discharged are thinned while being cooled and taken off.
- a web is formed by picking up with an ejector having an aspirator function and shaking it on a transport net to open and laminate the fiber arrangement in a random state.
- the fiber may be delayed and recovered within the elastic recovery limit, and the shape retention of the nonwoven fabric may be reduced, resulting in poor handling.
- a method of fixing the web form by immediately suppressing delayed recovery of the spread-laminated web is strongly recommended.
- a method of pinching and fixing with a take-off net and a method of fixing with a pressing roller can be illustrated. From this fact, the shape retention of the nonwoven fabric is remarkably improved.
- the amount of fiber to be shaken off is adjusted according to the take-up net speed so as to obtain a desired basis weight and then shaken off.
- the laminated web is continuously or discontinuously subjected to entanglement processing such as one-dollar punch force check, embossing, and hydroentanglement processing.
- entanglement processing such as one-dollar punch force check, embossing, and hydroentanglement processing.
- needle punching it is preferable to optimize the needle number density and needle shape according to the density and entanglement strength.
- embossing according to the required function of the surface of the nonwoven fabric, the embossed shape is selected and processed as the desired dot shape, density, or plain shape.
- the embossing temperature is suitably 180 ° C to 220 ° C for PTT and PBT
- the linear pressure is suitably 20 kN / m to 2 OOkNZm.
- the hydroentanglement process is performed on one or both sides as necessary.
- the water flow pressure is suitably 2MPa to 10MPa, and at low pressure, the entanglement effect is low. Too much is not preferable because it causes fiber damage.
- hydroentanglement is a particularly preferable embodiment for integrating a laminated structure of a dense layer and a dense layer.
- the spunbonded nonwoven fabric and / or embossed scaffolding and / or hydroentangled nonwoven fabric of the present invention obtained by caulking can be directly provided as a base fabric for various automobile interior materials.
- the production capacity of the resin is also processed into a molded body within a range not deteriorating the performance, and a function-imparting agent such as deodorant antibacterial, deodorant, antifungal, coloring, aroma, flame retardant, etc. is added at any stage of commercialization. Processing can be performed by giving.
- the illustrations in the present invention are not limited to these examples.
- the melting point is the endothermic peak temperature of the endothermic phenomenon caused by melting when the differential scanning calorimeter is heated from 20 ° C to 300 ° C in 20 ° CZ minutes.
- the load at the time of applying 5% elongation strain was measured from the strain Z load curve measured in a 120 ° C heating atmosphere.
- TPA terephthalic acid
- EG ethylene glycol
- NPG neopentyldaricol
- the ejector is installed at a point of 0.8m below the nozzle and is sucked at a speed of 4100mZ, and the net is moving at a speed of 50mZ at a point 1.5m below the nozzle.
- the fiber bundle was spun off and stacked while opening the fiber bundle.
- the web laminated on the net surface was immediately pre-compressed with a temporary pressing roller and wound around a bow I take-off roller.
- a spunbond nonwoven fabric obtained by embossing the wound nonwoven fabric with a 4 mm pitch dot embossing nozzle at 210 ° C. and a linear pressure of 50 kNZm was obtained.
- the thickness of the obtained embossed spunbonded nonwoven fabric is 0.17mm, weight per unit 25gZm 2 , load at 5% elongation per unit length in the machine direction (MD) 0.5NZ5cm, tensile strength 40NZ5cm, elongation 25 %, Load per unit area in the transverse direction (CD) at 5% elongation was 0.4 NZ5 cm, tensile strength was 30 N / 5 cm, and elongation was 28%.
- the fineness of the fibers constituting the nonwoven fabric is 1.7 dtex, the melting point is 226 ° C, the flow initiation temperature is 198 ° C, and most of the contact points between the fibers are bonded.
- the performance evaluation of the obtained spunbonded nonwoven fabric was applied to a ceiling material for evaluation.
- Spangbon Z Non-woven fabric adhesive layer z olefin layer z adhesive layer z glass fiber layer z heat insulation sound insulation layer z glass fiber layer Z adhesive layer Z surface layer laminated on the mold and ceiling molded by thermoforming at 130 ° C was joined to the ceiling of the car body.
- the obtained ceiling material was a ceiling with good quality, following the ceiling shape with floating, sagging, tearing, exudation of grease and irregularities. That is, Example 1 satisfied all the requirements for the invention, and exhibited excellent performance as a backing fabric for ceiling materials.
- MD machine direction
- the fineness of the fibers constituting the nonwoven fabric is 1.7 dtex
- the melting point is 229 ° C
- the flow start temperature is 204 ° C
- Example 2 Performance evaluation of the obtained spunbonded nonwoven fabric was performed in the same manner as in Example 1.
- the obtained ceiling material was a ceiling with good quality, following the ceiling shape with floating, sagging, tearing, exudation of grease and irregularities. That is, Example 2 satisfied all the requirements of the invention and exhibited excellent performance as a backing fabric for ceiling materials.
- the load was 0.4NZ5cm
- the tensile strength was 27NZ5cm
- the elongation was 20%
- the load at 5% elongation per unit weight in the cross direction (CD) was 0.2N / 5cm
- the tensile strength was 19NZ5cm
- the elongation was 25%.
- the fineness of the fibers constituting the nonwoven fabric is 1.7 dtex
- the melting point is 230 ° C
- the flow start temperature is 21 3 ° C
- the obtained ceiling material was free from floating, sagging, tearing, exudation of grease, and unevenness, but a portion where the backing of the nonwoven fabric was poor was found at one corner.
- the ceiling shape was slightly inferior, and the ceiling was acceptable. That is, Comparative Example 1 satisfies the strength and elongation characteristics of the nonwoven fabric of the present invention except that the composition of the fibers is different. The performance was slightly inferior to the woven fabric.
- Comparative Example 2 satisfies the strength and elongation characteristics of the nonwoven fabric of the present invention except that the fiber composition is different, but the performance as a backing fabric in the ceiling material is inferior to that of the nonwoven fabric of the present invention. To the eye.
- the embossed spunbond nonwoven fabric obtained in the same manner as in Example 1 except that 25 parts of COPES-B and 75 parts of PBT were used has a thickness of 0.15 mm, a basis weight of 25 gZm 2 , and a machine direction (MD ) 5% extension load per unit weight 0.8 N / 5 cm, tensile strength 46 NZ 5 cm, elongation 12%, lateral direction (CD) per unit weight 5% extension load 0.6 N / 5 cm, tensile strength 37 NZ 5 cm
- MD machine direction
- CD lateral direction
- the resulting ceiling material had raised corners, irregularities, and tearing of the backing fabric.
- the ceiling shape was poor, and the ceiling was out of the acceptable range. That is, in Comparative Example 3, the performance of the back base fabric for ceiling materials was inferior to that of the nonwoven fabric of the present invention.
- the embossed spunbond nonwoven fabric obtained in this way has a thickness of 0.14mm, weight per unit of 25g Zm2, load at 5% elongation per unit length in the machine direction (MD) 1.4N / 5cm, tensile strength 58NZ 5cm, The elongation was 12%, the load at 5% elongation per unit weight in the transverse direction (CD) was 1.2N / 5cm, the tensile strength was 44NZ5cm, and the elongation was 16%.
- the fiber flow start temperature was 149 ° C, and the deformation start temperature was no problem!
- Performance evaluation of the obtained spunbonded nonwoven fabric was carried out on the ceiling material in the same manner as in Example 1.
- the resulting ceiling material had raised corners and irregularities, and the backing fabric was insufficiently stretched.
- the ceiling shape was inferior, and the ceiling was out of tolerance. That is, in Comparative Example 4, the performance of the back base fabric for ceiling materials was inferior to that of the nonwoven fabric of the present invention.
- the spunbonded nonwoven fabric obtained in the same manner as in Comparative Example 4 except that only embossing was pre-embossed had a thickness of 0.9mm, a basis weight of 25gZm2, and a 5% elongation load per unit area in the machine direction (MD) 0 05N / 5cm, Tensile strength lNZ5cm, Elongation 143%, Load 5% per unit area in the cross direction (CD) at elongation 0.04NZ5cm, Tensile strength 8NZ5cm, Elongation 165%.
- the fiber flow start temperature is 149 ° C, and the deformation start temperature is a problem-free temperature.
- the resulting ceiling material had raised corners, irregularities, sagging, tearing of the back base fabric, and exudation of adhesive to the back base fabric.
- the ceiling shape was poor, and the ceiling was out of the acceptable range. That is, in Comparative Example 5, the performance of the back base fabric for ceiling materials 1S was inferior to that of the nonwoven fabric of the present invention even when the elongation of the back base fabric was increased.
- Tml aromatic polyester
- Tm2 aromatic copolymer polyester
- TPA terephthalic acid
- EG ethylene glycol
- NPG neopentyldaricol
- TPA 100 parts of TPA, 70 parts of 1 ⁇ 4 butanediol (hereinafter abbreviated as BG) are charged with a small amount of catalyst, and are subjected to ester exchange and one polymerization in a conventional manner, and then pelletized to have a melting point of 230 ° C and an intrinsic viscosity of 1.205. P BT was obtained.
- the suction net surface that is moving at a speed of 50 mZ at a point 1.5 m below the nozzle is pulled while sucking at a speed of 4100 mZ of the yarn speed with an ejeter installed at a point of 0.8 m below the nozzle.
- the fiber bundle was spun off and laminated while opening the fiber bundle.
- the web laminated on the net surface was immediately pre-compressed with a temporary pressing roller and wound around a take-up outlet.
- a spunbonded nonwoven fabric was obtained by embossing the wound nonwoven fabric with a 6 mm pitch dot embossing roller at 210 ° C. and a linear pressure of 50 kNZm.
- the thickness of the resulting embossed caloe spunbond nonwoven fabric is 0.7mm, weight per unit is 115gZm 2 , 120 ° C atmosphere, machine direction (MD) tensile strength 30NZ50mm, elongation 75%, per unit weight 5% elongation
- MD machine direction
- tensile strength 30NZ50mm
- elongation 75% per unit weight 5% elongation
- the load was 0.02N / 50mm
- the transverse (CD) tensile strength was 25NZ50mm
- the elongation was 81%
- the weight per unit weight was 5% when the load was 0.01NZ50mm.
- the fineness of the fibers constituting the nonwoven fabric is 1.7 dte X, the melting point is 226 ° C, the endothermic onset temperature is 189 ° C, and the entanglement between the fibers is made up of embossed dots!
- Adhesive layer Z cushion layer (foamed urethane) Z adhesive layer Z skin layer is laminated on the spunbond nonwoven fabric and placed in the mold, and 200 ° C polypropylene original resin is injected to create a door trim in the usual way. did.
- the surface of the door trim of the obtained door trim is free from floating, sagging, tearing, wrinkles, unevenness, and side leakage.
- the resin layer and the non-woven fabric layer which did not exude to the surface of the non-woven fabric examined by peeling the skin layer and the cushion layer, were sufficiently tightly bonded, and the door trim had good quality.
- Example 3 satisfied all the invention requirements and exhibited excellent performance as a backing fabric for door trims.
- PTMG polytetramethylene glycol with a molecular weight of 1000
- COPES-B aromatic copolymer polyester A having a melting point of 226 ° C. and an intrinsic viscosity of 1.580 was obtained.
- the obtained COPES-B was dried and subjected to spinning.
- Spinning temperature is 260 ° C
- orifice shape is 0.04mm wide and 0.40mm long slit hole nozzle, spinning at a single hole discharge of 0.3gZ, and air at 20 ° C from 50mm below nozzle While cooling at a wind speed of 0.5mZ seconds, take the bow I while sucking the bow at a speed of 4000mZ with the ejector installed at a point of 0.8m below the nozzle and 45mZ at the 1.5m point below the nozzle.
- the fiber bundle was spun off and laminated on the surface of the take-up net moving at a speed of minutes.
- the web laminated on the net surface was immediately pre-compressed with a temporary holding port and wound around a take-up roller.
- the obtained nonwoven fabric (B1) had a basis weight of 40 gZm 2 and the average fineness of the single fibers was 0.75 dtex.
- the web laminated on the net surface was immediately pre-compressed with a temporary pressing roller and wound up on a take-up roller.
- the nonwoven fabric (B2) obtained had a basis weight of 80 gZm 2 and the single fiber fineness was 3.3 dtex.
- the non-woven fabrics B1 and B2 are laminated and placed on a conveyor of speed 50mZ, entangled with a water stream pressurized at a pressure of 3MPa from a jet nozzle with a nozzle hole diameter of 0.15mm and a hole pitch of 8mm, and dried. Then, emboss with a plain roller at 180 ° C and linear pressure 20kN / m. A laminated spunbonded nonwoven fabric was obtained. The resulting spunbonded nonwoven fabric has a thickness of 0.9 mm and a basis weight of 120 gZm 2 , 120. C atmosphere
- the skin material part of the door trim obtained is free from floating, sagging, tearing, wrinkles, unevenness, and side leakage. No exudation of grease on the nonwoven fabric surface that was examined by peeling the skin layer and the cushion layer. The grease layer and the non-woven fabric layer were sufficiently tightly joined, and the door trim had good quality. That is, Example 4 satisfied all the requirements of the invention, and showed excellent performance as a backing fabric for door trim.
- TPA trimethylene glycol
- TG trimethylene glycol
- the laminated spunbonded nonwoven fabric obtained by laminating the nonwoven fabrics B2 and C1 obtained in Example 4 and performing hydroentanglement treatment and embossing in the same manner as in Example 4, has a thickness of 0.8 mm and a basis weight of 120 gZ m 2.
- MD Longitudinal direction
- tensile strength 29NZ50mm tensile strength 29NZ50mm
- elongation rate 78% 120 ° C atmosphere
- the 5% elongation load per contact was 0.02N / 50mm
- the transverse (CD) tensile strength was 24NZ50mm
- the elongation was 87%
- the 5% elongation load per unit weight was 0.01NZ50mm.
- the fineness of the fibers constituting the nonwoven fabric is 0.665 dtex and 3.3 dtex, melting points 221 ° C and 226 ° C, endothermic onset temperatures 182 ° C and 189 ° C, and the entanglement between the fibers is joined by hydroentanglement Yes.
- the performance evaluation of the obtained laminated spunbonded nonwoven fabric was applied to a door trim material and evaluated in the same manner as in Example 3.
- the skin material part of the obtained door trim is free from floating, sagging, tearing, wrinkles, unevenness, and side leakage. No exudation of grease on the surface of the nonwoven fabric examined by peeling off the skin layer and the cushion layer. The grease layer and the non-woven fabric layer were sufficiently tightly joined, and the door trim had good quality. In other words, Example 5 satisfied all the requirements of the invention, and exhibited excellent performance as a backing fabric for door trim.
- the thickness of the embossed spunbond nonwoven fabric obtained in the same manner as in Example 3 was 0.7 mm, the basis weight was 110 gZm 2 , and the longitudinal direction (MD ) Tensile strength 192NZ50mm, elongation 38%, load per unit weight 5% elongation 0.81NZ50mm, transverse (CD) tensile strength 114NZ50mm, elongation 67%, per unit weight 5% elongation load 0 It was 33NZ50mm.
- the fineness of the fibers that make up the nonwoven fabric is 5.2 dtex, the melting point is 256 ° C, the endothermic temperature is 237 ° C, and the entanglement between the fibers is joined by the embossed dot.
- the performance evaluation of the obtained embossed spunbonded nonwoven fabric was evaluated in the same manner as in Example 3.
- the skin material part of the obtained door trim is floating, wrinkled, and uneven, and the exudation of the grease on the nonwoven fabric surface, which was examined by peeling off the skin layer and the tassillon layer, was around the injection part. Had occurred. Although the resin layer and the nonwoven fabric layer were sufficiently closely joined, the door trim was very poor. That is, since Comparative Example 6 did not satisfy most of the requirements of the present invention, it showed very inferior performance as a backing fabric for the door trim.
- An embossed spanbond nonwoven fabric obtained in the same manner as in Example 3 except that COPES-C was used has a thickness of 0.6 mm, a basis weight of 115 gZm 2 , and a longitudinal direction (MD) in an atmosphere of 120 ° C.
- the fineness of the fibers constituting the nonwoven fabric is 1.2 dtex, the melting point is 184 ° C, the endothermic start temperature is 137 ° C, and the entanglement between the fibers is joined by embossing.
- the performance evaluation of the obtained spunbonded nonwoven fabric was performed in the same manner as in Example 3.
- the skin material part of the door trim that was obtained had wrinkles and irregularities that were severely leaked.
- the exudation of greaves on the surface of the nonwoven fabric examined by peeling the skin layer and the cushion layer is remarkable.
- the resin layer and the nonwoven fabric layer were sufficiently tightly joined.
- the door trim was extremely inferior in strength. In other words, Comparative Example 7 deviated from the requirements of the invention, and the leakage of the grease became significant due to the low flow start temperature, so that it could not be used as the backing fabric for the door trim.
- pre-compressed and wound spunbond nonwoven fabric obtained in the same manner as in Example 3 except that spinning was performed at a take-off speed of 2500 mZ with a single-hole discharge of 0.30 gZ. was then punched for one dollar with pene 60 to obtain a needle punched spunbond nonwoven fabric.
- the thickness of the resulting embossed spunbonded nonwoven fabric was 0.9 mm, basis weight 115 gZm 2 , and longitudinal strength (MD) tensile strength 20 NZ 50 mm, elongation 135%, weight per unit area at 20 ° C.
- the load at the time of 5% elongation was 0.006NZ50mm, the tensile strength in the transverse direction (CD) was 15NZ50mm, the elongation was 151%, and the load at 5% elongation per unit weight was 0.002NZ50mm.
- the fineness of the fibers constituting the non-woven fabric is 1.2 dtex, the melting point is 226 ° C, the endothermic onset temperature is 197 ° C, and the entanglement between the fibers is fixed by entanglement with a one-dollar punch.
- the obtained one-dollar punch spunbond nonwoven was applied to a door trim as in Example 3 and evaluated. [0085] The skin material portion of the obtained door trim was lifted, sagged, and wrinkled. There was no exudation of the grease on the surface of the nonwoven fabric, which was examined by peeling the skin layer and the tackle layer. The resin layer and the nonwoven fabric layer were sufficiently closely joined, and the quality of the door trim was slightly inferior. In other words, Comparative Example 8 did not satisfy some of the requirements of the invention, and thus showed an inferior and inferior performance as a backing fabric for the door trim.
- the spunbonded nonwoven fabric of the present invention contains 80 mol% or more of aromatic polyester units, and in the temperature rising process in the differential scanning calorimeter.
- the non-woven fabric with continuous fiber strength having an endothermic peak of 160 ° C. or higher indicating the melting point when the non-woven fabric is heated at 120 ° C., the elongation is 40% or more and 100% or less, and when the elongation is 5%.
- Polyester spunbond that is optimal for door trims that cause large deformations even in the interior backing material of automobile interiors by using a spunbonded nonwoven fabric characterized by a load of 0.2 N / 50 mm or less per g / m 2 basis weight.
- a nonwoven fabric can be provided.
- the spunbond nonwoven fabric of the present invention is the main component of polybutylene terephthalate having a high crystallinity, a melting point of 220 ° C or higher, a good thermal stability, and a slightly low modulus.
- the heat distortion temperature is set low to maintain excellent extensibility, high extensibility, excellent moldability and followability, and dimensional stability after molding. It can be provided at low cost as a polyester spunbond nonwoven fabric suitable for automobile interior material backing base fabric with excellent properties. Furthermore, by making the basis weight and thickness desired, it can be provided as a non-woven fabric that is useful for applications other than automobile interior materials.
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05755399A EP1767681A4 (en) | 2004-06-29 | 2005-06-28 | NON-WOVEN FILE-LIE FABRIC |
US11/571,402 US20080038980A1 (en) | 2004-06-29 | 2005-06-28 | Spunbonded Nonwoven Fabrics |
CN200580019559.8A CN1969074B (zh) | 2004-06-29 | 2005-06-28 | 纺粘型无纺布 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2004-191058 | 2004-06-29 | ||
JP2004191059A JP2006009215A (ja) | 2004-06-29 | 2004-06-29 | スパンボンド不織布 |
JP2004191058A JP4120883B2 (ja) | 2004-06-29 | 2004-06-29 | スパンボンド不織布 |
JP2004-191059 | 2004-06-29 |
Publications (1)
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WO2006001439A1 true WO2006001439A1 (ja) | 2006-01-05 |
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PCT/JP2005/011796 WO2006001439A1 (ja) | 2004-06-29 | 2005-06-28 | スパンボンド不織布 |
Country Status (4)
Country | Link |
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US (1) | US20080038980A1 (ja) |
EP (1) | EP1767681A4 (ja) |
KR (1) | KR20070028376A (ja) |
WO (1) | WO2006001439A1 (ja) |
Cited By (1)
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JP2023508484A (ja) * | 2019-12-27 | 2023-03-02 | トーレ・アドバンスド・マテリアルズ・コリア・インコーポレーテッド | 自動車内装材用繊維集合体及びこれを含む自動車内装材 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101108471B1 (ko) * | 2009-06-09 | 2012-01-31 | 에스케이씨 주식회사 | 이축연신 폴리에스터 필름 및 이의 제조방법 |
DK2644763T3 (en) * | 2010-11-25 | 2017-02-20 | Mitsui Chemicals Inc | Spunbond nonwoven fabric laminate |
JP5684687B2 (ja) * | 2011-10-04 | 2015-03-18 | ダイハツ工業株式会社 | 天井材 |
ITBO20120229A1 (it) * | 2012-04-26 | 2013-10-27 | Spal Automotive Srl | Macchina elettrica. |
JP6011253B2 (ja) | 2012-11-02 | 2016-10-19 | 東洋紡株式会社 | 成型性の優れた熱圧着長繊維不織布 |
Citations (3)
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JPH06116484A (ja) * | 1992-10-06 | 1994-04-26 | Toyobo Co Ltd | 耐熱性に優れた熱融着用樹脂組成物とそれを接着成分とした不織布 |
JPH11240088A (ja) * | 1998-02-24 | 1999-09-07 | Bridgestone Corp | 繊維積層成形体 |
JP2002180366A (ja) * | 2000-12-15 | 2002-06-26 | Asahi Kasei Corp | 成型性に優れた長繊維不織布 |
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US4699619A (en) * | 1984-08-31 | 1987-10-13 | Kimberly-Clark Corporation | Absorbent structure designed for absorbing body fluids |
US6475618B1 (en) * | 2001-03-21 | 2002-11-05 | Kimberly-Clark Worldwide, Inc. | Compositions for enhanced thermal bonding |
US6770356B2 (en) * | 2001-08-07 | 2004-08-03 | The Procter & Gamble Company | Fibers and webs capable of high speed solid state deformation |
-
2005
- 2005-06-28 KR KR1020067024682A patent/KR20070028376A/ko not_active Application Discontinuation
- 2005-06-28 WO PCT/JP2005/011796 patent/WO2006001439A1/ja active Application Filing
- 2005-06-28 US US11/571,402 patent/US20080038980A1/en not_active Abandoned
- 2005-06-28 EP EP05755399A patent/EP1767681A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06116484A (ja) * | 1992-10-06 | 1994-04-26 | Toyobo Co Ltd | 耐熱性に優れた熱融着用樹脂組成物とそれを接着成分とした不織布 |
JPH11240088A (ja) * | 1998-02-24 | 1999-09-07 | Bridgestone Corp | 繊維積層成形体 |
JP2002180366A (ja) * | 2000-12-15 | 2002-06-26 | Asahi Kasei Corp | 成型性に優れた長繊維不織布 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2023508484A (ja) * | 2019-12-27 | 2023-03-02 | トーレ・アドバンスド・マテリアルズ・コリア・インコーポレーテッド | 自動車内装材用繊維集合体及びこれを含む自動車内装材 |
JP7419540B2 (ja) | 2019-12-27 | 2024-01-22 | トーレ・アドバンスド・マテリアルズ・コリア・インコーポレーテッド | 自動車内装材用繊維集合体及びこれを含む自動車内装材 |
Also Published As
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KR20070028376A (ko) | 2007-03-12 |
EP1767681A1 (en) | 2007-03-28 |
EP1767681A4 (en) | 2010-02-24 |
US20080038980A1 (en) | 2008-02-14 |
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