WO2022092303A1 - Molded article having reversible thermal stretchability, fiber product, actuator, and assist suit - Google Patents
Molded article having reversible thermal stretchability, fiber product, actuator, and assist suit Download PDFInfo
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- WO2022092303A1 WO2022092303A1 PCT/JP2021/040167 JP2021040167W WO2022092303A1 WO 2022092303 A1 WO2022092303 A1 WO 2022092303A1 JP 2021040167 W JP2021040167 W JP 2021040167W WO 2022092303 A1 WO2022092303 A1 WO 2022092303A1
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- Prior art keywords
- molded product
- product according
- coil
- fiber
- actuator
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/60—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the warp or weft elements other than yarns or threads
- D03D15/67—Metal wires
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
- F03G1/00—Spring motors
- F03G1/02—Spring motors characterised by shape or material of spring, e.g. helical, spiral, coil
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
- F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
- F03G7/06—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for using expansion or contraction of bodies due to heating, cooling, moistening, drying or the like
Definitions
- the present invention relates to a molded body, a textile product, an actuator and an assist suit having reversible thermal elasticity.
- Actuator is a general term for devices that create movement and force, such as motors, pneumatic / pneumatic cylinders, piezoelectric elements, and artificial muscles.
- An actuator is a driving body whose material itself is deformed by energy such as electricity, heat, light, and fuel, and its basic deformation pattern is expansion / contraction, bending / stretching, twisting, expansion / contraction.
- Patent Document 1 discloses that nylon fibers are twisted and a coil-shaped actuator exhibits reversible thermal expansion and contraction.
- Patent Document 2 and Non-Patent Document 1 disclose an actuator in which a linear low-density polyethylene fiber is formed into a coil shape to have a high heat shrinkage rate per unit temperature and achieve a high displacement with a small temperature change.
- Patent Document 3 discloses a fiber for an actuator that expands and contracts reversibly by heating and cooling and has abundant flexibility, and describes that a nylon fiber has a coil shape and a spring index is increased to a specific value or more. ..
- Non-Patent Document 2 discloses an actuator in which a fiber having reversible thermal elasticity is formed into a coil shape.
- a means for heating the actuator for example, in Non-Patent Document 3, a method of using nylon fibers coated with silver paste as a heating wire, or a coil made of fibers is coated with a conductive paste to obtain a coil capable of energization heating. The method is disclosed.
- Patent Document 4 discloses a method of arranging an electric heating member and an insulating member on the outer periphery of a coil made of fibers.
- Patent Document 1 the heat shrinkage rate of the nylon fiber itself per unit temperature was about 0.002% / ° C, which was low.
- Patent Document 2 and Non-Patent Document 1 although the heat shrinkage of the linear low-density polyethylene fiber itself is higher than that of nylon, it is not sufficient as an actuator.
- Patent Document 3 since nylon is used, the heat shrinkage rate per unit temperature of the fiber itself is low, and there is a limitation that the shrinkage rate cannot be increased unless the spring index of the coil is increased.
- Non-Patent Document 2 nylon fibers covered with a silver film are used as a method of using a plurality of fibers side by side, and short circuit does not occur due to contact between the nylon fibers covered with the silver film during energization heating. As described above, it is a woven fabric sandwiched between polyester fibers and cotton fibers. However, since the nylon fiber covered with the silver film is not insulated, the possibility of short circuit remains. In addition, when water is used as the coolant, there is a risk of electric leakage.
- Non-Patent Document 3 a conductive film is applied to a double-threaded coil made of two fibers, but an insulating film is not provided. Further, in this method, a defect is likely to occur in the conductive film each time the coil expands and contracts, and a problem in repeated durability tends to occur. In addition, it is difficult to control the resistance value because the state such as the thickness of the conductive film changes and the resistance value changes every time the expansion and contraction movement is performed, and there is a risk of short circuit. Further, when a coil made of fibers is used on a scale of several hundreds, a great cost is required.
- Patent Document 4 describes how to arrange an electric heating member and an insulating member with respect to a coil made of fibers or two coils made of fibers in a twin-thread shape.
- a coil made of fibers is used on a scale of several hundreds, enormous cost and labor are required.
- the number of coils made of fibers that can be arranged per volume is reduced.
- a first object of the present invention is to provide a molded product, a textile product, and an actuator having excellent reversible thermal elasticity.
- a second object of the present invention is to provide an assist suit that has high repeatability and can be used safely, and an actuator module that is a part thereof.
- 2. A molded product having a gel fraction of 10% or more, a crystal orientation degree of 60% or more, and a coil shape.
- 3. The molded product according to 1 or 2, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher.
- 4. The molded product according to any one of 1 to 3, wherein the shrinkage rate when a temperature change of 50 ° C. is applied by heating is 3.5% or more. 5.
- the molded product according to any one of 1 to 4 which has a crosslinked structure inside the molded product. 6. 5.
- the molded product according to any one of 1 to 11 made of polyethylene.
- the molded product according to any one of 1 to 12, wherein the molded product is in the form of a fiber, a plate, a sheet, or a film, or has one or more of these multilayer structures.
- 14. 13 The molded product according to 13, wherein the molded product is fibrous and the fineness of the single fiber of the fibrous molded product is 50 to 10000 dtex. 15. 13.
- (1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2 ⁇ 10 ° to 30 °. (2) There is no peak other than the peak with the highest intensity, or the intensity of the peak with the highest intensity is more than double the intensity of the peak with the next highest intensity.
- the degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material. 18. 16. The molded product according to 16 or 17, wherein the spring index D / d is 0.5 or more, and the average diameter D of the coil shape is 100 to 2000 ⁇ m. D indicates the coil average diameter ( ⁇ m), and d indicates the single fiber diameter ( ⁇ m). 19.
- One or more polyethylenes 20-80 selected from linear low density polyethylene with a density of 0.881 to 0.941 g / cm 3 and high density polyethylene with a density of 0.942 to 0.970 g / cm 3 .
- the textile product according to 23, which is a woven fabric, a knitted fabric, a non-woven fabric, or a string.
- the textile product according to 25, wherein the heating wire is one continuous heating wire.
- the textile product according to 25, wherein the heating wire is composed of a plurality of heating wires. 28.
- An assist suit including the actuator module according to 32 as a drive unit.
- a molded product a textile product and an actuator having excellent reversible thermal elasticity.
- an assist suit having high repeatability and safe use, and an actuator module as a part thereof.
- the first aspect of the molded product of the embodiment of the present invention is a gel fraction of 10% or more, a crystal orientation degree of 80% or more, and a crystallinity of 60% or less.
- the molded product of the embodiment of the present invention preferably has a gel fraction of 10% or more.
- the gel fraction indicates the degree of cross-linking, and the higher the value, the higher the degree of cross-linking.
- the gel fraction can be measured by the method for measuring the gel fraction described later.
- the effect of heat shrinkage is more likely to be obtained as the degree of cross-linking increases. Therefore, when the gel fraction is 10% or more, the heat shrinkage rate per unit temperature due to heating can be sufficiently increased. ..
- the gel fraction is more preferably 30% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more.
- the gel fraction can be increased by increasing the degree of cross-linking of the polymer and increasing the molecular weight.
- the upper limit of the gel fraction is not particularly limited, but can be set to 100% or less, or can be set to 95% or less or 90% or less.
- the molded product of the embodiment of the present invention preferably has a crystal orientation degree of 80% or more, more preferably 84% or more, still more preferably 90% or more.
- the upper limit of the degree of crystal orientation is not particularly limited, but can be set to 100% or less, or 98% or less or 95% or less.
- the molded product of the second embodiment described later has a coil shape, and the degree of crystal orientation thereof is preferably 60% or more.
- the degree of crystal orientation of the molded product according to the embodiment of the present invention can be increased by performing a stretching operation.
- the stretching operation can be performed in one stage or in multiple stages of two or more stages.
- the draw ratio can be sufficiently increased if the draw ratio is 2 times or more, preferably 3 times or more.
- the stretching ratio of the first stage is set to 2 times or more, preferably 3 times or more, and the stretching ratio of the second stage is smaller than that of the first stage.
- it can be set in the range of 1.05 times or more and less than 2.0 times, or 1.05 to 1.5 times.
- the upper limit of the draw ratio is not particularly limited, but 20 times or less is preferable, 10 times or less is more preferable, and 6 times or less is further preferable, from the viewpoint of preventing the occurrence of defects due to excessive stretching.
- the molded product of the embodiment of the present invention preferably has a crystallinity of 60% or less.
- the lower the crystallinity the more amorphous that can contribute to heat shrinkage during heating, and a better heat shrinkage effect can be exhibited. Therefore, the crystallinity is preferably 60% or less, more preferably 50% or less, and more preferably 40% or less. Is even more preferable.
- the lower limit of the crystallinity is not particularly limited, but can be set to 0% or more, or can be set to 5% or more or 10% or more.
- the second aspect of the molded product of the embodiment of the present invention has a gel fraction of 10% or more, a crystal orientation degree of 60% or more, and a coil shape.
- the molded body of the embodiment of the present invention can be formed into a coil shape.
- the coil-shaped molded body can significantly amplify the heat shrinkage of the formed molded body.
- FIG. 2 shows an example of a coil-shaped molded body.
- d indicates the single fiber diameter of the fibers constituting the coil
- D indicates the coil average diameter (coil average diameter: the average of the coil outer diameter and the coil inner diameter).
- the method for producing the coil-shaped molded body is not particularly limited, but for example, a stable coil is formed by continuously twisting one to a plurality of fibers under a constant load to form a coil shape and then annealing. The shape can be obtained. Further, by inserting the core rod immediately before coiling and coiling, the coil average diameter D can be increased as shown in FIG. 3 according to the diameter of the core rod, and the obtained coil shape can be increased.
- the molded body can obtain a good contraction displacement.
- the coil-shaped molded body may be composed of a plurality of fibrous molded bodies or coil-shaped molded bodies.
- the shape of the coil formed from a plurality of fibrous molded bodies is not particularly limited, but the coil shape is covered by winding the fibrous molded body or the coil-shaped molded body around the core fibrous molded body or the coil-shaped molded body.
- a stable contraction displacement can be obtained by forming the coil shape (for example, the form shown in FIG. 4) or the coil shape twisted together (for example, the form shown in FIG. 5).
- FIG. 4 shows an example of a coil-shaped molded body in which the fibrous molded body of the present invention is wound and covered around a coil-shaped molded body of the present invention as a core.
- FIG. 5 shows an example of a coil-shaped molded body obtained by twisting and twisting the coil-shaped molded body of the present invention.
- the degree of crystal orientation of the coil-shaped molded product according to the embodiment of the present invention is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more.
- the upper limit of the degree of crystal orientation is not particularly limited, but can be set to 100% or less, or 98% or less or 95% or less.
- the coil-shaped molded body of the embodiment of the present invention has a crystal orientation degree of 60% or more because the crystal orientation degree tends to decrease when the coil shape is formed.
- the degree of crystal orientation of the molded product can be increased by performing a stretching operation of the molded product before forming the coil shape.
- the stretching operation can be performed in one stage or in multiple stages of two or more stages. From the viewpoint of increasing the degree of crystal orientation, the draw ratio can be sufficiently increased if the draw ratio is 2 times or more, preferably 3 times or more.
- the stretching ratio of the first stage is set to 2 times or more, preferably 3 times or more, and the stretching ratio of the second stage is smaller than that of the first stage.
- the draw ratio is not particularly limited, but 20 times or less is preferable, 10 times or less is more preferable, and 6 times or less is further preferable, from the viewpoint of preventing the occurrence of defects due to excessive stretching.
- the molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
- the molded product according to the embodiment of the present invention can be sufficiently displaced as an actuator as long as the heat shrinkage rate per unit temperature when heated under an arbitrary load is 0.07% / ° C. or higher.
- the heat shrinkage rate per unit temperature is more preferably 0.08% / ° C. or higher, further preferably 0.10% / ° C. or higher.
- the higher the heat shrinkage rate per unit temperature, the higher the industrial applicability as an actuator, and the upper limit is not particularly limited, but if it is 0.20% / ° C, the performance as an actuator is very high, 0.18. % / ° C is sufficiently effective. Therefore, the heat shrinkage rate per unit temperature can be set in the range of 0.07% / ° C.
- the shrinkage rate in this case is the shrinkage rate when a load is applied so that the tensile stress becomes 5 MPa.
- the actuator in the present invention is sometimes called a soft actuator, and the material itself has elasticity.
- the molded product according to the embodiment of the present invention preferably has a shrinkage rate of 3.5% or more when a temperature change of 50 ° C. is applied by heating.
- the molded product according to the embodiment of the present invention preferably has a shrinkage rate of 3.5% or more when a temperature change of 50 ° C. is applied in a temperature range of ⁇ 30 ° C. to 200 ° C. If the shrinkage rate is 3.5% or more when a temperature change of 50 ° C is applied in the temperature range of -30 ° C to 200 ° C, it is possible to take a high displacement as an actuator with a feasible change, so this is an application. It is effective as an excellent actuator with a wide range of applications. From the above viewpoint, the shrinkage rate is preferably 4.0% or more, more preferably 5.0% / ° C. or higher. The upper limit of this shrinkage rate is not particularly limited, but if it is 10.0%, it is sufficiently effective as an actuator. Therefore, this shrinkage rate can be set in the range of 3.5 to 10.0%.
- the molded body of the embodiment of the present invention preferably has a crosslinked structure inside the molded body.
- the crosslinked structure means a structure in which the polymers constituting the molded product are crosslinked. By having a crosslinked structure, it is easy to obtain a high heat shrinkage rate per unit temperature due to the entropy elasticity.
- cross-linking is not particularly limited, but is cross-linked by the reaction of phenol with a base catalyst and excess formamide, the reaction with amine, carboxylic acid anhydride, dicyandiamide, ketimine or acid catalyst using the ring-opening reaction of the epoxy group.
- Cross-linking by the reaction in cross-linking by the reaction of condensing urea, melamine, benzoguanamine and formaldehyde in the presence of a weak alkaline catalyst, reaction of a compound having two or more isosianate groups with a bifunctional or higher hydroxyl group or amine compound.
- Cross-linking by urethane bond or urea bond cross-linking by condensation reaction of silanol, cross-linking by reaction under peroxide of compound having double bond in side chain or main chain, alkoxide or chelate compound of Al, Ti, Zr Examples thereof include cross-linking by a coordination bond used as a cross-linking agent and cross-linking by a reaction using a photoradical polymerization initiator.
- a silane crosslink formed by a bond (silane bond) by a condensation reaction between silanol groups is preferable.
- the graft ratio (modification amount) of alkoxysilane (unsaturated silane compound) in the silane-modified polyolefin by increasing the graft ratio (modification amount) of alkoxysilane (unsaturated silane compound) in the silane-modified polyolefin, the type and blending amount of the silanol condensation catalyst, the conditions (temperature, time) for crosslinking, etc. are changed.
- the gel fraction of the silane crosslinked polyolefin molded product can be adjusted.
- the unstretched product is stretch-oriented to obtain a crystal-oriented stretched molded product, and then the cross-linking treatment is performed, so that the mechanical properties and crystal orientation of the molded product are not impaired.
- the crosslinked structure can be formed while maintaining the above.
- the molded product of the embodiment of the present invention preferably has a silane crosslink as the crosslinked structure. Since the molded product of the embodiment of the present invention has a silane crosslink, it is easy to obtain a high heat shrinkage rate per unit temperature.
- Silane cross-linking can be formed by exposing a pre-silane-modified polymer to a water-containing atmosphere and allowing the reaction between silanol groups (so-called silane bond) to proceed. More specifically, in a silane-modified polymer, a hydrolyzable alkoxy group derived from a graft-introduced alkoxysilane (for example, an unsaturated silane compound) reacts with water to hydrolyze in the presence of a silanol condensation catalyst.
- silanol groups are generated, and the silanol groups are dehydrated and condensed, so that the cross-linking reaction proceeds between the silane-modified polymers, and as a result, the silane-modified polymers are bonded to each other to form a silane bridge.
- the silane-modified polymer can be produced by graft-introducing alkoxysilane into a polymer such as polyolefin and silane-modifying.
- the method of silane modification can be carried out according to a known method and is not particularly limited. For example, solution denaturation, melt denaturation, solid phase denaturation by irradiation with electron beam or ionizing radiation, denaturation in a supercritical fluid, and the like are preferably used. Among these, melt modification with excellent equipment and cost competitiveness is preferable, and melt kneading modification using an extruder with excellent continuous productivity is more preferable.
- Examples of the apparatus used for melt-kneading modification include a single-screw screw extruder, a twin-screw screw extruder, a Banbury mixer, a roll mixer, and the like. Among these, a single-screw extruder and a twin-screw screw extruder having excellent continuous productivity are preferable.
- the conditions for forming the silane bridge are determined by the conditions of exposure to the water-containing atmosphere, and are not particularly limited, but are usually preferably in a temperature range of 20 to 130 ° C. and a time range of 1 minute to 1 week, more preferably 20 to 130 ° C. It is in a temperature range and a time range of 1 hour to 160 hours. When air containing moisture is used, the relative humidity may be appropriately adjusted within the range of 1 to 100%.
- the silane-modified polymer is a composition containing a polymer before modification (pre-modification composition) and an olefinically unsaturated silane compound having a hydrolyzable organic group (hereinafter, also simply referred to as “unsaturated silane compound”). Can be obtained by copolymerizing in the presence of a radical generator. In this reaction, the unsaturated silane compound is grafted onto each polymer in the pre-modification composition (graft modification).
- a silane compound represented by the following general formula (1) is preferably used as the olefinically unsaturated silane compound having a hydrolyzable organic group.
- RSiR'n Y 3-n 1 (In the general formula (1), R represents a monovalent olefinically unsaturated hydrocarbon group, R'represents a monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group, and Y can be hydrolyzed. Indicates an organic group, where n indicates 0, 1 or 2).
- examples of the monovalent olefinically unsaturated hydrocarbon group represented by R include a vinyl group, an allyl group, an isopropenyl group, a butenyl group and the like.
- examples of the monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group represented by R'in include an alkyl group such as a methyl group, an ethyl group, a propyl group and a decyl group; and an aryl group such as a phenyl group.
- Examples of the hydrolyzable organic group represented by Y include an alkoxy group such as a methoxy group and an ethoxy group; an acyloxy group such as a formyloxy group, an acetoxy group and a propionoxy group; an alkylamino group or an arylamino group.
- a compound represented by the following general formula (2) can be mentioned.
- CH 2 CHSi (OA) 3 (2)
- A represents a monovalent hydrocarbon group having 1 to 8 carbon atoms.
- examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms represented by A include an alkyl group such as a methyl group, an ethyl group and an isopropyl group.
- Specific examples of the unsaturated silane compound represented by the general formula (2) include vinyltrimethoxysilane and vinyltriethoxysilane.
- a compound represented by the following general formula (3) can also be preferably used.
- CH 2 C (CH 3 ) COOC 3 H 6 Si (OA) 3 (3)
- A is synonymous with A in the general formula (2).
- Examples of the unsaturated silane compound represented by the above general formula (3) include ⁇ -methacryloyloxypropyltrimethoxysilane and ⁇ -methacryloyloxypropyltriethoxysilane.
- unsaturated silane compound vinyltrimethoxysilane, vinyltriethoxysilane, and ⁇ -methacryloyloxypropyltriethoxysilane are preferable.
- unsaturated silane compounds may be used alone, or two or more thereof may be used in combination in any combination.
- the lower limit of the amount of the unsaturated silane compound added for graft modification is not particularly limited from the viewpoint of forming a crosslinked structure, but is preferably 0.01% by mass or more based on the total mass of the pre-modification composition. .. From the above viewpoint, the amount of the unsaturated silane compound added is more preferably 0.1% by mass or more, further preferably 0.7% by mass or more.
- the upper limit of the amount of the unsaturated silane compound added is not particularly limited, but from the viewpoint of economy, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass, based on the total mass of the pre-modification composition. % Or less is more preferable.
- Radical generators used for graft modification include various organic peroxides and peresters having a strong polymerization initiation action, such as dicumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxydiisopropyl) benzene, and di-. t-butyl peroxide, t-butyl cumyl peroxide, di-benzoyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxypivalate, t-butyl Examples thereof include peroxy-2-ethylhexanoate. Of these, dicumyl peroxide, benzoyl peroxide, and di-t-butyl peroxide are preferable. One of these radical generators may be used alone, or two or more of them may be used in combination in any combination.
- the amount of the radical generator added is adjusted so that the MFR (190 ° C., load 2.16 kg) of the obtained silane-modified polymer composition is finally in the range of 0.05 g / 10 minutes or more and 50 g / 10 minutes or less.
- the amount of the radical generator added is usually 0.005% by mass or more, preferably 0.01% by mass or more, more preferably 0, based on the total mass of the obtained silane-modified polymer composition. It is 0.02% by mass or more, usually 0.5% by mass or less, preferably 0.4% by mass or less, and more preferably 0.2% by mass or less. If the amount of the radical generator used is too small, sufficient grafting tends to be difficult. Further, if the amount of the radical generator used is too large, the MFR of the obtained silane-modified polymer composition is lowered, the extrusion processability is lowered, and the molded surface tends to be deteriorated.
- the silane-modified polymer can be produced according to a known method and is not particularly limited.
- solution denaturation, melt denaturation, solid phase denaturation by irradiation with electron beam or ionizing radiation, denaturation in a supercritical fluid, and the like are preferably used.
- melt modification with excellent equipment and cost competitiveness is preferable, and melt kneading modification using an extruder with excellent continuous productivity is more preferable.
- the apparatus used for melt-kneading modification include a single-screw screw extruder, a twin-screw screw extruder, a Banbury mixer, a roll mixer, and the like.
- a single-screw screw extruder and a twin-screw screw extruder having excellent continuous productivity are preferable.
- a silanol condensation catalyst is preferably used as the cross-linking catalyst used for the cross-linking reaction of the silane-modified polymer.
- the silanol condensation catalyst will be described in detail.
- silanol condensation catalyst examples include tin catalysts such as dibutyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctate, and dioctyltin dilaurate; lead catalysts such as lead naphthenate and lead stearate; zinc caprylate, Zinc catalysts such as zinc stearate; cobalt catalysts such as cobalt naphthenate, titanium catalysts such as tetrabutyl ester titanate; cadmium catalysts such as cadmium stearate; organic earth metal catalysts such as barium stearate and calcium stearate Examples include metal catalysts. Among these, a tin catalyst is preferable. One of these silanol condensation catalysts may be used alone, or two or more of them may be used in combination in any combination.
- the amount of the silanol condensation catalyst added is usually 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.05, based on the total mass of the silane-modified polymer composition to which the silanol condensation catalyst is added. It is 5% by mass or less, usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. If the addition amount of the silanol condensation catalyst is too small, the sufficient cross-linking reaction does not proceed, and if the addition amount is too large, it is disadvantageous in terms of cost.
- the master batch of the silanol condensation catalyst can be produced, for example, by adding the silanol condensation catalyst to one or more of the silane-modified polymer compositions and kneading them.
- the content of the silanol condensation catalyst in the master batch is not particularly limited, but is usually 0.1 to 5.0% by mass. Is preferable.
- additives such as stabilizers, lubricants, fillers, colorants, foaming agents and other auxiliary materials to the silanol condensation catalyst-containing masterbatch, if necessary. Can be done. These additives may be those that are known and commonly used in their own right. It is also possible to add these additives to the silane-modified polymer composition as the third component together with the silanol condensation catalyst.
- a composition obtained by blending a silanol condensation catalyst with a silane-modified polymer is usually molded by various molding methods such as extrusion molding, injection molding, and press molding, and then exposed to an aqueous atmosphere or warm water.
- the cross-linking reaction between silanol groups is allowed to proceed by immersing in.
- Various conditions can be adopted as the method of exposing to the water atmosphere, the method of leaving in the air containing water, the method of blowing air containing water vapor, the method of immersing in a water bath, and the method of atomizing hot water. Examples include a method of sprinkling water.
- a hydrolyzable alkoxy group derived from an unsaturated silane compound used for graft modification of a polymer for silane modification reacts with water in the presence of a silanol condensation catalyst to hydrolyze the silanol group. Is generated. Then, the reaction proceeds by dehydration condensation of the produced silanol groups, and the silane-modified polymers are bonded to each other to obtain a silane crosslinked product.
- the rate of progress of the crosslinking reaction is determined by the conditions under which the silane-modified polymer composition is exposed to the water atmosphere.
- the silane-modified polymer composition may be exposed to the water atmosphere under the conditions of a temperature range of 20 to 130 ° C. and a temperature range of 10 minutes to 1 week.
- Particularly preferred conditions are a temperature range of 20 to 130 ° C. and a range of 1 hour to 160 hours.
- the relative humidity is selected from the range of 1-100%.
- Arbitrary cross-linking structure can be formed by changing the graft ratio (modification amount) of the unsaturated silane compound of the silane-modified polymer, the type and blending amount of the silanol condensation catalyst, and the conditions (temperature, time) for cross-linking. Can be done.
- the molded product according to the embodiment of the present invention preferably has reversible thermal elasticity and a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
- the molded product of the embodiment of the present invention preferably has reversible thermal elasticity in an arbitrary temperature and load region, and has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
- Reversible thermal elasticity means that shrinkage due to heating and expansion due to cooling are repeated with approximately constant displacement, but the scope of the present invention is particularly the temperature range for heating and the characteristic change due to deterioration phenomenon due to repeated operation. Is not restricted in.
- expansion and contraction with a restoration rate of 90% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more.
- a more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 95% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more.
- a more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 97% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and further preferably 1000 times or more.
- the restoration rate in the reversible thermal elasticity is preferably maintained at 90% or more, more preferably 95% or more, still more preferably 97% or more in order to function as an actuator with respect to the initial measurement length.
- the number of times to maintain the restoration rate is preferably 10 times or more, more preferably 100 times or more, still more preferably 1000 times or more.
- the portion of the molded product having reversible thermal expansion and contraction is preferably 50% or more, more preferably 80% or more, and most preferably 100% in the direction of thermal expansion and contraction of the molded product.
- the molded body by making the molded body into a coil shape, it is possible to increase the elasticity due to heat, but by making the molded body into a molded body with a high thermal expansion / contraction rate, it is lightweight and space-saving. Can be achieved.
- the molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature in a temperature range of ⁇ 30 ° C. to 200 ° C. If the shrinkage rate per unit temperature is 0.07% / ° C. or higher in the temperature range of -30 ° C to 200 ° C, the application is highly applicable as an actuator, and it can be said that the actuator is excellent.
- the lower limit of the operating temperature range in which the shrinkage rate is 0.07% / ° C or higher is not particularly limited as it can be operated even in a low temperature environment and can be used as an actuator, but it may be 20 ° C or higher. For example, it is preferable as an actuator that can be realized near room temperature.
- the lower limit of the operating temperature region is 0 ° C. or higher, it is preferable as an actuator that can be realized even in a cold region, and when it is ⁇ 30 ° C. or higher, it is preferable as an actuator that is practical even in an extremely cold region.
- the upper limit of the operating temperature range is not particularly limited, but if it is 90 ° C. or lower, it is preferable as an actuator that can be relatively easily heated and can be realized in a general environment, and if it is 150 ° C. or lower, it is preferable as an actuator that can be realized in a high temperature atmosphere. , 200 ° C. or lower is preferable as an actuator that can be realized in a high temperature atmosphere such as near an engine.
- the operable temperature range can be arbitrarily adjusted by the glass transition temperature of the polymer, and the present invention is not limited by the usage environment, and the material can be designed according to the desired usage environment.
- the molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating under a tensile load of 1 to 20 MPa.
- shrinkage rate per unit temperature due to heating is 0.07% / ° C or higher under a tensile load of 1 MPa or more in the thermal expansion / contraction direction of the molded body, shrinkage stress is applied even with a small number of molded bodies or a thinner molded body. It can be expressed and is effective as an actuator. From the above viewpoint, the tensile load state when the shrinkage rate per unit temperature due to heating satisfies 0.07% / ° C.
- the tensile load state is not particularly limited, but if the shrinkage rate per unit temperature when heated under the tensile load state of 10 MPa satisfies 0.07% / ° C. or higher, the application can be used as an actuator. It is highly applicable and can be said to be an excellent actuator. Therefore, the tensile load state when the shrinkage rate satisfies 0.07% / ° C. or higher can be set in the range of 1 to 20 MPa or 1 to 10 MPa.
- the molded product according to the embodiment of the present invention preferably has a restoration rate of 90% or more when the temperature is lowered by 50 ° C. after shrinking by heating at a temperature change of 50 ° C.
- a restoration rate of 90% or more when the temperature is lowered by 50 ° C. after shrinking by heating at a temperature change of 50 ° C.
- the restoration rate of the length in the heat shrinkage direction of the molded product of the present invention when the temperature is lowered to the temperature before shrinkage after being heated and shrunk is 90% or more, it can be sufficiently used as an actuator.
- the restoration rate is more preferably 95% or more, further preferably 97% or more.
- the number of times to maintain the restoration rate is preferably 2 times or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more.
- the molded product of the embodiment of the present invention is preferably made of an olefin polymer. Since it is easy to increase the number of entanglements and the number of crosslinks of the olefin polymer such as polyolefin which is a flexible polymer, it is possible to obtain a molded product having a high heat shrinkage rate per unit temperature.
- the olefin-based polymer includes polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer, as well as ethylene-based polymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-ethyl acrylate copolymer.
- olefin polymers such as polymers, fluoropolymers such as polyvinylidene fluoride, and chlorine-based polymers such as polyvinylidene chloride.
- Polymers and additives other than olefin-based polymers can be contained as long as the required reversible thermal stretchability can be obtained.
- the molded product of the embodiment of the present invention is preferably made of polyethylene. Since the molded product of the embodiment of the present invention is made of polyethylene, the polyethylene material is relatively inexpensive, has excellent spinnability, and is easy to introduce crosslinks, so that a molded product having a high heat shrinkage rate can be obtained at low cost. be able to.
- the MFR (190 ° C., load 2.16 kg) of the silane crosslinkable polyethylene composition (composition containing silane-modified polyethylene as a silane-modified polymer) in the embodiment of the present invention is usually 0.5 to 50 g from the viewpoint of spinnability. It is / 10 minutes, preferably 0.5 to 40 g / 10 minutes, and more preferably 0.5 to 30 g / 10 minutes.
- the molded product of the embodiment of the present invention is preferably in the form of fibers, plates, sheets or films, or preferably has one or more multilayer structures selected from these.
- the shape of the molded body may be any shape as long as it is thermally expanded and contracted in one direction. If it is fibrous, it can be easily formed into a coil shape, the shrinkage stress can be increased, and the flexibility can be imparted. If it is plate-shaped, it is easy to take a large cross-sectional area that expands and contracts with heat, it can be used in places where stress is applied such as compressive load, and it can be obtained with high shrinkage stress. Further, in the case of a plate shape, a coil shape may be used as an elongated shape.
- a multilayer body If it is in the form of a sheet or film, it can be laminated to form a multilayer body, or the shape can be rounded to form a cylindrical structure, so that it is easy to take a large cross-sectional area that expands and contracts with heat, and it becomes easy to increase the shrinkage force. .. Further, depending on the intended use as an actuator, a plurality of molded bodies having the same shape may be used to form a multi-layer structure, or molded bodies having different shapes may be combined to form a multi-layer structure.
- the fibrous molded product of the present invention various conventionally known methods such as melt spinning, wet spinning, dry spinning, and dry / wet can be adopted.
- the stage of forming the crosslinked structure is not particularly limited, but by drawing-oriented the undrawn yarn and performing the cross-linking treatment after obtaining the crystal-oriented drawn fiber, the mechanical properties of the fiber can be obtained without impairing the productivity of the spinning yarn. It is preferable because a crosslinked structure can be formed while maintaining the crystal orientation.
- the single fiber fineness of the fibrous molded product is 50 to 10000 dtex.
- the single fiber fineness (dtex) means the weight (g) per 10,000 m of one fiber.
- the lower limit of the single fiber fineness is not particularly limited because it depends on the strength and elastic modulus of the material, but the single fiber fineness is preferably 50 dtex or more from the viewpoint of the strength of post-processing and the increase of the spring index when coiled. 100 dtex or more is more preferable, and 200 dtex or more is further preferable.
- the upper limit of the single fiber fineness is not particularly limited because it depends on the flexibility of the material, but the single fiber fineness is preferably 10,000 dtex or less, more preferably 5000 dtex or less, and 1000 dtex or less from the viewpoint of flexibility and ease of post-processing. More preferred.
- the diameter of the single fiber of the fibrous molded product is 80 to 1200 ⁇ m.
- the lower limit of the diameter of the single fiber is not particularly limited because it depends on the strength of the material, the elastic modulus, etc. From the viewpoint of increasing the index, the diameter of the single fiber is preferably 80 ⁇ m or more, more preferably 120 ⁇ m or more, still more preferably 170 ⁇ m or more.
- the upper limit of the diameter of the single fiber is not particularly limited because it depends on the flexibility of the material, but if the diameter of the single fiber is small, it is flexible and easy to post-process, so the diameter of the single fiber is preferably 1200 ⁇ m or less. , 840 ⁇ m or less is more preferable, and 380 ⁇ m or less is further preferable.
- the molded body of the embodiment of the present invention is preferably formed in a coil shape.
- the coiled fibrous molded product of the embodiment of the present invention can be manufactured, for example, as follows. First, the silane-modified polymer composition is melt-spun and stretched 2 to 20 times. Further, the cross-linking treatment is preferably carried out by allowing it to stand for 12 hours or more, and the obtained fiber of the silane cross-linked polyethylene or the silane cross-linked polyethylene composition is twisted and coiled while applying a tension of 3 to 20 MPa. , Coiled fibers can be produced.
- the coil shape becomes good, and by setting the tension to 20 MPa or less, preferably 8 MPa or less, it is possible to reduce the breakage of the coil during heat shrinkage. .. From these viewpoints, the tension at the time of coiling is more preferably 3.5 to 7 MPa, further preferably 4 to 6 MPa.
- the cross-linking treatment is preferably carried out by allowing it to stand for 12 hours or more, so that the cross-linking is sufficiently performed and the reversible elasticity is improved.
- the time for performing the crosslinking treatment is more preferably 16 hours or more, further preferably 20 hours or more. Further, if it is 36 hours, it is considered that the crosslinking is sufficiently performed and the crosslinking is unlikely to proceed any further. Therefore, the upper limit of the time for performing the crosslinking treatment can be set to 36 hours or less.
- the molded product of the embodiment of the present invention satisfies all of the following conditions (1) to (3).
- (1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2 ⁇ 10 ° to 30 °.
- the degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material.
- the molded body of the embodiment of the present invention preferably has a spring index D / d of 0.5 or more and an average diameter D of the coil shape of 100 to 2000 ⁇ m.
- the molded product according to the embodiment of the present invention is preferably fibrous and has a spring index D / d of 0.5 or more.
- D represents the coil average diameter (coil average diameter) ( ⁇ m)
- d represents the diameter ( ⁇ m) of the single fiber constituting the coil.
- 2 and 3 show the positions of the coil average diameter D and the single fiber diameter d. Note that D'in FIG. 3 indicates the outer diameter of the coil.
- the spring index is 0.5 or more, the heat shrinkage rate per unit length of the coil can be increased.
- the spring index is more preferably 0.6 or more, and further preferably 0.7 or more.
- the spring index is preferably 10.0 or less, more preferably 6.0 or less. 0 or less is more preferable, and 1.5 or less is most preferable.
- the average diameter D of the coil shape is 100 ⁇ m or more, it is rigid and easy to handle when incorporated into an apparatus as an actuator, which is preferable. Further, when it is 2000 ⁇ m or less, the flexibility is high, which is preferable. From these viewpoints, the average diameter D of the coil shape is more preferably 120 to 1500 ⁇ m, further preferably 140 to 1000 ⁇ m, and most preferably 160 to 500 ⁇ m.
- the molded body of the embodiment of the present invention is selected from linear low-density polyethylene having a density of 0.881 to 0.941 g / cm 3 and high-density polyethylene having a density of 0.942 to 0.970 g / cm 3 . It is preferable to contain a mixture containing 20 to 80% by mass of one or more polyethylenes to be made and 20 to 80% by mass of linear low density polyethylene having a density of 0.860 to 0.880 g / cm 3 . .. In order to obtain such a molded product, it is preferable that the pre-modification composition at the time of production contains the above mixture as the polymer before modification.
- linear low density polyethylene having a density of 0.881 to 0.941 g / cm 3 and high density polyethylene having a density of 0.942 to 0.970 g / cm 3 The content of polyethylene in the above mixture is preferably 20% by mass or more, preferably 30% by mass or more, and even more preferably 50% by mass or more. Further, when the content is 80% by mass or less, the melt tension at the time of melt spinning is stable, and the productivity of the molded product can be increased. From this viewpoint, the content is more preferably 70% by mass or less in the mixture. Density can be measured by ASTM D792.
- the linear low-density polyethylene is preferably polymerized using a metallocene catalyst.
- a metallocene catalyst By using a metallocene catalyst, it is easy to obtain a linear polymer, and as a result, the stretchability at the time of stretching is improved, and the heat shrinkage rate is easily increased.
- the density of the mixture is preferably 0.860 to 0.940 g / cm 3 .
- the density is 0.940 g / cm 3 or less, amorphous materials that can contribute to heat shrinkage during heating are sufficient, and a good heat shrinkage effect can be exhibited.
- the density is more preferably 0.930 g / cm 3 or less, and further preferably 0.920 g / cm 3 or less. Density can be measured by ASTM D792.
- the molded product according to the embodiment of the present invention preferably has a twist number of 1 to 30 times / mm.
- the number of twists is the number of times the molded product is twisted per 1 mm in the axial direction of the coil. As the number of twists increases, the heat shrinkage rate per unit length of the coil can be increased, so that the upper limit of the number of twists is not particularly limited.
- the number of twists is preferably 30 times / mm or less, more preferably 20 times / mm or less, further preferably 15 times / mm or less, and 10 times / mm or less. Most preferred.
- the number of twists is preferably 1 time / mm or more, more preferably 3 times / mm or more, further preferably 5 times / mm or more, and most preferably 7 times / mm or more.
- the molded product according to the embodiment of the present invention is a molded product having reversible thermal elasticity and partially has a portion that does not have reversible thermal elasticity.
- the molded product of the embodiment of the present invention can partially have the molded product of the above-described embodiment, that is, can partially have a portion that does not shrink heat.
- the main fiber portion a including the central portion of the fibrous molded body (the fibrous portion of the embodiment) and the end portions b including the fiber ends on both sides thereof may be provided.
- can. a is a portion having a high heat shrinkage rate per unit temperature due to heating, for example, 0.07% / ° C.
- La is the length of the main fiber portion a
- b is a heat shrinkage rate per unit temperature.
- Lb indicates the length of the end portion b.
- the fixed portion has low thermal elasticity or does not thermally expand or contract.
- the total length along the fiber axis direction (fiber length direction) (in FIG. 1, the sum of the length La of the main fiber portion a, the length Lb of one end b, and the length Lb of the other end b).
- the ratio of the length of the portion having high heat shrinkage (La in FIG. 1) is preferably 50% or more, more preferably 80% or more in order to obtain good heat shrinkage, and fixing of both ends is performed. It is preferably 98% or less from the point of fixing without loosening.
- thermo shrinkage heat shrinkage
- not thermally expanding or contracting for example, a state in which a cross-linking reaction is unlikely to occur or does not occur at both ends of the fiber during cross-linking (in the case of silane cross-linking, for example).
- the textile product of the embodiment of the present invention is a textile product containing the molded product of the embodiment, and the textile product of the embodiment of the present invention is preferably a woven fabric, a knitted fabric, a non-woven fabric, or a string.
- the textile product is a woven fabric, one of the warp and weft contains the molded body, and the other contains a heating wire that does not contain the molded body and is covered with an insulating film. Is preferable.
- the woven fabric of the embodiment of the present invention contains a heating wire in which one of the warp and weft is a fiber A having reversible thermal elasticity and the other has no reversible thermal elasticity and is covered with an insulating film. ..
- having a reversible thermal elasticity means having a property of repeating shrinkage due to heating and expansion due to cooling with a substantially constant displacement.
- the technical scope of the present invention is not limited by the heating temperature range or the characteristic change due to the deterioration phenomenon due to the repeated operation.
- a plurality of fibers A having reversible thermal elasticity are arranged side by side to form a woven fabric.
- the force of expansion and contraction can be increased.
- the heating wires covered with the insulating film in multiple directions, heat can be efficiently transferred to the fibers A, and since it is not necessary to arrange extra fibers, weight reduction can be realized.
- a preferred embodiment having reversible thermal elasticity is preferably to be able to expand and contract with a restoration rate of 90% or more once or more, more preferably 5 times or more, and even more preferably 10 times or more.
- a more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 97% or more is preferably possible once or more, more preferably 5 times or more, further preferably 10 times or more, and particularly preferably 100 times or more. ..
- the fiber A having reversible thermal elasticity is not particularly limited, and for example, nylon fiber, polyester fiber, aramid fiber, polyvinyl chloride fiber, Teflon (registered trademark) fiber, vinylon fiber, polyurethane fiber, and the like.
- nylon fiber, polyester fiber, aramid fiber, polyvinyl chloride fiber, Teflon (registered trademark) fiber, vinylon fiber, polyurethane fiber, and the like examples thereof include polylactic acid fiber, acrylic fiber, polyolefin fiber, and silane crosslinked polyethylene fiber.
- nylon fiber and silane cross-linked polyethylene fiber are preferable from the viewpoint of reversible thermal elasticity.
- the heating wire means a heating element wire coated with an insulating film.
- the material and dimensions of the heating element are not particularly limited, but nickel-chromium alloy is preferable from the viewpoint of resistance value and cost.
- the heating element may be wound around the winding core and used.
- polyarylate fiber or aramid fiber is suitable as the winding core from the viewpoint of heat resistance, insulation, and scratch resistance.
- the heating wire is covered with an insulating film, there is no risk of accidental short circuit during energization heating, and there is no risk of electric shock even if a person comes into contact with it. Further, when the woven fabric is used as an actuator, water or the like may be used for cooling, but there is no risk of electric shock or electric leakage.
- the material of the insulating coating is not particularly limited as long as it has good insulating properties, but vinyl chloride is preferable as the most versatile and inexpensive material.
- the insulating coating has heat resistance and abrasion resistance capable of withstanding the expansion and contraction movement of the actuator, and as an example, polytetrafluoroethylene or tetrafluoroethylene and a copolymer of perfluoroalkoxyethylene Examples thereof include a coalescence, an ethylene-tetrafluoroethylene copolymer, a fluororesin such as polyvinylidenefluoride, formal, polyurethane, polyester, polyamideimide, enamel, crosslinked polyethylene, vinyl chloride resin, and silicone resin.
- a fluororesin such as polyvinylidenefluoride, formal, polyurethane, polyester, polyamideimide, enamel, crosslinked polyethylene, vinyl chloride resin, and silicone resin.
- the warp or weft including the heating wire may include other yarns having no reversible thermal elasticity other than the heating wire.
- yarns that do not have reversible thermal elasticity either chemical fibers or natural fibers can be used, but from the viewpoint of preventing breakage of the heating wire, high-strength yarns are preferable, and yarns containing polyester fibers are preferable. preferable. Further, wool and cotton are preferable from the viewpoint of heat resistance and the like.
- the woven fabric of the embodiment of the present invention it is preferable that the woven fabric has a plain weave, a twill weave, a kalami weave, a satin weave, or a combination of these weaves.
- Plain weave is preferable when flatness, symmetry, and abrasion resistance of the woven fabric are important, and twill weave or satin weave is preferable from the viewpoint of bending flexibility and designability of coil-shaped fibers. From the viewpoint of satisfactorily exhibiting the expansion and contraction of the fiber or the coil-shaped fiber, the Karami weave is preferable.
- the heating wire is a continuous heating wire.
- FIG. 7 is a schematic view showing an example of a woven fabric in which the fiber A (1) is used as a warp and a continuous heating wire 2 is used as a weft. As shown in FIG. 7, by folding and using one continuous heating wire 2 in a loop, a woven fabric can be manufactured more easily without cutting a long heating wire. As an extreme example, one heating wire can be used for all of one woven fabric. That is, it can be considered that the heating wires are made into a series circuit in one woven fabric.
- the circuit of energization becomes simple and the weight of the woven fabric can be easily reduced. Further, by using the heating wire as a warp and weft, it becomes easy to arrange one in series.
- the heating wire may be composed of a plurality of heating wires.
- FIG. 8 is a schematic view showing an example of a woven fabric in which the fiber A (1) is used as a warp and a plurality of heating wires 2 are used as a weft.
- a woven fabric consisting of multiple heating wires is used as an actuator, for example, even if a trouble such as breakage of the heating wire occurs due to repeated friction, the heating wire of one warp or weft breaks. It is only possible to prevent the fabric from failing.
- the diameter of the heating wire is preferably 20 to 2000 ⁇ m.
- the fiber A has a coil shape.
- the coil shape means the coil shape formed when the fiber material is continuously twisted.
- the coil shape there is an over-twist type in which the coil is naturally formed by simply continuing twisting without using a core rod, etc., and when the coil shape begins to be formed, it becomes a core rod at this point.
- a mandrel type in which a coil is formed by inserting something or winding a fiber material around a core rod from the beginning. In either case, the material shrinks when heated and expands when cooled, and in the embodiment of the present invention, both can be used properly according to the desired generated stress and heat shrinkage rate.
- the coil-shaped fiber A can be produced by appropriately adjusting the size of the load, the number and speed of twisting, the temperature conditions, etc. so that the outer diameter and heat shrinkage of the desired coil shape can be obtained. can.
- the outer diameter D'of the coil shape is preferably 100 to 2000 ⁇ m.
- the outer diameter D'of the coil shape in the present invention means the outer diameter of the coil itself, as shown in FIGS. 3 and 6. Since the outer diameter D'of the coil shape can be regarded as the thread diameter of the warp or weft in the woven fabric, it greatly contributes to the three-dimensional structure of the woven fabric. From the above viewpoint, the outer diameter D'of the coil shape is preferably 100 to 2000 ⁇ m. When the outer diameter D'of the coil shape is 100 ⁇ m or more, the coil is less likely to break when the coil is manufactured, and the coil can be easily manufactured.
- the outer diameter D'of the coil shape is 2000 ⁇ m or less, a flat woven fabric can be manufactured without making one woven fabric unnecessarily thick.
- the outer diameter D'of the coil shape is more preferably 150 to 1500 ⁇ m, further preferably 200 to 1000 ⁇ m, particularly preferably 250 to 900 ⁇ m, and most preferably 300 to 800 ⁇ m.
- the method for measuring the outer diameter D'of the coil shape is not particularly limited as long as it is a means capable of precise measurement, but measurement with an optical microscope or a microscope is preferable in terms of dimensional accuracy.
- the diameter of the heating wire is preferably 20 to 2000 ⁇ m.
- the diameter of the heating wire in the present invention means the outer diameter of the wire including the insulating coating. Since the diameter of the heating wire can be regarded as the diameter of the warp or weft in the woven fabric, it greatly contributes to the three-dimensional structure of the woven fabric. The smaller the diameter of the heating wire, the larger the contact area with the non-heated portion when weaving, and the amount of heat generated by energization heating can be satisfactorily transferred to the non-heated portion.
- the lower limit of the diameter of the heating wire is not particularly limited, but if the diameter of the heating wire is 20 ⁇ m or more, it is possible to produce a woven fabric that is resistant to scratching and has high repeatability. Further, if the diameter of the heating wire is 2000 ⁇ m or less, a flat woven fabric can be manufactured without making one woven fabric unnecessarily thick. From the above viewpoint, the diameter of the heating wire is more preferably 30 to 1500 ⁇ m, further preferably 40 to 1500 ⁇ m, particularly preferably 50 to 1300 ⁇ m, and most preferably 100 to 1000 ⁇ m. As a method for measuring the diameter of the heating wire, it is preferable to measure with an optical microscope or a microscope in terms of dimensional accuracy, as in the case of the outer diameter of the coil shape.
- the woven fabric of the embodiment of the present invention preferably has reversible thermal elasticity and a thermal shrinkage rate of 3% or more. If the heat shrinkage rate of the woven fabric is 3% or more, it can be easily used as an actuator. The larger the heat shrinkage rate, the wider the range of uses, which is preferable. From this viewpoint, the heat shrinkage rate is more preferably 4% or more, further preferably 5% or more. Further, the heat shrinkage rate is preferably 30% or less. When the heat shrinkage rate is 30% or less, the shape of the woven fabric before shrinkage can be easily maintained. From this viewpoint, the heat shrinkage rate is more preferably 20% or less, still more preferably 15% or less.
- the heat shrinkage rate of the woven fabric can be considered to be substantially equal to the heat shrinkage rate of the fiber A having reversible heat stretchability.
- the coil-shaped fibers A may be arranged in a meandering manner, so that the heat shrinkage rate of the woven fabric may be slightly increased.
- the heat shrinkage rate of the woven fabric is 3% or more, is within the above range, or the heat shrinkage rate of the fiber A having reversible heat elasticity constituting the woven fabric is 3% or more, as described above. It is desirable to be within the range.
- the temperature for heat shrinkage is preferably in the range of 50 to 150 ° C.
- the temperature for heat shrinkage is preferably high, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher.
- the heat shrinkage temperature is 150 ° C. or lower, the time until the temperature rise can be shortened and the shrinkage can be performed quickly. From this point of view, the heat shrinkage temperature is more preferably 120 ° C. or lower, further preferably 100 ° C. or lower.
- the textile product of the embodiment of the present invention preferably has a side length of 50 to 1000 mm and a side length of 5 to 200 mm. It can be a rectangle or a long shape consisting of a long side and a short side, and each side may be a square having the same length.
- the textile product of the embodiment of the present invention is a woven fabric, it is preferable that the length of the long side is 50 to 1000 mm and the length of the short side is 5 to 200 mm.
- the length of the long side of the woven fabric of the embodiment of the present invention may be 50 to 1000 mm when considering application to an assist suit.
- the length of the long side is appropriately selected according to the place and method of use of the woven fabric, the physique of the user, the expansion and contraction length of the coil-shaped fiber as an actuator, and the like.
- the length of the long side is 80 to 500 mm in the case of the waist assist assist suit.
- the length of the short side of the woven fabric according to the embodiment of the present invention may be 5 to 200 mm when considering application to an assist suit.
- the length of the short side is appropriately selected according to the required stress generated as the module, the dimensions of the module, and the like. For example, in an assist suit of a system carried on the back side, when it is used as two modules divided into left and right, if the length of the short side is 200 mm or less, it can be used without impairing the wearing feeling.
- the compacts of the embodiment are arranged in parallel and / or in series.
- the contraction force can be increased, and by arranging them in series, the contraction displacement can be increased.
- the molded product is a fibrous molded product, it may be used as a fabric such as a woven fabric or a knitted fabric for parallel arrangement and / or serial arrangement.
- the actuator of the embodiment of the present invention can have at least a structure including a molded body of the embodiment of the present invention and heating means.
- the actuator may further include cooling means.
- the heating means is not particularly limited, but for example, in addition to direct heating with warm air, heating can also be performed by an electric field by combining a metal coating or a heating wire. Further, although the cooling means is not always essential, efficient cooling can be achieved by combining air cooling with a fan or a Pelche element.
- the actuator module of the embodiment of the present invention includes a laminate in which 2 to 30 textile products of the above embodiment are laminated.
- the actuator module according to the embodiment of the present invention preferably includes a laminate in which 2 to 30 sheets of the above-mentioned fabric are laminated.
- the present invention by laminating the woven fabrics so that the heat shrinkage directions are the same, the number of coil-shaped fibers can be increased and the stretching force can be increased also in the thickness direction. Further, by laminating the woven fabrics, when the heating wire is heated, the heat loss to the surrounding air or the like is reduced, and the coil-shaped fibers can be efficiently heated. For example, when 10 plain weave fabrics are laminated at the same position so as to increase in the thickness direction, as shown in FIG.
- the coil-shaped fibers 1 are not only the heating wires 2 and 2'constituting the fabric, but also the heating wires 2 and 2'. It is also heated in contact with the heating wire in the surrounding woven fabric. Therefore, it is possible to further reduce the loss of heat energy during heating and efficiently operate the actuator.
- the number of laminated fabrics can be determined according to the required generated stress. As the number of laminated fabrics increases, the ratio of the surface area to the size of the module decreases, so that the coil-shaped fibers can be heated efficiently.
- the laminate of the woven fabric can be made into an actuator module by attaching a power supply, a cooling unit, or the like.
- the power source is not particularly limited as long as it can supply the required power, and there is no particular limitation on the fixed type or the portable type.
- the cooling unit include air cooling with cold air and cooling with a liquid.
- natural cooling may be used unless special control is required.
- Liquid cooling is useful when rapid cooling is required. In that case, since the woven fabric of the embodiment of the present invention has an insulating coating on the heating wire, it can be used even with a liquid such as water that easily conducts electricity. In addition, of course, an insulating liquid may be used to ensure further safety.
- the insulating liquid examples include silicone oil and perfluoropolyether. Since perfluoropolyether is also generally known as a refrigerant, it is suitable for the laminate of the embodiment of the present invention. Further, it is effective to use a Pelche element in order to efficiently use both heating and cooling.
- the actuator of the embodiment of the present invention is an actuator including the molded body of the embodiment, or an actuator formed by arranging the molded bodies of the embodiment in parallel and / or in series.
- the actuator of the embodiment of the present invention is sometimes called a soft actuator, and the material itself has elasticity.
- the actuator of the present embodiment can have at least a configuration including the molded body and a heater. In addition, it can also have a cooler. By arranging the molded bodies in parallel, the contraction force can be increased. Further, by arranging them in series, the contraction displacement can be increased.
- the method for heating the actuator according to the embodiment of the present invention is not particularly limited, but for example, in addition to direct heating with warm air, heating by an electric field can also be performed by combining a metal coating or a heating wire.
- a heating wire having an insulating coating it is possible to prevent electric shock and impart durability.
- cooling is not always essential, efficient cooling can be achieved by combining air cooling with a fan or a Pelche element.
- the actuator of the embodiment of the present invention it can be preferably used for a power assist suit, a robot arm, a robot hand, and other robot driving parts that require a high contraction generating force and a high expansion / contraction displacement. ..
- the drive unit of in-vehicle sensors the drive unit of in-vehicle louvers, the drive unit of in-vehicle seats, the drive unit of in-vehicle cameras, and the drive unit of other in-vehicle devices, which are required to be lightweight and quiet. Can be done.
- medical devices such as endoscopes and hemostatic bands that are required to be lightweight and generate high contraction, home appliances such as camera lens drives, aircraft parts such as drone gimbals, and industrial endoscopes. It can be used for drive units, bed drives, indoor air-conditioning louver drives, air-conditioning sensors / camera drives, textile products such as inner / outer wear, and nursing mats. It can also be used as a thermostat that is required to be driven by temperature changes, such as a mixing valve, shower hot water temperature adjustment, and burn prevention device.
- the assist suit of the embodiment of the present invention includes the actuator module of the embodiment as a drive unit.
- the woven fabric and the actuator module can be used for various purposes, they are particularly suitable for use in assist suits because of the high stress generated per mass of coil-shaped fibers.
- An assist suit is an exoskeleton-type or clothing-type device that acts as an auxiliary in addition to human power in fields such as medical / nursing care and logistics / cargo handling.
- the assist suit can include a belt, a supporter, and the like to be attached to the human body in addition to the actuator module as a drive unit.
- the assist suit may be provided with a gear or the like for manipulating the operating width and the operating direction, and may include a mechanical mechanism such as a link mechanism, if necessary.
- a gear or the like for manipulating the operating width and the operating direction
- a mechanical mechanism such as a link mechanism, if necessary.
- various types of assist suits such as waist assist, walking assist, and arm assist can be mentioned.
- the fabric and the actuator module are applicable to any type as components of these various assist suits.
- thermomechanical analyzer manufactured by Hitachi High-Tech Science Corporation, model: TMA6100
- the heat shrinkage rate and the restoration rate were measured as follows. First, a load is applied to the molded product sample so that the tensile stress is 1, 3, 5, 10 MPa based on the cross-sectional area calculated from the diameter, and marks are made at two places at intervals of about 5 mm. Next, with the tensile load applied, the temperature is raised from 35 ° C to 85 ° C and then lowered to 35 ° C.
- the heat shrinkage rate is obtained by the following formula.
- the diameter of the single fiber was measured with an ultra-high speed and high precision dimensional measuring instrument (manufactured by KEYENCE, model: LS-9006).
- the gel fraction was measured by the following method. This gel fraction represents the degree of cross-linking, and the higher the value, the higher the degree of cross-linking.
- M1 mass of the fiber sample to be measured
- M2 mass of the fiber sample to be measured
- the drawn yarn was cut to a length of about 5 cm, aligned in the uniaxial direction so that the fibers did not overlap, and attached to the sample holder.
- the tube voltage was 40 kV
- the tube current was 200 mA
- the irradiation time was 120 minutes
- the imaging plate was exposed.
- the crystal peak In separating the one-dimensional profile into a crystal peak and an amorphous peak, the crystal peak is set at a diffraction angle known in the literature, and the amorphous peak is set so as to complement the difference from the profile. Fitting was performed using the waveform separation analysis software Fitik (open source software). The crystallinity was calculated by dividing the sum of the crystal peak integrated intensities by all the peak integrated intensities. As the fitted peak function, a pseudo Voigt function, which is a superposition of the Gaussian function and the Lorentz function, was used, and the ratio of the Gaussian function and the Lorentz function was fixed at 1: 1.
- the fibers were cut to about 5 cm, aligned in the uniaxial direction so that the fibers did not overlap, and attached to the sample holder.
- the tube voltage is 50 kV
- the tube current is 300 mA
- the scanning range is 5 to 40 °
- the scan speed is 10 ° / min.
- the detector is fixed at the angle of the maximum intensity crystal peak.
- the fiber density was measured by the density gradient tube method based on JIS K 7112.
- the coil-shaped outer diameter D', coil-shaped fiber length, single fiber diameter d, and heating wire diameter are determined using a digital microscope (trade name: DSX500, manufactured by Olympus Corporation). It was measured.
- the spring index D / d was calculated using the coil average diameter D ( ⁇ m) and the single fiber diameter d ( ⁇ m).
- a silanol condensation catalyst masterbatch (manufactured by Mitsubishi Chemical Co., Ltd., LZ082) was charged into an extruder of a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of a silane crosslinkable polyethylene resin, and melted at 220 ° C. After kneading, the resin at 220 ° C.
- the obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 50 ° C. and a draw ratio of 3.5 times for the first-stage drawing.
- the second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 55 ° C. and a drawing ratio of 1.2 times.
- the heat annealing treatment was performed at a yarn temperature of 70 ° C. and a draw ratio of 1.0 times.
- the annealed fiber was immersed in warm water at 90 ° C. for 24 hours under constant length tension to carry out a cross-linking treatment, and a fiber having a cross-linked structure was obtained. Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
- the tensile stress for measuring the heat shrinkage was measured as 5 MPa. Compared with the comparative example, it can be seen that the shrinkage rate is high and the shrinkage force is high even with the same tensile stress.
- Crosslinked fibers were obtained in the same manner as in Example 1 except that they were replaced with 16 kg, 10 minutes)). Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
- a silanol condensation catalyst masterbatch (manufactured by Mitsubishi Chemical Co., Ltd., LZ082) was put into a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of a silane crosslinkable polyethylene resin, and melt-kneaded at a maximum of 210 ° C.
- a spinning nozzle with a discharge hole diameter of 1.6 mm ⁇ and a number of discharge holes of 1 hole discharges at a discharge rate of 1.56 g / min and is wound around a bobbin at a take-up speed of 14.4 m / min to obtain undrawn yarn. rice field.
- the obtained undrawn yarn was subjected to the first dry heat drawing at a yarn temperature of 80 ° C. and a draw ratio of 5.90 times.
- the second stage dry heat drawing was continuously performed at a yarn temperature of 95 ° C. and a draw ratio of 1.07 times.
- a thermal annealing treatment was performed while relaxing at a yarn temperature of 103 ° C.
- the obtained fiber was subjected to a cross-linking treatment for 48 hours while repeatedly raising and lowering the temperature so as to reach the conditions of a maximum temperature of 85 ° C. and a humidity of 85% RH in a high-temperature and humidity chamber while the obtained fiber was wound around a bobbin, and a silane cross-linking structure was performed. (Diameter: 0.2 mm) was obtained. Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
- Example 4 The heat shrinkage of the fibers obtained in Example 3 was measured with a tensile stress of 3 MPa for measuring the heat shrinkage.
- Example 5 The heat shrinkage of the fibers obtained in Example 3 was measured with a tensile stress of 1 MPa for measuring the heat shrinkage.
- the obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 3.5 times for the first-stage drawing.
- the second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 90 ° C. and a drawing ratio of 1.1 times.
- thermal annealing treatment was performed at a yarn temperature of 110 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinks. Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
- the obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 9.4 times in the first step.
- the second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 100 ° C. and a drawing ratio of 1.1 times.
- thermal annealing treatment was performed at a yarn temperature of 110 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure. Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
- the obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 3.5 times for the first-stage drawing.
- the second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 85 ° C. and a drawing ratio of 1.1 times.
- thermal annealing treatment was performed at a yarn temperature of 100 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure. Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
- the obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 50 ° C. and a draw ratio of 3.5 times for the first-stage drawing.
- the second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 55 ° C. and a drawing ratio of 1.2 times.
- thermal annealing treatment was performed at a yarn temperature of 70 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure. Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
- the obtained undrawn yarn was immersed in warm water at 90 ° C. for 24 hours under constant length tension to carry out a cross-linking treatment to obtain a fiber having a cross-linked structure. Measurements were carried out to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage rate, and restoration rate of the obtained crosslinked fiber. When I tried to measure the heat shrinkage rate, it stretched due to heat and broke, so I could not measure it. This is considered to be one of the causes due to the low degree of crystal orientation. These results are shown in Table 1.
- the hot plate was continuously stretched under the conditions of a yarn temperature of 95 ° C. and a draw ratio of 1.1 times.
- the third stage was subjected to thermal annealing treatment under the conditions of a yarn temperature of 105 ° C. and a draw ratio of 1.0 times. Further, it was allowed to stand for 24 hours in an environment of 85 ° C. and 85% RH under constant length tension and subjected to cross-linking treatment to obtain a fiber made of a silane cross-linked polyethylene composition. The degree of crystallinity and the degree of crystal orientation of the obtained fibers were measured. The results are shown in Table 2.
- the obtained fiber was cut to a length of 20 cm, the upper end was fixed to a rotating shaft, and a 12 g weight was attached to the lower end to apply a tension of 5 MPa. Subsequently, a twisting operation was performed on the rotation axis in the longitudinal direction of the fiber until the fiber became a coil shape, and a coil-shaped fiber was produced. After producing another coil-shaped fiber by the same method, the two coil-shaped fibers were reverse-twisted and twisted together while applying a tension of 5 MPa until the twisting torque disappeared.
- the single fiber diameter d and the coil outer diameter D' were observed with a digital microscope, and the coil average diameter D and the spring index D / d were calculated. In addition, the density and gel fraction of the obtained fibers were measured, and thermal expansion and contraction evaluation was performed. These results are shown in Table 2.
- An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 2.0 m / min.
- the obtained undrawn yarn was drawn on a hot plate under the conditions of a yarn temperature of 90 ° C. and a draw ratio of 9.4 times as the first drawing.
- hot plate stretching was performed under the conditions of yarn temperature: 100 ° C. and drawing ratio: 1.1 times.
- a thermal annealing treatment was performed under the conditions of a yarn temperature of 110 ° C. and a draw ratio of 1.0 times.
- the degree of crystallinity and the degree of crystal orientation of the obtained fibers were measured. The results are shown in Table 2.
- the obtained fiber was cut to a length of 20 cm, the upper end was fixed to a rotating shaft, and a weight of 49 g was attached to the lower end to apply a tension of 20 MPa. Subsequently, a twisting operation was performed until the fibers were folded into a coil shape to produce coil-shaped fibers. In the same manner, another coil-shaped fiber was produced, and two coil-shaped fibers were twisted together.
- the single fiber diameter d and the coil outer diameter D' were observed with a digital microscope, and the coil average diameter D and the spring index D / d were calculated.
- the density and gel fraction of the obtained fibers were measured, and thermal expansion and contraction evaluation was performed. Since the obtained fiber does not have a crosslinked structure, the heat shrinkage rate was low.
- Example 7 As the fiber A having reversible thermal elasticity, a nylon fiber having a diameter of 0.21 mm (trade name: Ginscale (registered trademark) No. 1.5, manufactured by Toray Industries, Inc.) was used, and a load of 70 g was applied to the fiber 60 cm. By twisting 350 times, an overtwist type coil-shaped fiber having a length of 140 mm was produced. At the time of production, the load was controlled not to rotate due to twisting. The twisting speed was 6 rotations per second. The obtained coil-shaped fiber was held at 180 ° C. for 60 minutes in a state of being stretched by 20% to perform heat setting. The diameter of the coil shape of the produced coil-shaped fiber was 480 ⁇ m.
- heating wire manufactured by Tokyo Special Electric Wire Co., Ltd., core: polyarylate, heating element wire: nichrome alloy, insulating coating: ethylene-tetrafluoroethylene copolymer, diameter: 930 ⁇ m
- FIG. 7 A plain weave woven fabric as shown in FIG. 7 was produced using a resistance value of 300 ⁇ / m (at 20 ° C.) as a warp and weft.
- FIG. 6 is a photograph showing a part of the coil-shaped fibers used in this woven fabric.
- FIG. 10 is a photograph showing a part of the produced woven fabric.
- the heating wires were arranged so as to be folded back in a loop at every place, and only one heating wire was used in one woven fabric.
- eight coil-shaped fibers were used in one woven fabric.
- the length of the long side of the produced woven fabric was 100 mm, and the length of the short side was 5 mm.
- Two pieces of this woven fabric were stacked to form an actuator module. A load of 10 g was applied to each coil-shaped fiber.
- the heating wire of this actuator module was energized using a DC power supply device, and energized and heated until the surface temperature of the woven fabric reached about 90 ° C. to perform heat shrinkage.
- the surface temperature was confirmed using a thermal image camera A6700SC (trade name, manufactured by Chino Co., Ltd.).
- the woven fabric shrank by 5% (heat shrinkage rate: 5%) and then returned to its original length by air cooling. Heating and air cooling were repeated 5 times (6 times in total) under the same conditions, but the length of the woven fabric was the same as that before the energization heating (restoration rate: 100%). That is, it was confirmed that the produced woven fabric had reversible thermal elasticity.
- the temperature of the heating wire reached by energization did not change, and it was confirmed that the obtained actuator module can maintain high durability.
- Example 7 A coil-shaped fiber was produced in the same manner as in Example 1, and a silver-containing paste (trade name: PE874, manufactured by DuPont) was applied to the surface thereof so that the film thickness was 200 ⁇ m. Ten fibers of the coil shape were arranged side by side, and ten fibers at both ends were fixed together, and a load of 10 g was applied to each fiber.
- the silver-containing paste applied to the coil-shaped fiber is used to energize using a DC power supply device, and as in Example 1, energization heating is performed until the surface temperature of the fiber reaches about 90 ° C. to heat shrinkage. gone. The surface temperature was confirmed using a thermal image camera A6700SC (trade name, manufactured by Chino Co., Ltd.).
- the coil-shaped fibers shrank by 5% and then returned to their original length by air cooling.
- heating and air cooling were repeated 5 more times under the same conditions (6 times in total)
- the surface temperature of the coil-shaped fibers reached by energization became lower than the surface temperature at the time of the first energization heating, and a problem occurred in durability. ..
- D Coil average diameter d: Single fiber diameter
- D' Coil outer diameter
- La Length of part a that shrinks due to heating
- Lb Length of part b that does not shrink due to heating or has low heat shrinkage
- 1'Reversible Coil-shaped fiber A with thermal elasticity 2 2'heating wire 3 outer frame of actuator module
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Abstract
The purpose of the present invention is to provide a molded article having excellent reversible thermal stretchability, a fiber product, an actuator, an assist suit, and an actuator module. Provided are: a molded article which has a specified gel fraction and a specified crystal orientation degree and which has a crystal orientation degree of 60% or less or has a coil-like shape; a fiber product and an actuator each including the molded article; and an assist suit and an actuator module.
Description
本発明は、可逆的熱伸縮性を有する成形体、繊維製品、アクチュエータ及びアシストスーツに関する。
The present invention relates to a molded body, a textile product, an actuator and an assist suit having reversible thermal elasticity.
先進国における高齢化社会の到来、ロボット工学の発達、人類の知的活動へのシフトなどから、様々な物品の動力化が求められており、種々のアクチュエータが提案されている。アクチュエータとは、例えば、モータ、油空圧シリンダ、圧電素子、人工筋肉といった、動きや力を作りだす装置の総称である。アクチュエータは、電気や熱、光、燃料などのエネルギーによって材料自体が変形する駆動体であり、その基本的な変形パターンは、伸縮、屈伸、捩り、膨張・収縮である。
Due to the advent of an aging society in developed countries, the development of robotics, and the shift to human intellectual activities, the motorization of various articles is required, and various actuators have been proposed. Actuator is a general term for devices that create movement and force, such as motors, pneumatic / pneumatic cylinders, piezoelectric elements, and artificial muscles. An actuator is a driving body whose material itself is deformed by energy such as electricity, heat, light, and fuel, and its basic deformation pattern is expansion / contraction, bending / stretching, twisting, expansion / contraction.
現在、最も広く利用されているモータは、硬い、重い、動作音が大きいなどの問題がある。それに対して、小型軽量、様々な駆動源、無音、極限条件下の水中や大気中で動くなどの様々な特徴を有する人工筋肉のようなソフトアクチュエータの開発が近年、進められている。
Currently, the most widely used motors have problems such as being hard, heavy, and making a loud noise. On the other hand, in recent years, the development of soft actuators such as artificial muscles having various characteristics such as small size and light weight, various drive sources, silence, and movement in water or air under extreme conditions has been promoted.
例えば、特許文献１には、ナイロン繊維が捩られ、コイル形状のアクチュエータが可逆的な熱伸縮を示すことが開示されている。
特許文献２、非特許文献１には、直鎖状低密度ポリエチレン繊維をコイル形状にすることで、単位温度あたりの熱収縮率が高く、小さい温度変化で、高変位を達成したアクチュエータが開示されている。
特許文献３では、加熱冷却によって可逆的に伸縮動作し、柔軟性に富んだアクチュエータ用繊維が開示され、ナイロン繊維をコイル形状とし、バネ指数を特定の数値以上に高くすることが記載されている。 For example,Patent Document 1 discloses that nylon fibers are twisted and a coil-shaped actuator exhibits reversible thermal expansion and contraction.
Patent Document 2 and Non-Patent Document 1 disclose an actuator in which a linear low-density polyethylene fiber is formed into a coil shape to have a high heat shrinkage rate per unit temperature and achieve a high displacement with a small temperature change. ing.
Patent Document 3 discloses a fiber for an actuator that expands and contracts reversibly by heating and cooling and has abundant flexibility, and describes that a nylon fiber has a coil shape and a spring index is increased to a specific value or more. ..
特許文献２、非特許文献１には、直鎖状低密度ポリエチレン繊維をコイル形状にすることで、単位温度あたりの熱収縮率が高く、小さい温度変化で、高変位を達成したアクチュエータが開示されている。
特許文献３では、加熱冷却によって可逆的に伸縮動作し、柔軟性に富んだアクチュエータ用繊維が開示され、ナイロン繊維をコイル形状とし、バネ指数を特定の数値以上に高くすることが記載されている。 For example,
Patent Document 3 discloses a fiber for an actuator that expands and contracts reversibly by heating and cooling and has abundant flexibility, and describes that a nylon fiber has a coil shape and a spring index is increased to a specific value or more. ..
近年では、熱による可逆的伸縮性（以下、「可逆的熱伸縮性」とも称する）を有する繊維を使用したアクチュエータの開発が進んでいる。非特許文献２には、可逆的熱伸縮性を有する繊維をコイル形状にしたアクチュエータが開示されている。
アクチュエータを加熱する手段として、例えば、非特許文献３には、銀ペーストにより被膜したナイロン繊維を電熱線として用いる方法や、繊維からなるコイルに導電ペーストを塗布し、通電加熱が可能なコイルとする方法が開示されている。また、特許文献４には、繊維からなるコイルの外周に電熱部材と絶縁部材を配置する方法が開示されている。 In recent years, the development of actuators using fibers having reversible elasticity due to heat (hereinafter, also referred to as "reversible thermal elasticity") has been progressing. Non-PatentDocument 2 discloses an actuator in which a fiber having reversible thermal elasticity is formed into a coil shape.
As a means for heating the actuator, for example, in Non-Patent Document 3, a method of using nylon fibers coated with silver paste as a heating wire, or a coil made of fibers is coated with a conductive paste to obtain a coil capable of energization heating. The method is disclosed. Further, Patent Document 4 discloses a method of arranging an electric heating member and an insulating member on the outer periphery of a coil made of fibers.
アクチュエータを加熱する手段として、例えば、非特許文献３には、銀ペーストにより被膜したナイロン繊維を電熱線として用いる方法や、繊維からなるコイルに導電ペーストを塗布し、通電加熱が可能なコイルとする方法が開示されている。また、特許文献４には、繊維からなるコイルの外周に電熱部材と絶縁部材を配置する方法が開示されている。 In recent years, the development of actuators using fibers having reversible elasticity due to heat (hereinafter, also referred to as "reversible thermal elasticity") has been progressing. Non-Patent
As a means for heating the actuator, for example, in Non-Patent Document 3, a method of using nylon fibers coated with silver paste as a heating wire, or a coil made of fibers is coated with a conductive paste to obtain a coil capable of energization heating. The method is disclosed. Further, Patent Document 4 discloses a method of arranging an electric heating member and an insulating member on the outer periphery of a coil made of fibers.
しかしながら、特許文献１では、ナイロンの繊維自体の単位温度当たりの熱収縮率は、０．００２％／℃程度であり、低いものであった。特許文献２、非特許文献１では、直鎖状低密度ポリエチレンの繊維自体の熱収縮率がナイロンより高いものの、アクチュエータとして十分ではなかった。特許文献３では、ナイロンを使っているため、繊維自体の単位温度当たりの熱収縮率は低く、コイルのバネ指数を高くしなければ収縮率を高くすることができないという制限があった。
However, in Patent Document 1, the heat shrinkage rate of the nylon fiber itself per unit temperature was about 0.002% / ° C, which was low. In Patent Document 2 and Non-Patent Document 1, although the heat shrinkage of the linear low-density polyethylene fiber itself is higher than that of nylon, it is not sufficient as an actuator. In Patent Document 3, since nylon is used, the heat shrinkage rate per unit temperature of the fiber itself is low, and there is a limitation that the shrinkage rate cannot be increased unless the spring index of the coil is increased.
可逆的熱伸縮性を有する繊維と電熱線等とを組み合わせて、複数本を並べて使用する場合、安全かつ効率の良い加熱手段が求められる。
例えば、非特許文献２では、複数本の繊維等を並べて使用する方法として、銀被膜で覆われたナイロン繊維を使用し、通電加熱時に銀被膜で覆われたナイロン繊維の接触によるショートが起きないように、ポリエステル繊維やコットン繊維を挟んだ織物としている。
しかしながら、銀被膜で覆われたナイロン繊維に絶縁被覆がされていないため、ショートする可能性は残っている。また、冷却液として水を使用する場合には漏電の恐れがある。 When a plurality of fibers having reversible thermal elasticity and a heating wire or the like are combined and used side by side, a safe and efficient heating means is required.
For example, in Non-PatentDocument 2, nylon fibers covered with a silver film are used as a method of using a plurality of fibers side by side, and short circuit does not occur due to contact between the nylon fibers covered with the silver film during energization heating. As described above, it is a woven fabric sandwiched between polyester fibers and cotton fibers.
However, since the nylon fiber covered with the silver film is not insulated, the possibility of short circuit remains. In addition, when water is used as the coolant, there is a risk of electric leakage.
例えば、非特許文献２では、複数本の繊維等を並べて使用する方法として、銀被膜で覆われたナイロン繊維を使用し、通電加熱時に銀被膜で覆われたナイロン繊維の接触によるショートが起きないように、ポリエステル繊維やコットン繊維を挟んだ織物としている。
しかしながら、銀被膜で覆われたナイロン繊維に絶縁被覆がされていないため、ショートする可能性は残っている。また、冷却液として水を使用する場合には漏電の恐れがある。 When a plurality of fibers having reversible thermal elasticity and a heating wire or the like are combined and used side by side, a safe and efficient heating means is required.
For example, in Non-Patent
However, since the nylon fiber covered with the silver film is not insulated, the possibility of short circuit remains. In addition, when water is used as the coolant, there is a risk of electric leakage.
非特許文献３では、繊維からなるコイル２本を双糸状にした物に対して導電被膜を塗布しているが、絶縁被膜は備えていない。また、この方法では、コイルが伸縮運動をする度に導電被膜に欠陥が発生しやすく、繰り返し耐久性に問題が生じやすい。また、伸縮運動の度に導電被膜の厚み等の状態が変化し抵抗値が変わるため、抵抗値の制御が困難であり、ショートする恐れもあった。また、繊維からなるコイルを数百本規模で使用する場合においては、多大なコストがかかってしまう。
In Non-Patent Document 3, a conductive film is applied to a double-threaded coil made of two fibers, but an insulating film is not provided. Further, in this method, a defect is likely to occur in the conductive film each time the coil expands and contracts, and a problem in repeated durability tends to occur. In addition, it is difficult to control the resistance value because the state such as the thickness of the conductive film changes and the resistance value changes every time the expansion and contraction movement is performed, and there is a risk of short circuit. Further, when a coil made of fibers is used on a scale of several hundreds, a great cost is required.
特許文献４には、繊維からなるコイル１本、もしくは繊維からなるコイル２本を双糸状にした物に対する、電熱部材と絶縁部材の配置の仕方が記載されている。しかしながら、繊維からなるコイルを数百本規模で使用する場合においては、莫大なコストと手間がかかってしまう。また、繊維からなるコイル１本、もしくは繊維からなるコイル２本を双糸状にした物に対して最適化を図るため、体積当たりに配置できる繊維からなるコイルの数が少なくなってしまう。
Patent Document 4 describes how to arrange an electric heating member and an insulating member with respect to a coil made of fibers or two coils made of fibers in a twin-thread shape. However, when a coil made of fibers is used on a scale of several hundreds, enormous cost and labor are required. Further, in order to optimize for one coil made of fibers or two coils made of fibers in a twin thread shape, the number of coils made of fibers that can be arranged per volume is reduced.
本発明の第１の目的は、可逆的熱伸縮性に優れる成形体、繊維製品、およびアクチュエータを提供することにある。
また、本発明の第２の目的は、繰り返し耐久性が高く、安全に使用できるアシストスーツ、およびそのパーツとなるアクチュエータモジュールを提供することにある。 A first object of the present invention is to provide a molded product, a textile product, and an actuator having excellent reversible thermal elasticity.
A second object of the present invention is to provide an assist suit that has high repeatability and can be used safely, and an actuator module that is a part thereof.
また、本発明の第２の目的は、繰り返し耐久性が高く、安全に使用できるアシストスーツ、およびそのパーツとなるアクチュエータモジュールを提供することにある。 A first object of the present invention is to provide a molded product, a textile product, and an actuator having excellent reversible thermal elasticity.
A second object of the present invention is to provide an assist suit that has high repeatability and can be used safely, and an actuator module that is a part thereof.
１．ゲル分率が１０％以上であり、結晶配向度が８０％以上であり、結晶化度が６０％以下である成形体。
２．ゲル分率が１０％以上であり、結晶配向度が６０％以上であり、コイル形状である成形体。
３．加熱による単位温度当たりの収縮率が０．０７％／℃以上である１または２に記載の成形体。
４．加熱により５０℃の温度変化を与えた時の収縮率が３．５％以上である１～３のいずれかに記載の成形体。
５．成形体内部に架橋構造を有する１～４のいずれかに記載の成形体。
６．前記架橋構造がシラン架橋を含む５に記載の成形体。
７．可逆的熱伸縮性を有し、加熱による単位温度当たりの収縮率が０．０７％／℃以上である１～６のいずれかに記載の成形体。
８．－３０℃から２００℃の温度領域において、単位温度当たりの収縮率が０．０７％／℃以上である１～７のいずれかに記載の成形体。
９．１～２０ＭＰａの引張荷重状態で、加熱による単位温度当たりの収縮率が０．０７％／℃以上である１～８のいずれかに記載の成形体。
１０．５０℃の温度変化の加熱による収縮後に５０℃降温したときの復元率が、９０％以上である１～９のいずれかに記載の成形体。
１１．オレフィン系重合体からなる１～１０のいずれかに記載の成形体。
１２．ポリエチレンからなる１～１１のいずれかに記載の成形体。
１３．前記成形体が、繊維状、板状、シート状もしくはフィルム状であり、又はこれらの１種以上の多層構造を有する１～１２のいずれかに記載の成形体。
１４．前記成形体が繊維状であり、該繊維状成形体の単繊維の繊度が５０～１００００ｄｔｅｘである１３に記載の成形体。
１５．前記成形体が繊維状であり、該繊維状成形体の単繊維の直径が８０～１２００μｍである１３または１４に記載の成形体。
１６．コイル形状に形成された１～１５のいずれかに記載の成形体。
１７．以下（１）～（３）をすべて満たす１６に記載の成形体。
（１）繊維軸に対して垂直方向から測定したX線回折パターンについて、２θ＝１０°から３０°の区間に１つ以上のピークがある。
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上である。
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下である。
１８．バネ指数Ｄ／ｄが０．５以上であり、前記コイル形状の平均直径Ｄが１００～２０００μｍである１６または１７に記載の成形体。
Ｄはコイル平均直径（μｍ）を示し、ｄは単繊維直径（μｍ）を示す。
１９．密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレン２０～８０質量％と、密度が０．８６０～０．８８０ｇ／ｃｍ３である直鎖状低密度ポリエチレン２０～８０質量％と、を含有する混合物を含む１６～１８のいずれかに記載の成形体。
２０．前記混合物の密度が０．８６０～０．９４０ｇ／ｃｍ３である１９に記載の成形体。
２１．撚数が１～３０回／ｍｍである１６～２０のいずれかに記載の成形体。
２２．可逆的伸縮性を有する成形体であって、可逆的熱伸縮性を有さない部分を部分的に有する１～２１のいずれかに記載の成形体。
２３．前記１～２２のいずれかに記載の成形体を含む繊維製品。
２４．織物、編物、不織布、又は紐である２３に記載の繊維製品。
２５．前記繊維製品が織物であって、経糸または緯糸の一方が前記成形体を含み、他方が前記成形体を含まず且つ絶縁被膜で覆われた電熱線を含む２３に記載の繊維製品。
２６．前記電熱線が、連続した１本の電熱線である２５に記載の繊維製品。
２７．前記電熱線が、複数本の電熱線からなる２５に記載の繊維製品。
２８．前記電熱線の直径が２０～２０００μｍである２５～２７のいずれかに記載の繊維製品。
２９．前記織物の組織が、平織、綾織、カラミ織および朱子織のいずれか、またはこれらの組織の組み合わせである２３～２８のいずれかに記載の繊維製品。
３０．一辺の長さが５０～１０００ｍｍ、他の辺の長さが５～２００ｍｍである２３～２９のいずれかに記載の繊維製品。
３１．前記１～２２のいずれかに記載の成形体が並行配列および／または直列配列されているアクチュエータ。
３２．前記２３～２９のいずれかに記載の繊維製品が積層した積層物を含むアクチュエータモジュール。
３３．前記３２に記載のアクチュエータモジュールを駆動部として備えるアシストスーツ。 1. 1. A molded product having a gel fraction of 10% or more, a crystal orientation degree of 80% or more, and a crystallinity of 60% or less.
2. 2. A molded product having a gel fraction of 10% or more, a crystal orientation degree of 60% or more, and a coil shape.
3. 3. The molded product according to 1 or 2, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher.
4. The molded product according to any one of 1 to 3, wherein the shrinkage rate when a temperature change of 50 ° C. is applied by heating is 3.5% or more.
5. The molded product according to any one of 1 to 4, which has a crosslinked structure inside the molded product.
6. 5. The molded product according to 5, wherein the crosslinked structure includes a silane crosslink.
7. The molded product according to any one of 1 to 6, which has reversible thermal elasticity and has a shrinkage rate of 0.07% / ° C. or higher per unit temperature due to heating.
8. The molded product according to any one of 1 to 7, wherein the shrinkage rate per unit temperature is 0.07% / ° C. or higher in the temperature range of −30 ° C. to 200 ° C.
9. The molded product according to any one of 1 to 8, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher under a tensile load of 9.1 to 20 MPa.
10. The molded product according to any one of 1 to 9, wherein the restoration rate when the temperature is lowered to 50 ° C. after shrinking due to heating with a temperature change of 10.50 ° C. is 90% or more.
11. The molded product according to any one of 1 to 10, which is made of an olefin polymer.
12. The molded product according to any one of 1 to 11 made of polyethylene.
13. The molded product according to any one of 1 to 12, wherein the molded product is in the form of a fiber, a plate, a sheet, or a film, or has one or more of these multilayer structures.
14. 13. The molded product according to 13, wherein the molded product is fibrous and the fineness of the single fiber of the fibrous molded product is 50 to 10000 dtex.
15. 13. The molded product according to 13 or 14, wherein the molded product is fibrous and the diameter of a single fiber of the fibrous molded product is 80 to 1200 μm.
16. The molded product according to any one of 1 to 15 formed in a coil shape.
17. 16. The molded product according to 16, which satisfies all of the following (1) to (3).
(1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the peak with the highest intensity, or the intensity of the peak with the highest intensity is more than double the intensity of the peak with the next highest intensity.
(3) The degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material.
18. 16. The molded product according to 16 or 17, wherein the spring index D / d is 0.5 or more, and the average diameter D of the coil shape is 100 to 2000 μm.
D indicates the coil average diameter (μm), and d indicates the single fiber diameter (μm).
19. One or more polyethylenes 20-80 selected from linear low density polyethylene with a density of 0.881 to 0.941 g / cm 3 and high density polyethylene with a density of 0.942 to 0.970 g / cm 3 . The molded product according to any one of 16 to 18, which comprises a mixture containing 20 to 80% by mass of linear low-density polyethylene having a density of 0.860 to 0.880 g / cm 3 and 20 to 80% by mass.
20. 19. The molded article according to 19, wherein the density of the mixture is 0.860 to 0.940 g / cm 3 .
21. The molded product according to any one of 16 to 20, wherein the number of twists is 1 to 30 times / mm.
22. The molded product according to any one of 1 to 21, which is a molded product having reversible elasticity and partially has a portion not having reversible thermal elasticity.
23. A textile product containing the molded product according to any one of 1 to 22 above.
24. 23. The textile product according to 23, which is a woven fabric, a knitted fabric, a non-woven fabric, or a string.
25. 23. The textile product according to 23, wherein the textile product is a woven fabric, one of which is a warp or a weft containing the molded body, and the other is a heating wire which does not contain the molded body and is covered with an insulating coating.
26. 25. The textile product according to 25, wherein the heating wire is one continuous heating wire.
27. 25. The textile product according to 25, wherein the heating wire is composed of a plurality of heating wires.
28. The textile product according to any one of 25 to 27, wherein the heating wire has a diameter of 20 to 2000 μm.
29. The textile product according to any one of 23 to 28, wherein the texture of the woven fabric is any of plain weave, twill weave, Karami weave and satin weave, or a combination of these textures.
30. The textile product according to any one of 23 to 29, wherein the length of one side is 50 to 1000 mm and the length of the other side is 5 to 200 mm.
31. An actuator in which the compacts according to any one of 1 to 22 are arranged in parallel and / or in series.
32. An actuator module including a laminate in which the textile products according to any one of 23 to 29 are laminated.
33. An assist suit including the actuator module according to 32 as a drive unit.
２．ゲル分率が１０％以上であり、結晶配向度が６０％以上であり、コイル形状である成形体。
３．加熱による単位温度当たりの収縮率が０．０７％／℃以上である１または２に記載の成形体。
４．加熱により５０℃の温度変化を与えた時の収縮率が３．５％以上である１～３のいずれかに記載の成形体。
５．成形体内部に架橋構造を有する１～４のいずれかに記載の成形体。
６．前記架橋構造がシラン架橋を含む５に記載の成形体。
７．可逆的熱伸縮性を有し、加熱による単位温度当たりの収縮率が０．０７％／℃以上である１～６のいずれかに記載の成形体。
８．－３０℃から２００℃の温度領域において、単位温度当たりの収縮率が０．０７％／℃以上である１～７のいずれかに記載の成形体。
９．１～２０ＭＰａの引張荷重状態で、加熱による単位温度当たりの収縮率が０．０７％／℃以上である１～８のいずれかに記載の成形体。
１０．５０℃の温度変化の加熱による収縮後に５０℃降温したときの復元率が、９０％以上である１～９のいずれかに記載の成形体。
１１．オレフィン系重合体からなる１～１０のいずれかに記載の成形体。
１２．ポリエチレンからなる１～１１のいずれかに記載の成形体。
１３．前記成形体が、繊維状、板状、シート状もしくはフィルム状であり、又はこれらの１種以上の多層構造を有する１～１２のいずれかに記載の成形体。
１４．前記成形体が繊維状であり、該繊維状成形体の単繊維の繊度が５０～１００００ｄｔｅｘである１３に記載の成形体。
１５．前記成形体が繊維状であり、該繊維状成形体の単繊維の直径が８０～１２００μｍである１３または１４に記載の成形体。
１６．コイル形状に形成された１～１５のいずれかに記載の成形体。
１７．以下（１）～（３）をすべて満たす１６に記載の成形体。
（１）繊維軸に対して垂直方向から測定したX線回折パターンについて、２θ＝１０°から３０°の区間に１つ以上のピークがある。
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上である。
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下である。
１８．バネ指数Ｄ／ｄが０．５以上であり、前記コイル形状の平均直径Ｄが１００～２０００μｍである１６または１７に記載の成形体。
Ｄはコイル平均直径（μｍ）を示し、ｄは単繊維直径（μｍ）を示す。
１９．密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレン２０～８０質量％と、密度が０．８６０～０．８８０ｇ／ｃｍ３である直鎖状低密度ポリエチレン２０～８０質量％と、を含有する混合物を含む１６～１８のいずれかに記載の成形体。
２０．前記混合物の密度が０．８６０～０．９４０ｇ／ｃｍ３である１９に記載の成形体。
２１．撚数が１～３０回／ｍｍである１６～２０のいずれかに記載の成形体。
２２．可逆的伸縮性を有する成形体であって、可逆的熱伸縮性を有さない部分を部分的に有する１～２１のいずれかに記載の成形体。
２３．前記１～２２のいずれかに記載の成形体を含む繊維製品。
２４．織物、編物、不織布、又は紐である２３に記載の繊維製品。
２５．前記繊維製品が織物であって、経糸または緯糸の一方が前記成形体を含み、他方が前記成形体を含まず且つ絶縁被膜で覆われた電熱線を含む２３に記載の繊維製品。
２６．前記電熱線が、連続した１本の電熱線である２５に記載の繊維製品。
２７．前記電熱線が、複数本の電熱線からなる２５に記載の繊維製品。
２８．前記電熱線の直径が２０～２０００μｍである２５～２７のいずれかに記載の繊維製品。
２９．前記織物の組織が、平織、綾織、カラミ織および朱子織のいずれか、またはこれらの組織の組み合わせである２３～２８のいずれかに記載の繊維製品。
３０．一辺の長さが５０～１０００ｍｍ、他の辺の長さが５～２００ｍｍである２３～２９のいずれかに記載の繊維製品。
３１．前記１～２２のいずれかに記載の成形体が並行配列および／または直列配列されているアクチュエータ。
３２．前記２３～２９のいずれかに記載の繊維製品が積層した積層物を含むアクチュエータモジュール。
３３．前記３２に記載のアクチュエータモジュールを駆動部として備えるアシストスーツ。 1. 1. A molded product having a gel fraction of 10% or more, a crystal orientation degree of 80% or more, and a crystallinity of 60% or less.
2. 2. A molded product having a gel fraction of 10% or more, a crystal orientation degree of 60% or more, and a coil shape.
3. 3. The molded product according to 1 or 2, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher.
4. The molded product according to any one of 1 to 3, wherein the shrinkage rate when a temperature change of 50 ° C. is applied by heating is 3.5% or more.
5. The molded product according to any one of 1 to 4, which has a crosslinked structure inside the molded product.
6. 5. The molded product according to 5, wherein the crosslinked structure includes a silane crosslink.
7. The molded product according to any one of 1 to 6, which has reversible thermal elasticity and has a shrinkage rate of 0.07% / ° C. or higher per unit temperature due to heating.
8. The molded product according to any one of 1 to 7, wherein the shrinkage rate per unit temperature is 0.07% / ° C. or higher in the temperature range of −30 ° C. to 200 ° C.
9. The molded product according to any one of 1 to 8, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher under a tensile load of 9.1 to 20 MPa.
10. The molded product according to any one of 1 to 9, wherein the restoration rate when the temperature is lowered to 50 ° C. after shrinking due to heating with a temperature change of 10.50 ° C. is 90% or more.
11. The molded product according to any one of 1 to 10, which is made of an olefin polymer.
12. The molded product according to any one of 1 to 11 made of polyethylene.
13. The molded product according to any one of 1 to 12, wherein the molded product is in the form of a fiber, a plate, a sheet, or a film, or has one or more of these multilayer structures.
14. 13. The molded product according to 13, wherein the molded product is fibrous and the fineness of the single fiber of the fibrous molded product is 50 to 10000 dtex.
15. 13. The molded product according to 13 or 14, wherein the molded product is fibrous and the diameter of a single fiber of the fibrous molded product is 80 to 1200 μm.
16. The molded product according to any one of 1 to 15 formed in a coil shape.
17. 16. The molded product according to 16, which satisfies all of the following (1) to (3).
(1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the peak with the highest intensity, or the intensity of the peak with the highest intensity is more than double the intensity of the peak with the next highest intensity.
(3) The degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material.
18. 16. The molded product according to 16 or 17, wherein the spring index D / d is 0.5 or more, and the average diameter D of the coil shape is 100 to 2000 μm.
D indicates the coil average diameter (μm), and d indicates the single fiber diameter (μm).
19. One or more polyethylenes 20-80 selected from linear low density polyethylene with a density of 0.881 to 0.941 g / cm 3 and high density polyethylene with a density of 0.942 to 0.970 g / cm 3 . The molded product according to any one of 16 to 18, which comprises a mixture containing 20 to 80% by mass of linear low-density polyethylene having a density of 0.860 to 0.880 g / cm 3 and 20 to 80% by mass.
20. 19. The molded article according to 19, wherein the density of the mixture is 0.860 to 0.940 g / cm 3 .
21. The molded product according to any one of 16 to 20, wherein the number of twists is 1 to 30 times / mm.
22. The molded product according to any one of 1 to 21, which is a molded product having reversible elasticity and partially has a portion not having reversible thermal elasticity.
23. A textile product containing the molded product according to any one of 1 to 22 above.
24. 23. The textile product according to 23, which is a woven fabric, a knitted fabric, a non-woven fabric, or a string.
25. 23. The textile product according to 23, wherein the textile product is a woven fabric, one of which is a warp or a weft containing the molded body, and the other is a heating wire which does not contain the molded body and is covered with an insulating coating.
26. 25. The textile product according to 25, wherein the heating wire is one continuous heating wire.
27. 25. The textile product according to 25, wherein the heating wire is composed of a plurality of heating wires.
28. The textile product according to any one of 25 to 27, wherein the heating wire has a diameter of 20 to 2000 μm.
29. The textile product according to any one of 23 to 28, wherein the texture of the woven fabric is any of plain weave, twill weave, Karami weave and satin weave, or a combination of these textures.
30. The textile product according to any one of 23 to 29, wherein the length of one side is 50 to 1000 mm and the length of the other side is 5 to 200 mm.
31. An actuator in which the compacts according to any one of 1 to 22 are arranged in parallel and / or in series.
32. An actuator module including a laminate in which the textile products according to any one of 23 to 29 are laminated.
33. An assist suit including the actuator module according to 32 as a drive unit.
本発明の一態様によれば、可逆的熱伸縮性に優れる成形体、繊維製品及びアクチュエータを提供することができる。
また、本発明の他の態様によれば、繰り返し耐久性が高く、安全に使用できるアシストスーツ、およびそのパーツとなるアクチュエータモジュールを提供することができる。 According to one aspect of the present invention, it is possible to provide a molded product, a textile product and an actuator having excellent reversible thermal elasticity.
Further, according to another aspect of the present invention, it is possible to provide an assist suit having high repeatability and safe use, and an actuator module as a part thereof.
また、本発明の他の態様によれば、繰り返し耐久性が高く、安全に使用できるアシストスーツ、およびそのパーツとなるアクチュエータモジュールを提供することができる。 According to one aspect of the present invention, it is possible to provide a molded product, a textile product and an actuator having excellent reversible thermal elasticity.
Further, according to another aspect of the present invention, it is possible to provide an assist suit having high repeatability and safe use, and an actuator module as a part thereof.
本発明の実施形態の成形体の第１の態様は、ゲル分率が１０％以上であり、結晶配向度が８０％以上であり、結晶化度が６０％以下である。
The first aspect of the molded product of the embodiment of the present invention is a gel fraction of 10% or more, a crystal orientation degree of 80% or more, and a crystallinity of 60% or less.
本発明の実施形態の成形体は、ゲル分率が１０％以上であることが好ましい。
ゲル分率は架橋度を表すものであり、数値が高いほど架橋度が高いことを示す。ゲル分率は、後述のゲル分率の測定方法により測定することができる。
本発明の実施形態の成形体は、架橋度が高くなるほど熱収縮の効果が得られやすいため、ゲル分率が１０％以上であると、加熱による単位温度当たりの熱収縮率を十分に高くできる。この観点から、前記ゲル分率は３０％以上がより好ましく、５０％以上がさらに好ましく、６０％以上が特に好ましく、７０％以上が最も好ましい。ゲル分率は、ポリマーの架橋度を高くし、分子量を増大させることで高くすることができる。ゲル分率の上限は、特に制限されないが、１００％以下に設定でき、又は９５％以下もしくは９０％以下に設定することができる。 The molded product of the embodiment of the present invention preferably has a gel fraction of 10% or more.
The gel fraction indicates the degree of cross-linking, and the higher the value, the higher the degree of cross-linking. The gel fraction can be measured by the method for measuring the gel fraction described later.
In the molded product of the embodiment of the present invention, the effect of heat shrinkage is more likely to be obtained as the degree of cross-linking increases. Therefore, when the gel fraction is 10% or more, the heat shrinkage rate per unit temperature due to heating can be sufficiently increased. .. From this viewpoint, the gel fraction is more preferably 30% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more. The gel fraction can be increased by increasing the degree of cross-linking of the polymer and increasing the molecular weight. The upper limit of the gel fraction is not particularly limited, but can be set to 100% or less, or can be set to 95% or less or 90% or less.
ゲル分率は架橋度を表すものであり、数値が高いほど架橋度が高いことを示す。ゲル分率は、後述のゲル分率の測定方法により測定することができる。
本発明の実施形態の成形体は、架橋度が高くなるほど熱収縮の効果が得られやすいため、ゲル分率が１０％以上であると、加熱による単位温度当たりの熱収縮率を十分に高くできる。この観点から、前記ゲル分率は３０％以上がより好ましく、５０％以上がさらに好ましく、６０％以上が特に好ましく、７０％以上が最も好ましい。ゲル分率は、ポリマーの架橋度を高くし、分子量を増大させることで高くすることができる。ゲル分率の上限は、特に制限されないが、１００％以下に設定でき、又は９５％以下もしくは９０％以下に設定することができる。 The molded product of the embodiment of the present invention preferably has a gel fraction of 10% or more.
The gel fraction indicates the degree of cross-linking, and the higher the value, the higher the degree of cross-linking. The gel fraction can be measured by the method for measuring the gel fraction described later.
In the molded product of the embodiment of the present invention, the effect of heat shrinkage is more likely to be obtained as the degree of cross-linking increases. Therefore, when the gel fraction is 10% or more, the heat shrinkage rate per unit temperature due to heating can be sufficiently increased. .. From this viewpoint, the gel fraction is more preferably 30% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more. The gel fraction can be increased by increasing the degree of cross-linking of the polymer and increasing the molecular weight. The upper limit of the gel fraction is not particularly limited, but can be set to 100% or less, or can be set to 95% or less or 90% or less.
結晶配向度は高いほど、成形体の延伸方向にそって高分子鎖が配列し、成形体の延伸方向に対して異方的な熱収縮効果を十分に発現できる。そのため、本発明の実施形態の成形体は、その結晶配向度は８０％以上が好ましく、８４％以上がより好ましく、９０％以上がさらに好ましい。結晶配向度の上限は、特に制限されないが、１００％以下に設定でき、又は９８％以下もしくは９５％以下に設定できる。なお、後述の第２の実施形態の成形体は、コイル形状を有し、その結晶配向度は６０％以上が好ましい。
The higher the degree of crystal orientation, the more the polymer chains are arranged along the stretching direction of the molded body, and the anisotropic heat shrinkage effect can be sufficiently exhibited with respect to the stretching direction of the molded body. Therefore, the molded product of the embodiment of the present invention preferably has a crystal orientation degree of 80% or more, more preferably 84% or more, still more preferably 90% or more. The upper limit of the degree of crystal orientation is not particularly limited, but can be set to 100% or less, or 98% or less or 95% or less. The molded product of the second embodiment described later has a coil shape, and the degree of crystal orientation thereof is preferably 60% or more.
本発明の実施形態の成形体の結晶配向度は、延伸操作を行うことによって上げることができる。延伸操作は一段あるいは二段以上の多段で行うことができる。延伸倍率は、結晶配向度を上げる観点から、延伸倍率は２倍以上、好ましくは３倍以上であれば十分に結晶配向度を上げることができる。延伸操作を二段以上の多段で行う場合は、一段目の延伸倍率を２倍以上、好ましくは３倍以上に設定し、二段目の延伸倍率は、一段目より小さい延伸倍率であって、例えば１．０５倍以上２．０倍未満、あるいは１．０５～１．５倍の範囲に設定できる。延伸倍率の上限は特に制限されないが、過剰な延伸による不具合の発生を防ぐ点から、２０倍以下が好ましく、１０倍以下がより好ましく、６倍以下がさらに好ましい。
The degree of crystal orientation of the molded product according to the embodiment of the present invention can be increased by performing a stretching operation. The stretching operation can be performed in one stage or in multiple stages of two or more stages. From the viewpoint of increasing the degree of crystal orientation, the draw ratio can be sufficiently increased if the draw ratio is 2 times or more, preferably 3 times or more. When the stretching operation is performed in multiple stages of two or more stages, the stretching ratio of the first stage is set to 2 times or more, preferably 3 times or more, and the stretching ratio of the second stage is smaller than that of the first stage. For example, it can be set in the range of 1.05 times or more and less than 2.0 times, or 1.05 to 1.5 times. The upper limit of the draw ratio is not particularly limited, but 20 times or less is preferable, 10 times or less is more preferable, and 6 times or less is further preferable, from the viewpoint of preventing the occurrence of defects due to excessive stretching.
本発明の実施形態の成形体は、結晶化度が６０％以下であることが好ましい。
結晶化度が低いほど、加熱時の熱収縮に寄与できる非晶が多く、良好な熱収縮効果を発現できるため、結晶化度は６０％以下が好ましく、５０％以下がより好ましく、４０％以下がさらに好ましい。結晶化度の下限は特に制限されないが、０％以上に設定でき、又は５％以上もしくは１０％以上に設定することができる。 The molded product of the embodiment of the present invention preferably has a crystallinity of 60% or less.
The lower the crystallinity, the more amorphous that can contribute to heat shrinkage during heating, and a better heat shrinkage effect can be exhibited. Therefore, the crystallinity is preferably 60% or less, more preferably 50% or less, and more preferably 40% or less. Is even more preferable. The lower limit of the crystallinity is not particularly limited, but can be set to 0% or more, or can be set to 5% or more or 10% or more.
結晶化度が低いほど、加熱時の熱収縮に寄与できる非晶が多く、良好な熱収縮効果を発現できるため、結晶化度は６０％以下が好ましく、５０％以下がより好ましく、４０％以下がさらに好ましい。結晶化度の下限は特に制限されないが、０％以上に設定でき、又は５％以上もしくは１０％以上に設定することができる。 The molded product of the embodiment of the present invention preferably has a crystallinity of 60% or less.
The lower the crystallinity, the more amorphous that can contribute to heat shrinkage during heating, and a better heat shrinkage effect can be exhibited. Therefore, the crystallinity is preferably 60% or less, more preferably 50% or less, and more preferably 40% or less. Is even more preferable. The lower limit of the crystallinity is not particularly limited, but can be set to 0% or more, or can be set to 5% or more or 10% or more.
本発明の実施形態の成形体の第２の態様は、ゲル分率が１０％以上であり、結晶配向度が６０％以上であり、コイル形状である。
The second aspect of the molded product of the embodiment of the present invention has a gel fraction of 10% or more, a crystal orientation degree of 60% or more, and a coil shape.
本発明の実施形態の成形体は、コイル形状に形成することができる。
コイル形状の成形体は、構成される成形体の熱収縮性を大幅に増幅することができる。
図２に、コイル形状の成形体の一例を示す。図中のｄはコイルを構成する繊維の単繊維直径、Ｄはコイル平均直径（コイル平均径：コイル外径とコイル内径の平均）を示す。
コイル形状の成形体の作製方法は、特に限定されないが、例えば、一定荷重下で１本から複数本の繊維を捩じり続けて、コイル形状とした後、アニール処理をすることで安定なコイル形状を得ることができる。また、コイル化する直前に芯棒を入れて、コイル化することにより、芯棒の直径に応じて、図３に示すようにコイル平均直径Ｄを大きくすることができ、得られたコイル形状の成形体は良好な収縮変位を得ることができる。 The molded body of the embodiment of the present invention can be formed into a coil shape.
The coil-shaped molded body can significantly amplify the heat shrinkage of the formed molded body.
FIG. 2 shows an example of a coil-shaped molded body. In the figure, d indicates the single fiber diameter of the fibers constituting the coil, and D indicates the coil average diameter (coil average diameter: the average of the coil outer diameter and the coil inner diameter).
The method for producing the coil-shaped molded body is not particularly limited, but for example, a stable coil is formed by continuously twisting one to a plurality of fibers under a constant load to form a coil shape and then annealing. The shape can be obtained. Further, by inserting the core rod immediately before coiling and coiling, the coil average diameter D can be increased as shown in FIG. 3 according to the diameter of the core rod, and the obtained coil shape can be increased. The molded body can obtain a good contraction displacement.
コイル形状の成形体は、構成される成形体の熱収縮性を大幅に増幅することができる。
図２に、コイル形状の成形体の一例を示す。図中のｄはコイルを構成する繊維の単繊維直径、Ｄはコイル平均直径（コイル平均径：コイル外径とコイル内径の平均）を示す。
コイル形状の成形体の作製方法は、特に限定されないが、例えば、一定荷重下で１本から複数本の繊維を捩じり続けて、コイル形状とした後、アニール処理をすることで安定なコイル形状を得ることができる。また、コイル化する直前に芯棒を入れて、コイル化することにより、芯棒の直径に応じて、図３に示すようにコイル平均直径Ｄを大きくすることができ、得られたコイル形状の成形体は良好な収縮変位を得ることができる。 The molded body of the embodiment of the present invention can be formed into a coil shape.
The coil-shaped molded body can significantly amplify the heat shrinkage of the formed molded body.
FIG. 2 shows an example of a coil-shaped molded body. In the figure, d indicates the single fiber diameter of the fibers constituting the coil, and D indicates the coil average diameter (coil average diameter: the average of the coil outer diameter and the coil inner diameter).
The method for producing the coil-shaped molded body is not particularly limited, but for example, a stable coil is formed by continuously twisting one to a plurality of fibers under a constant load to form a coil shape and then annealing. The shape can be obtained. Further, by inserting the core rod immediately before coiling and coiling, the coil average diameter D can be increased as shown in FIG. 3 according to the diameter of the core rod, and the obtained coil shape can be increased. The molded body can obtain a good contraction displacement.
また、コイル形状の成形体は、複数本の繊維状成形体又はコイル形状の成形体から構成されてもよい。複数本の繊維状成形体から形成されるコイル形状は特に限定されないが、芯となる繊維状成形体又はコイル形状の成形体に、繊維状成形体又はコイル形状の成形体を巻き付けるカバリングしたコイル形状（例えば図４に示す形態）や、互いに合撚されたコイル形状（例えば図５に示す形態）にすることで、安定した収縮変位を得ることができる。図４は、芯となる本発明のコイル形状の成形体に、本発明の繊維状成形体を巻き付けてカバリングしたコイル形状の成形体の一例を示している。図５は、本発明のコイル形状の成形体を合撚したコイル形状の成形体の一例を示している。
Further, the coil-shaped molded body may be composed of a plurality of fibrous molded bodies or coil-shaped molded bodies. The shape of the coil formed from a plurality of fibrous molded bodies is not particularly limited, but the coil shape is covered by winding the fibrous molded body or the coil-shaped molded body around the core fibrous molded body or the coil-shaped molded body. A stable contraction displacement can be obtained by forming the coil shape (for example, the form shown in FIG. 4) or the coil shape twisted together (for example, the form shown in FIG. 5). FIG. 4 shows an example of a coil-shaped molded body in which the fibrous molded body of the present invention is wound and covered around a coil-shaped molded body of the present invention as a core. FIG. 5 shows an example of a coil-shaped molded body obtained by twisting and twisting the coil-shaped molded body of the present invention.
結晶配向度は高いほど、成形体の延伸方向にそって高分子鎖が配列し、成形体の延伸方向に対して異方的な熱収縮効果を十分に発現できる。そのため、本発明の実施形態のコイル形状の成形体の結晶配向度は６０％以上が好ましく、６５％以上がより好ましく、７０％以上がさらに好ましい。結晶配向度の上限は、特に制限されないが、１００％以下に設定でき、又は９８％以下もしくは９５％以下に設定できる。
なお、成形体をコイル形状にすると結晶配向度が下がる傾向にある。 The higher the degree of crystal orientation, the more the polymer chains are arranged along the stretching direction of the molded body, and the anisotropic heat shrinkage effect can be sufficiently exhibited with respect to the stretching direction of the molded body. Therefore, the degree of crystal orientation of the coil-shaped molded product according to the embodiment of the present invention is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more. The upper limit of the degree of crystal orientation is not particularly limited, but can be set to 100% or less, or 98% or less or 95% or less.
When the molded body is formed into a coil shape, the degree of crystal orientation tends to decrease.
なお、成形体をコイル形状にすると結晶配向度が下がる傾向にある。 The higher the degree of crystal orientation, the more the polymer chains are arranged along the stretching direction of the molded body, and the anisotropic heat shrinkage effect can be sufficiently exhibited with respect to the stretching direction of the molded body. Therefore, the degree of crystal orientation of the coil-shaped molded product according to the embodiment of the present invention is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more. The upper limit of the degree of crystal orientation is not particularly limited, but can be set to 100% or less, or 98% or less or 95% or less.
When the molded body is formed into a coil shape, the degree of crystal orientation tends to decrease.
本発明の実施形態のコイル形状の成形体は、その結晶配向度が６０％以上であるのは、コイル形状にすると結晶配向度が下がる傾向にあるためである。
成形体の結晶配向度は、コイル形状にする前の成形体の延伸操作を行うことによって上げることができる。延伸操作は一段あるいは二段以上の多段で行うことができる。延伸倍率は、結晶配向度を上げる観点から、延伸倍率は２倍以上、好ましくは３倍以上であれば十分に結晶配向度を上げることができる。延伸操作を二段以上の多段で行う場合は、一段目の延伸倍率を２倍以上、好ましくは３倍以上に設定し、二段目の延伸倍率は、一段目より小さい延伸倍率であって、例えば１．０５倍以上２．０倍未満、あるいは１．０５～１．５倍の範囲に設定できる。延伸倍率の上限は特に制限されないが、過剰な延伸による不具合の発生を防ぐ点から、２０倍以下が好ましく、１０倍以下がより好ましく、６倍以下がさらに好ましい。 The coil-shaped molded body of the embodiment of the present invention has a crystal orientation degree of 60% or more because the crystal orientation degree tends to decrease when the coil shape is formed.
The degree of crystal orientation of the molded product can be increased by performing a stretching operation of the molded product before forming the coil shape. The stretching operation can be performed in one stage or in multiple stages of two or more stages. From the viewpoint of increasing the degree of crystal orientation, the draw ratio can be sufficiently increased if the draw ratio is 2 times or more, preferably 3 times or more. When the stretching operation is performed in multiple stages of two or more stages, the stretching ratio of the first stage is set to 2 times or more, preferably 3 times or more, and the stretching ratio of the second stage is smaller than that of the first stage. For example, it can be set in the range of 1.05 times or more and less than 2.0 times, or 1.05 to 1.5 times. The upper limit of the draw ratio is not particularly limited, but 20 times or less is preferable, 10 times or less is more preferable, and 6 times or less is further preferable, from the viewpoint of preventing the occurrence of defects due to excessive stretching.
成形体の結晶配向度は、コイル形状にする前の成形体の延伸操作を行うことによって上げることができる。延伸操作は一段あるいは二段以上の多段で行うことができる。延伸倍率は、結晶配向度を上げる観点から、延伸倍率は２倍以上、好ましくは３倍以上であれば十分に結晶配向度を上げることができる。延伸操作を二段以上の多段で行う場合は、一段目の延伸倍率を２倍以上、好ましくは３倍以上に設定し、二段目の延伸倍率は、一段目より小さい延伸倍率であって、例えば１．０５倍以上２．０倍未満、あるいは１．０５～１．５倍の範囲に設定できる。延伸倍率の上限は特に制限されないが、過剰な延伸による不具合の発生を防ぐ点から、２０倍以下が好ましく、１０倍以下がより好ましく、６倍以下がさらに好ましい。 The coil-shaped molded body of the embodiment of the present invention has a crystal orientation degree of 60% or more because the crystal orientation degree tends to decrease when the coil shape is formed.
The degree of crystal orientation of the molded product can be increased by performing a stretching operation of the molded product before forming the coil shape. The stretching operation can be performed in one stage or in multiple stages of two or more stages. From the viewpoint of increasing the degree of crystal orientation, the draw ratio can be sufficiently increased if the draw ratio is 2 times or more, preferably 3 times or more. When the stretching operation is performed in multiple stages of two or more stages, the stretching ratio of the first stage is set to 2 times or more, preferably 3 times or more, and the stretching ratio of the second stage is smaller than that of the first stage. For example, it can be set in the range of 1.05 times or more and less than 2.0 times, or 1.05 to 1.5 times. The upper limit of the draw ratio is not particularly limited, but 20 times or less is preferable, 10 times or less is more preferable, and 6 times or less is further preferable, from the viewpoint of preventing the occurrence of defects due to excessive stretching.
本発明の実施形態の成形体は、加熱による単位温度当たりの収縮率が０．０７％／℃以上であることが好ましい。
The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
本発明の実施形態の成形体は、任意の荷重下で、加熱した場合の単位温度当たりの熱収縮率が０．０７％／℃以上であれば、アクチュエータとして十分な変位をとることが可能である。前記観点から、単位温度当たりの熱収縮率は０．０８％／℃以上がより好ましく、０．１０％／℃以上がさらに好ましい。
単位温度当たりの熱収縮率が高いほどアクチュエータとして産業上の応用性が高く、上限は特に制限は無いが、０．２０％／℃であれば、アクチュエータとしての性能が非常に高く、０．１８％／℃であれば十分有効である。したがって、単位温度当たりの熱収縮率は０．０７％／℃以上０．２０％／℃以下の範囲、もしくは０．０７％／℃以上０．１８％／℃以下の範囲に設定することができる。
この場合の収縮率は、引張応力が５ＭＰａとなるように荷重をかけたときの収縮率である。
本発明におけるアクチュエータは、ソフトアクチュエータと呼ばれることもあり、素材自体が伸縮性を有するものである。 The molded product according to the embodiment of the present invention can be sufficiently displaced as an actuator as long as the heat shrinkage rate per unit temperature when heated under an arbitrary load is 0.07% / ° C. or higher. be. From the above viewpoint, the heat shrinkage rate per unit temperature is more preferably 0.08% / ° C. or higher, further preferably 0.10% / ° C. or higher.
The higher the heat shrinkage rate per unit temperature, the higher the industrial applicability as an actuator, and the upper limit is not particularly limited, but if it is 0.20% / ° C, the performance as an actuator is very high, 0.18. % / ° C is sufficiently effective. Therefore, the heat shrinkage rate per unit temperature can be set in the range of 0.07% / ° C. or higher and 0.20% / ° C. or lower, or 0.07% / ° C. or higher and 0.18% / ° C. or lower. ..
The shrinkage rate in this case is the shrinkage rate when a load is applied so that the tensile stress becomes 5 MPa.
The actuator in the present invention is sometimes called a soft actuator, and the material itself has elasticity.
単位温度当たりの熱収縮率が高いほどアクチュエータとして産業上の応用性が高く、上限は特に制限は無いが、０．２０％／℃であれば、アクチュエータとしての性能が非常に高く、０．１８％／℃であれば十分有効である。したがって、単位温度当たりの熱収縮率は０．０７％／℃以上０．２０％／℃以下の範囲、もしくは０．０７％／℃以上０．１８％／℃以下の範囲に設定することができる。
この場合の収縮率は、引張応力が５ＭＰａとなるように荷重をかけたときの収縮率である。
本発明におけるアクチュエータは、ソフトアクチュエータと呼ばれることもあり、素材自体が伸縮性を有するものである。 The molded product according to the embodiment of the present invention can be sufficiently displaced as an actuator as long as the heat shrinkage rate per unit temperature when heated under an arbitrary load is 0.07% / ° C. or higher. be. From the above viewpoint, the heat shrinkage rate per unit temperature is more preferably 0.08% / ° C. or higher, further preferably 0.10% / ° C. or higher.
The higher the heat shrinkage rate per unit temperature, the higher the industrial applicability as an actuator, and the upper limit is not particularly limited, but if it is 0.20% / ° C, the performance as an actuator is very high, 0.18. % / ° C is sufficiently effective. Therefore, the heat shrinkage rate per unit temperature can be set in the range of 0.07% / ° C. or higher and 0.20% / ° C. or lower, or 0.07% / ° C. or higher and 0.18% / ° C. or lower. ..
The shrinkage rate in this case is the shrinkage rate when a load is applied so that the tensile stress becomes 5 MPa.
The actuator in the present invention is sometimes called a soft actuator, and the material itself has elasticity.
本発明の実施形態の成形体は、加熱により５０℃の温度変化を与えた時の収縮率が３．５％以上であることが好ましい。
The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 3.5% or more when a temperature change of 50 ° C. is applied by heating.
本発明の実施形態の成形体は、－３０℃から２００℃の温度領域において、５０℃の温度変化を与えたときの収縮率が３．５％以上であることが好ましい。
－３０℃から２００℃の温度領域において５０℃の温度変化を与えたときの、収縮率が３．５％以上であれば、実現可能な変化でアクチュエータとして高い変位をとることができるため、アプリケーションの応用範囲の広い優れたアクチュエータとして有効である。前記観点から、前記収縮率は４．０％以上が好ましく、５．０％／℃以上がより好ましい。この収縮率の上限は特に制限は無いが、１０．０％であれば、アクチュエータとしては十分有効である。したがって、この収縮率は３．５～１０．０％の範囲に設定できる。 The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 3.5% or more when a temperature change of 50 ° C. is applied in a temperature range of −30 ° C. to 200 ° C.
If the shrinkage rate is 3.5% or more when a temperature change of 50 ° C is applied in the temperature range of -30 ° C to 200 ° C, it is possible to take a high displacement as an actuator with a feasible change, so this is an application. It is effective as an excellent actuator with a wide range of applications. From the above viewpoint, the shrinkage rate is preferably 4.0% or more, more preferably 5.0% / ° C. or higher. The upper limit of this shrinkage rate is not particularly limited, but if it is 10.0%, it is sufficiently effective as an actuator. Therefore, this shrinkage rate can be set in the range of 3.5 to 10.0%.
－３０℃から２００℃の温度領域において５０℃の温度変化を与えたときの、収縮率が３．５％以上であれば、実現可能な変化でアクチュエータとして高い変位をとることができるため、アプリケーションの応用範囲の広い優れたアクチュエータとして有効である。前記観点から、前記収縮率は４．０％以上が好ましく、５．０％／℃以上がより好ましい。この収縮率の上限は特に制限は無いが、１０．０％であれば、アクチュエータとしては十分有効である。したがって、この収縮率は３．５～１０．０％の範囲に設定できる。 The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 3.5% or more when a temperature change of 50 ° C. is applied in a temperature range of −30 ° C. to 200 ° C.
If the shrinkage rate is 3.5% or more when a temperature change of 50 ° C is applied in the temperature range of -30 ° C to 200 ° C, it is possible to take a high displacement as an actuator with a feasible change, so this is an application. It is effective as an excellent actuator with a wide range of applications. From the above viewpoint, the shrinkage rate is preferably 4.0% or more, more preferably 5.0% / ° C. or higher. The upper limit of this shrinkage rate is not particularly limited, but if it is 10.0%, it is sufficiently effective as an actuator. Therefore, this shrinkage rate can be set in the range of 3.5 to 10.0%.
本発明の実施形態の成形体は、成形体内部に架橋構造を有することが好ましい。前記架橋構造とは、成形体を構成する高分子間が架橋している構造を意味する。
架橋構造を有することで、エントロピー弾性により、単位温度当たりの高い熱収縮率が得られやすい。 The molded body of the embodiment of the present invention preferably has a crosslinked structure inside the molded body. The crosslinked structure means a structure in which the polymers constituting the molded product are crosslinked.
By having a crosslinked structure, it is easy to obtain a high heat shrinkage rate per unit temperature due to the entropy elasticity.
架橋構造を有することで、エントロピー弾性により、単位温度当たりの高い熱収縮率が得られやすい。 The molded body of the embodiment of the present invention preferably has a crosslinked structure inside the molded body. The crosslinked structure means a structure in which the polymers constituting the molded product are crosslinked.
By having a crosslinked structure, it is easy to obtain a high heat shrinkage rate per unit temperature due to the entropy elasticity.
架橋の種類としては、特に限定されないが、フェノールと塩基触媒と過剰のホルムアミドとの反応による架橋、エポキシ基の開環反応を利用したアミン、カルボン酸無水物、ジシアンジアミド、ケチミンとの反応や酸触媒での反応による架橋、ウレアやメラミンやベンゾグアナミンとホルムアルデヒドを弱アルカリ触媒の存在下で縮合させる反応による架橋、二つ以上のイソシアナート基を有する化合物と、二官能以上の水酸基またはアミン化合物との反応によるウレタン結合または尿素結合による架橋、シラノールの縮合反応による架橋、側鎖や主鎖に二重結合を持つ化合物の過酸化物下での反応による架橋、Ａｌ、Ｔｉ、Ｚｒのアルコキシドやキレート化合物を架橋剤として用いた配位結合による架橋、光ラジカル重合開始剤を用いた反応による架橋などが挙げられる。
The type of cross-linking is not particularly limited, but is cross-linked by the reaction of phenol with a base catalyst and excess formamide, the reaction with amine, carboxylic acid anhydride, dicyandiamide, ketimine or acid catalyst using the ring-opening reaction of the epoxy group. Cross-linking by the reaction in, cross-linking by the reaction of condensing urea, melamine, benzoguanamine and formaldehyde in the presence of a weak alkaline catalyst, reaction of a compound having two or more isosianate groups with a bifunctional or higher hydroxyl group or amine compound. Cross-linking by urethane bond or urea bond, cross-linking by condensation reaction of silanol, cross-linking by reaction under peroxide of compound having double bond in side chain or main chain, alkoxide or chelate compound of Al, Ti, Zr Examples thereof include cross-linking by a coordination bond used as a cross-linking agent and cross-linking by a reaction using a photoradical polymerization initiator.
前記の架橋の中でも、シラノール基間の縮合反応による結合（シラン結合）で形成されたシラン架橋が好ましい。
一例として、シラン変性ポリオレフィンにおけるアルコキシシラン（不飽和シラン化合物）のグラフト率（変性量）を増やし、シラノール縮合触媒の種類と配合量、架橋させる際の条件（温度、時間）等を変えることにより、シラン架橋ポリオレフィン成形体のゲル分率を調整することができる。 Among the above-mentioned crosslinks, a silane crosslink formed by a bond (silane bond) by a condensation reaction between silanol groups is preferable.
As an example, by increasing the graft ratio (modification amount) of alkoxysilane (unsaturated silane compound) in the silane-modified polyolefin, the type and blending amount of the silanol condensation catalyst, the conditions (temperature, time) for crosslinking, etc. are changed. The gel fraction of the silane crosslinked polyolefin molded product can be adjusted.
一例として、シラン変性ポリオレフィンにおけるアルコキシシラン（不飽和シラン化合物）のグラフト率（変性量）を増やし、シラノール縮合触媒の種類と配合量、架橋させる際の条件（温度、時間）等を変えることにより、シラン架橋ポリオレフィン成形体のゲル分率を調整することができる。 Among the above-mentioned crosslinks, a silane crosslink formed by a bond (silane bond) by a condensation reaction between silanol groups is preferable.
As an example, by increasing the graft ratio (modification amount) of alkoxysilane (unsaturated silane compound) in the silane-modified polyolefin, the type and blending amount of the silanol condensation catalyst, the conditions (temperature, time) for crosslinking, etc. are changed. The gel fraction of the silane crosslinked polyolefin molded product can be adjusted.
架橋処理を行うには、まず、未延伸物を延伸配向し、結晶配向した延伸成形体を得た後に、架橋処理を行うことで、生産性を損なうことなく、成形体の力学物性と結晶配向を維持したまま架橋構造を形成することができる。
In order to carry out the cross-linking treatment, first, the unstretched product is stretch-oriented to obtain a crystal-oriented stretched molded product, and then the cross-linking treatment is performed, so that the mechanical properties and crystal orientation of the molded product are not impaired. The crosslinked structure can be formed while maintaining the above.
本発明の実施形態の成形体は、前記架橋構造としてシラン架橋を有することが好ましい。
本発明の実施形態の成形体は、シラン架橋を有することで、単位温度当たりの高い熱収縮率が得られやすい。
シラン架橋は、事前にシラン変性した重合体を、水含有雰囲気中に曝露し、シラノール基間の反応（いわゆるシラン結合）を進行させることで形成することができる。
詳述すると、シラン変性高分子においては、グラフト導入されたアルコキシシラン（例えば不飽和シラン化合物）由来の加水分解可能なアルコキシ基が、シラノール縮合触媒の存在下、水と反応して加水分解することによりシラノール基が生成し、さらにシラノール基同士が脱水縮合することにより、シラン変性高分子間で架橋反応が進行し、結果、シラン変性高分子同士が結合して、シラン架橋を形成する。 The molded product of the embodiment of the present invention preferably has a silane crosslink as the crosslinked structure.
Since the molded product of the embodiment of the present invention has a silane crosslink, it is easy to obtain a high heat shrinkage rate per unit temperature.
Silane cross-linking can be formed by exposing a pre-silane-modified polymer to a water-containing atmosphere and allowing the reaction between silanol groups (so-called silane bond) to proceed.
More specifically, in a silane-modified polymer, a hydrolyzable alkoxy group derived from a graft-introduced alkoxysilane (for example, an unsaturated silane compound) reacts with water to hydrolyze in the presence of a silanol condensation catalyst. As a result, silanol groups are generated, and the silanol groups are dehydrated and condensed, so that the cross-linking reaction proceeds between the silane-modified polymers, and as a result, the silane-modified polymers are bonded to each other to form a silane bridge.
本発明の実施形態の成形体は、シラン架橋を有することで、単位温度当たりの高い熱収縮率が得られやすい。
シラン架橋は、事前にシラン変性した重合体を、水含有雰囲気中に曝露し、シラノール基間の反応（いわゆるシラン結合）を進行させることで形成することができる。
詳述すると、シラン変性高分子においては、グラフト導入されたアルコキシシラン（例えば不飽和シラン化合物）由来の加水分解可能なアルコキシ基が、シラノール縮合触媒の存在下、水と反応して加水分解することによりシラノール基が生成し、さらにシラノール基同士が脱水縮合することにより、シラン変性高分子間で架橋反応が進行し、結果、シラン変性高分子同士が結合して、シラン架橋を形成する。 The molded product of the embodiment of the present invention preferably has a silane crosslink as the crosslinked structure.
Since the molded product of the embodiment of the present invention has a silane crosslink, it is easy to obtain a high heat shrinkage rate per unit temperature.
Silane cross-linking can be formed by exposing a pre-silane-modified polymer to a water-containing atmosphere and allowing the reaction between silanol groups (so-called silane bond) to proceed.
More specifically, in a silane-modified polymer, a hydrolyzable alkoxy group derived from a graft-introduced alkoxysilane (for example, an unsaturated silane compound) reacts with water to hydrolyze in the presence of a silanol condensation catalyst. As a result, silanol groups are generated, and the silanol groups are dehydrated and condensed, so that the cross-linking reaction proceeds between the silane-modified polymers, and as a result, the silane-modified polymers are bonded to each other to form a silane bridge.
シラン変性高分子は、ポリオレフィン等の高分子にアルコキシシランをグラフト導入してシラン変性することにより製造することができる。シラン変性の方法は、公知の手法に従って行うことができ、特に限定されない。例えば、溶液変性、溶融変性、電子線や電離放射線の照射による固相変性、超臨界流体中での変性等が好適に用いられる。これらの中でも、設備やコスト競争力に優れた溶融変性が好ましく、連続生産性に優れた押出機を用いた溶融混練変性がさらに好ましい。溶融混練変性に用いられる装置としては、例えば単軸スクリュー押出機、二軸スクリュー押出機、バンバリーミキサー、ロールミキサー等が挙げられる。これらの中でも連続生産性に優れた単軸スクリュー押出機、二軸スクリュー押出機が好ましい。
The silane-modified polymer can be produced by graft-introducing alkoxysilane into a polymer such as polyolefin and silane-modifying. The method of silane modification can be carried out according to a known method and is not particularly limited. For example, solution denaturation, melt denaturation, solid phase denaturation by irradiation with electron beam or ionizing radiation, denaturation in a supercritical fluid, and the like are preferably used. Among these, melt modification with excellent equipment and cost competitiveness is preferable, and melt kneading modification using an extruder with excellent continuous productivity is more preferable. Examples of the apparatus used for melt-kneading modification include a single-screw screw extruder, a twin-screw screw extruder, a Banbury mixer, a roll mixer, and the like. Among these, a single-screw extruder and a twin-screw screw extruder having excellent continuous productivity are preferable.
シラン架橋の形成条件は水含有雰囲気中に曝す条件によって決まり、特に限定されないが、通常２０～１３０℃の温度範囲、且つ１分～１週間の時間範囲が好ましく、より好ましくは２０～１３０℃の温度範囲、且つ１時間～１６０時間の時間範囲である。水分を含む空気を使用する場合、相対湿度は１～１００％の範囲内で適宜調整すればよい。
The conditions for forming the silane bridge are determined by the conditions of exposure to the water-containing atmosphere, and are not particularly limited, but are usually preferably in a temperature range of 20 to 130 ° C. and a time range of 1 minute to 1 week, more preferably 20 to 130 ° C. It is in a temperature range and a time range of 1 hour to 160 hours. When air containing moisture is used, the relative humidity may be appropriately adjusted within the range of 1 to 100%.
シラン変性高分子は、変性前の高分子を含む組成物（変性前組成物）と、加水分解可能な有機基を有するオレフィン性不飽和シラン化合物（以下、単に「不飽和シラン化合物」とも称する）とを、ラジカル発生剤の存在下で共重合させることによって得ることができる。この反応において、不飽和シラン化合物は、変性前組成物中の各々の重合体にグラフト化される（グラフト変性）。
The silane-modified polymer is a composition containing a polymer before modification (pre-modification composition) and an olefinically unsaturated silane compound having a hydrolyzable organic group (hereinafter, also simply referred to as “unsaturated silane compound”). Can be obtained by copolymerizing in the presence of a radical generator. In this reaction, the unsaturated silane compound is grafted onto each polymer in the pre-modification composition (graft modification).
加水分解可能な有機基を有するオレフィン性不飽和シラン化合物としては、下記一般式（１）で表されるシラン化合物が好適に用いられる。
ＲＳｉＲ’ｎＹ３－ｎ （１）
（一般式（１）中、Ｒは１価のオレフィン性不飽和炭化水素基を示し、Ｒ’は脂肪族不飽和炭化水素基以外の１価の炭化水素基を示し、Ｙは加水分解し得る有機基を示し、ｎは０、１又は２を示す。） As the olefinically unsaturated silane compound having a hydrolyzable organic group, a silane compound represented by the following general formula (1) is preferably used.
RSiR'n Y 3-n ( 1)
(In the general formula (1), R represents a monovalent olefinically unsaturated hydrocarbon group, R'represents a monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group, and Y can be hydrolyzed. Indicates an organic group, where n indicates 0, 1 or 2).
ＲＳｉＲ’ｎＹ３－ｎ （１）
（一般式（１）中、Ｒは１価のオレフィン性不飽和炭化水素基を示し、Ｒ’は脂肪族不飽和炭化水素基以外の１価の炭化水素基を示し、Ｙは加水分解し得る有機基を示し、ｎは０、１又は２を示す。） As the olefinically unsaturated silane compound having a hydrolyzable organic group, a silane compound represented by the following general formula (1) is preferably used.
RSiR'n Y 3-n ( 1)
(In the general formula (1), R represents a monovalent olefinically unsaturated hydrocarbon group, R'represents a monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group, and Y can be hydrolyzed. Indicates an organic group, where n indicates 0, 1 or 2).
一般式（１）において、Ｒで示される１価のオレフィン性不飽和炭化水素基としては、ビニル基、アリル基、イソプロペニル基、ブテニル基等が挙げられる。Ｒ’で示される脂肪族不飽和炭化水素基以外の１価の炭化水素基としては、メチル基、エチル基、プロピル基、デシル基等のアルキル基；フェニル基等のアリール基が挙げられる。Ｙで示される加水分解し得る有機基としては、メトキシ基、エトキシ基等のアルコキシ基；ホルミルオキシ基、アセトキシ基、プロピオノキシ基等のアシルオキシ基；アルキルアミノ基又はアリールアミノ基等が挙げられる。
In the general formula (1), examples of the monovalent olefinically unsaturated hydrocarbon group represented by R include a vinyl group, an allyl group, an isopropenyl group, a butenyl group and the like. Examples of the monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group represented by R'include an alkyl group such as a methyl group, an ethyl group, a propyl group and a decyl group; and an aryl group such as a phenyl group. Examples of the hydrolyzable organic group represented by Y include an alkoxy group such as a methoxy group and an ethoxy group; an acyloxy group such as a formyloxy group, an acetoxy group and a propionoxy group; an alkylamino group or an arylamino group.
また、より好ましい不飽和シラン化合物としては、例えば、下記一般式（２）で表される化合物が挙げられる。
ＣＨ２＝ＣＨＳｉ（ＯＡ）３ （２）
（一般式（２）中、Ａは炭素数１～８の１価の炭化水素基を示す。） Further, as a more preferable unsaturated silane compound, for example, a compound represented by the following general formula (2) can be mentioned.
CH 2 = CHSi (OA) 3 (2)
(In the general formula (2), A represents a monovalent hydrocarbon group having 1 to 8 carbon atoms.)
ＣＨ２＝ＣＨＳｉ（ＯＡ）３ （２）
（一般式（２）中、Ａは炭素数１～８の１価の炭化水素基を示す。） Further, as a more preferable unsaturated silane compound, for example, a compound represented by the following general formula (2) can be mentioned.
CH 2 = CHSi (OA) 3 (2)
(In the general formula (2), A represents a monovalent hydrocarbon group having 1 to 8 carbon atoms.)
一般式（２）において、Ａで示される炭素数１～８の１価の炭化水素基としては、メチル基、エチル基、イソプロピル基等のアルキル基が挙げられる。上記一般式（２）で表される不飽和シラン化合物としては、具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシランが挙げられる。
In the general formula (2), examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms represented by A include an alkyl group such as a methyl group, an ethyl group and an isopropyl group. Specific examples of the unsaturated silane compound represented by the general formula (2) include vinyltrimethoxysilane and vinyltriethoxysilane.
不飽和シラン化合物としてはまた、下記一般式（３）で表される化合物も好ましく用いることができる。
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣ３Ｈ６Ｓｉ（ＯＡ）３ （３）
（一般式（３）中、Ａは一般式（２）におけるＡと同義である。） As the unsaturated silane compound, a compound represented by the following general formula (3) can also be preferably used.
CH 2 = C (CH 3 ) COOC 3 H 6 Si (OA) 3 (3)
(In the general formula (3), A is synonymous with A in the general formula (2).)
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＣ３Ｈ６Ｓｉ（ＯＡ）３ （３）
（一般式（３）中、Ａは一般式（２）におけるＡと同義である。） As the unsaturated silane compound, a compound represented by the following general formula (3) can also be preferably used.
CH 2 = C (CH 3 ) COOC 3 H 6 Si (OA) 3 (3)
(In the general formula (3), A is synonymous with A in the general formula (2).)
上記一般式（３）で表される不飽和シラン化合物としては、例えばγ－メタクリロイルオキシプロピルトリメトキシシラン、γ－メタクリロイルオキシプロピルトリエトキシシラン等が挙げられる。
Examples of the unsaturated silane compound represented by the above general formula (3) include γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltriethoxysilane.
これらの中でも、不飽和シラン化合物としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－メタクリロイルオキシプロピルトリエトキシシランが好ましい。
なお、これらの不飽和シラン化合物は１種を単独で用いてもよく、２種以上を任意の組合せで併用してもよい。 Among these, as the unsaturated silane compound, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloyloxypropyltriethoxysilane are preferable.
One of these unsaturated silane compounds may be used alone, or two or more thereof may be used in combination in any combination.
なお、これらの不飽和シラン化合物は１種を単独で用いてもよく、２種以上を任意の組合せで併用してもよい。 Among these, as the unsaturated silane compound, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloyloxypropyltriethoxysilane are preferable.
One of these unsaturated silane compounds may be used alone, or two or more thereof may be used in combination in any combination.
グラフト変性に用いる不飽和シラン化合物の添加量の下限は、架橋構造を形成させる観点から特に制限されないが、変性前組成物の全質量を基準にして、０．０１質量％以上であることが好ましい。前記観点から、不飽和シラン化合物の添加量は０．１質量％以上がより好ましく、０．７質量％以上がさらに好ましい。不飽和シラン化合物の添加量の上限は特に制限されないが、経済性の観点から、変性前組成物の全質量を基準にして、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下がさらに好ましい。
The lower limit of the amount of the unsaturated silane compound added for graft modification is not particularly limited from the viewpoint of forming a crosslinked structure, but is preferably 0.01% by mass or more based on the total mass of the pre-modification composition. .. From the above viewpoint, the amount of the unsaturated silane compound added is more preferably 0.1% by mass or more, further preferably 0.7% by mass or more. The upper limit of the amount of the unsaturated silane compound added is not particularly limited, but from the viewpoint of economy, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass, based on the total mass of the pre-modification composition. % Or less is more preferable.
グラフト変性に用いるラジカル発生剤としては、重合開始作用の強い種々の有機過酸化物及びパーエステル、例えば、ジクミルパーオキサイド、α，α’－ビス（ｔ－ブチルパーオキシジイソプロピル）ベンゼン、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ジ－ベンゾイルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルパーオキシピバレート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等が挙げられる。これらの中で、ジクミルパーオキサイド、ベンゾイルパーオキサイド、ジ－ｔ－ブチルパーオキサイドが好ましい。これらのラジカル発生剤は、１種を単独で用いてもよく、２種以上を任意の組合せで併用してもよい。
Radical generators used for graft modification include various organic peroxides and peresters having a strong polymerization initiation action, such as dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, and di-. t-butyl peroxide, t-butyl cumyl peroxide, di-benzoyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxypivalate, t-butyl Examples thereof include peroxy-2-ethylhexanoate. Of these, dicumyl peroxide, benzoyl peroxide, and di-t-butyl peroxide are preferable. One of these radical generators may be used alone, or two or more of them may be used in combination in any combination.
ラジカル発生剤の添加量は、得られるシラン変性高分子組成物のＭＦＲ（１９０℃、荷重２．１６ｋｇ）が最終的に０．０５ｇ／１０分以上、５０ｇ／１０分以下の範囲になるよう調整する必要がある。具体的には、ラジカル発生剤の添加量は、得られるシラン変性高分子組成物の全質量を基準にして、通常０．００５質量％以上、好ましくは０．０１質量％以上、より好ましくは０．０２質量％以上であり、通常０．５質量％以下、好ましくは０．４質量％以下、より好ましくは０．２質量％以下である。ラジカル発生剤の使用量が少なすぎると、充分なグラフト化が困難となる傾向がある。また、ラジカル発生剤の使用量が多すぎると、得られるシラン変性高分子組成物のＭＦＲが低下して、押出加工性が低下するとともに成形表面が悪くなる傾向がある。
The amount of the radical generator added is adjusted so that the MFR (190 ° C., load 2.16 kg) of the obtained silane-modified polymer composition is finally in the range of 0.05 g / 10 minutes or more and 50 g / 10 minutes or less. There is a need to. Specifically, the amount of the radical generator added is usually 0.005% by mass or more, preferably 0.01% by mass or more, more preferably 0, based on the total mass of the obtained silane-modified polymer composition. It is 0.02% by mass or more, usually 0.5% by mass or less, preferably 0.4% by mass or less, and more preferably 0.2% by mass or less. If the amount of the radical generator used is too small, sufficient grafting tends to be difficult. Further, if the amount of the radical generator used is too large, the MFR of the obtained silane-modified polymer composition is lowered, the extrusion processability is lowered, and the molded surface tends to be deteriorated.
その他、シラン変性高分子は、公知の手法に従って製造することができ、特に限定されない。例えば、溶液変性、溶融変性、電子線や電離放射線の照射による固相変性、超臨界流体中での変性等が好適に用いられる。これらの中でも、設備やコスト競争力に優れた溶融変性が好ましく、連続生産性に優れた押出機を用いた溶融混練変性がさらに好ましい。溶融混練変性に用いられる装置としては、例えば単軸スクリュー押出機、二軸スクリュー押出機、バンバリーミキサー、ロールミキサー等が挙げられる。これらの中でも、連続生産性に優れた単軸スクリュー押出機、二軸スクリュー押出機が好ましい。
In addition, the silane-modified polymer can be produced according to a known method and is not particularly limited. For example, solution denaturation, melt denaturation, solid phase denaturation by irradiation with electron beam or ionizing radiation, denaturation in a supercritical fluid, and the like are preferably used. Among these, melt modification with excellent equipment and cost competitiveness is preferable, and melt kneading modification using an extruder with excellent continuous productivity is more preferable. Examples of the apparatus used for melt-kneading modification include a single-screw screw extruder, a twin-screw screw extruder, a Banbury mixer, a roll mixer, and the like. Among these, a single-screw screw extruder and a twin-screw screw extruder having excellent continuous productivity are preferable.
シラン変性高分子の架橋反応に用いる架橋触媒としては、シラノール縮合触媒が好ましく使用される。以下、シラノール縮合触媒について詳述する。
A silanol condensation catalyst is preferably used as the cross-linking catalyst used for the cross-linking reaction of the silane-modified polymer. Hereinafter, the silanol condensation catalyst will be described in detail.
シラノール縮合触媒としては、例えば、ジブチル錫ジラウレート、酢酸第一錫、ジブチル錫ジアセテート、ジブチル錫ジオクトエート、ジオクチル錫ジラウレート等の錫触媒；ナフテン酸鉛、ステアリン酸鉛等の鉛触媒；カプリル酸亜鉛、ステアリン酸亜鉛等の亜鉛触媒；ナフテン酸コバルト等のコバルト触媒、チタン酸テトラブチルエステル等のチタン触媒；ステアリン酸カドミウム等のカドミウム触媒；ステアリン酸バリウム、ステアリン酸カルシウム等のアルカリ土類金属触媒等の有機金属触媒が挙げられる。これらの中でも、錫触媒が好ましい。これらのシラノール縮合触媒は、１種を単独で用いてもよく、２種以上を任意の組合せで併用してもよい。
Examples of the silanol condensation catalyst include tin catalysts such as dibutyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctate, and dioctyltin dilaurate; lead catalysts such as lead naphthenate and lead stearate; zinc caprylate, Zinc catalysts such as zinc stearate; cobalt catalysts such as cobalt naphthenate, titanium catalysts such as tetrabutyl ester titanate; cadmium catalysts such as cadmium stearate; organic earth metal catalysts such as barium stearate and calcium stearate Examples include metal catalysts. Among these, a tin catalyst is preferable. One of these silanol condensation catalysts may be used alone, or two or more of them may be used in combination in any combination.
シラノール縮合触媒の添加量は、シラノール縮合触媒を添加するシラン変性高分子組成物の全質量を基準として、通常０．０１質量％以上、好ましくは０．０２質量％以上、より好ましくは０．０５質量％以上であり、通常５質量％以下、好ましくは３質量％以下、より好ましくは２質量％以下である。シラノール縮合触媒の添加量が少なすぎると十分な架橋反応が進まず、また、添加量が多すぎるとコスト的に不利になる。
The amount of the silanol condensation catalyst added is usually 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.05, based on the total mass of the silane-modified polymer composition to which the silanol condensation catalyst is added. It is 5% by mass or less, usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. If the addition amount of the silanol condensation catalyst is too small, the sufficient cross-linking reaction does not proceed, and if the addition amount is too large, it is disadvantageous in terms of cost.
なお、シラノール縮合触媒は、一般的にマスターバッチ形式で添加することが簡便である。シラノール縮合触媒のマスターバッチは、例えば、シラノール縮合触媒をシラン変性高分子組成物の１種又は２種以上に添加して混練することにより製造することができる。
It is generally convenient to add the silanol condensation catalyst in the masterbatch format. The master batch of the silanol condensation catalyst can be produced, for example, by adding the silanol condensation catalyst to one or more of the silane-modified polymer compositions and kneading them.
シラノール縮合触媒として、シラン変性高分子組成物にシラノール縮合触媒を配合したマスターバッチを用いる場合、マスターバッチ中のシラノール縮合触媒の含有量は特に制限されないが、通常０．１～５．０質量％とすることが好ましい。
When a master batch in which a silanol condensation catalyst is mixed with a silane-modified polymer composition is used as the silanol condensation catalyst, the content of the silanol condensation catalyst in the master batch is not particularly limited, but is usually 0.1 to 5.0% by mass. Is preferable.
シラノール縮合触媒含有マスターバッチには、必要に応じて、混和可能な他の熱可塑性樹脂や、安定剤、滑剤、充填剤、着色剤、発泡剤、その他の補助資材等の添加剤を添加することができる。これらの添加剤は、それ自体既知の通常用いられるものであればよい。また、第３成分として、シラノール縮合触媒と共にこれらの添加剤をシラン変性高分子組成物に添加することも可能である。
Add other miscible thermoplastic resins and additives such as stabilizers, lubricants, fillers, colorants, foaming agents and other auxiliary materials to the silanol condensation catalyst-containing masterbatch, if necessary. Can be done. These additives may be those that are known and commonly used in their own right. It is also possible to add these additives to the silane-modified polymer composition as the third component together with the silanol condensation catalyst.
シラノール縮合触媒による架橋反応は、通常、シラン変性高分子にシラノール縮合触媒を配合した組成物を押出成形、射出成形、プレス成形等の各種成形方法により成形した後、水雰囲気中に曝したり、温水に浸漬したりすることにより、シラノール基間の架橋反応を進行させて行われる。水雰囲気中に曝す方法としては、各種の条件を採用することができ、水分を含む空気中に放置する方法、水蒸気を含む空気を送風する方法、水浴中に浸漬する方法、温水を霧状に散水させる方法等が挙げられる。
In the cross-linking reaction using a silanol condensation catalyst, a composition obtained by blending a silanol condensation catalyst with a silane-modified polymer is usually molded by various molding methods such as extrusion molding, injection molding, and press molding, and then exposed to an aqueous atmosphere or warm water. The cross-linking reaction between silanol groups is allowed to proceed by immersing in. Various conditions can be adopted as the method of exposing to the water atmosphere, the method of leaving in the air containing water, the method of blowing air containing water vapor, the method of immersing in a water bath, and the method of atomizing hot water. Examples include a method of sprinkling water.
この架橋反応では、シラン変性用の高分子のグラフト変性に用いた不飽和シラン化合物由来の加水分解可能なアルコキシ基が、シラノール縮合触媒の存在下、水と反応して加水分解することによりシラノール基が生成する。そして、生成したシラノール基同士が脱水縮合することにより反応が進行し、シラン変性高分子同士が結合してシラン架橋体が得られる。
In this cross-linking reaction, a hydrolyzable alkoxy group derived from an unsaturated silane compound used for graft modification of a polymer for silane modification reacts with water in the presence of a silanol condensation catalyst to hydrolyze the silanol group. Is generated. Then, the reaction proceeds by dehydration condensation of the produced silanol groups, and the silane-modified polymers are bonded to each other to obtain a silane crosslinked product.
架橋反応の進行速度は、シラン変性高分子組成物を水雰囲気中に曝す条件によって決まる。通常、２０～１３０℃の温度範囲、かつ１０分間～１週間の範囲の条件で、シラン変性高分子組成物を水雰囲気中に曝せばよい。特に好ましい条件は、２０～１３０℃の温度範囲、かつ１時間～１６０時間の範囲である。水分を含む空気を使用する場合、相対湿度は１～１００％の範囲から選択される。
The rate of progress of the crosslinking reaction is determined by the conditions under which the silane-modified polymer composition is exposed to the water atmosphere. Usually, the silane-modified polymer composition may be exposed to the water atmosphere under the conditions of a temperature range of 20 to 130 ° C. and a temperature range of 10 minutes to 1 week. Particularly preferred conditions are a temperature range of 20 to 130 ° C. and a range of 1 hour to 160 hours. When using moist air, the relative humidity is selected from the range of 1-100%.
シラン変性高分子の不飽和シラン化合物のグラフト率（変性量）、シラノール縮合触媒の種類や配合量、架橋させる際の条件（温度、時間）等を変えることにより、任意の架橋構造を形成することができる。
Arbitrary cross-linking structure can be formed by changing the graft ratio (modification amount) of the unsaturated silane compound of the silane-modified polymer, the type and blending amount of the silanol condensation catalyst, and the conditions (temperature, time) for cross-linking. Can be done.
本発明の実施形態の成形体は、可逆的熱伸縮性を有し、加熱による単位温度当たりの収縮率が０．０７％／℃以上であることが好ましい。
The molded product according to the embodiment of the present invention preferably has reversible thermal elasticity and a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
本発明の実施形態の成形体は、任意の温度と荷重領域において、可逆的熱伸縮性を有し、加熱による単位温度当たりの収縮率が０．０７％／℃以上であることが好ましい。
可逆的熱伸縮性とは、加熱による収縮、冷却による伸長をおおよそ一定の変位で繰り返えすことを示すが、本発明の範囲は特に、加熱する温度範囲や繰り返し動作に伴う劣化現象による特性変化において制約を受けるものではない。
可逆的熱伸縮性を有する好ましい態様は、復元率９０％の伸縮を１回以上できることが好ましく、１０回以上できることがより好ましく、１００回以上できることがさらに好ましく、１０００回以上できることが最も好ましい。可逆的熱伸縮性を有するより好ましい態様は、復元率９５％の伸縮を１回以上できることが好ましく、１０回以上できることがより好ましく、１００回以上できることがさらに好ましく、１０００回以上できることが最も好ましい。可逆的熱伸縮性を有するさらに好ましい態様は、復元率９７％の伸縮を１回以上できることが好ましく、１０回以上できることがより好ましく、１００回以上できることがさらに好ましく、１０００回以上できることがさらに好ましい。 The molded product of the embodiment of the present invention preferably has reversible thermal elasticity in an arbitrary temperature and load region, and has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
Reversible thermal elasticity means that shrinkage due to heating and expansion due to cooling are repeated with approximately constant displacement, but the scope of the present invention is particularly the temperature range for heating and the characteristic change due to deterioration phenomenon due to repeated operation. Is not restricted in.
In a preferred embodiment having reversible thermal elasticity, expansion and contraction with a restoration rate of 90% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more. A more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 95% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more. A more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 97% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and further preferably 1000 times or more.
可逆的熱伸縮性とは、加熱による収縮、冷却による伸長をおおよそ一定の変位で繰り返えすことを示すが、本発明の範囲は特に、加熱する温度範囲や繰り返し動作に伴う劣化現象による特性変化において制約を受けるものではない。
可逆的熱伸縮性を有する好ましい態様は、復元率９０％の伸縮を１回以上できることが好ましく、１０回以上できることがより好ましく、１００回以上できることがさらに好ましく、１０００回以上できることが最も好ましい。可逆的熱伸縮性を有するより好ましい態様は、復元率９５％の伸縮を１回以上できることが好ましく、１０回以上できることがより好ましく、１００回以上できることがさらに好ましく、１０００回以上できることが最も好ましい。可逆的熱伸縮性を有するさらに好ましい態様は、復元率９７％の伸縮を１回以上できることが好ましく、１０回以上できることがより好ましく、１００回以上できることがさらに好ましく、１０００回以上できることがさらに好ましい。 The molded product of the embodiment of the present invention preferably has reversible thermal elasticity in an arbitrary temperature and load region, and has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
Reversible thermal elasticity means that shrinkage due to heating and expansion due to cooling are repeated with approximately constant displacement, but the scope of the present invention is particularly the temperature range for heating and the characteristic change due to deterioration phenomenon due to repeated operation. Is not restricted in.
In a preferred embodiment having reversible thermal elasticity, expansion and contraction with a restoration rate of 90% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more. A more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 95% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more. A more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 97% can be performed once or more, more preferably 10 times or more, further preferably 100 times or more, and further preferably 1000 times or more.
可逆的熱伸縮性における復元率は、最初の測定長に対し、アクチュエータとして機能するためには９０％以上を維持することが好ましく、９５％以上がより好ましく、９７％以上がさらに好ましい。
また、前記復元率を維持する回数は、１０回以上が好ましく、１００回以上がより好ましく、１０００回以上がさらに好ましい。 The restoration rate in the reversible thermal elasticity is preferably maintained at 90% or more, more preferably 95% or more, still more preferably 97% or more in order to function as an actuator with respect to the initial measurement length.
The number of times to maintain the restoration rate is preferably 10 times or more, more preferably 100 times or more, still more preferably 1000 times or more.
また、前記復元率を維持する回数は、１０回以上が好ましく、１００回以上がより好ましく、１０００回以上がさらに好ましい。 The restoration rate in the reversible thermal elasticity is preferably maintained at 90% or more, more preferably 95% or more, still more preferably 97% or more in order to function as an actuator with respect to the initial measurement length.
The number of times to maintain the restoration rate is preferably 10 times or more, more preferably 100 times or more, still more preferably 1000 times or more.
成形体中、アクチュエータとしての機能を低下させない範囲で、可逆的熱伸縮性を有さない部分があっても良い。この場合、成形体中の可逆的熱伸縮性を有する部分は、成形体の熱伸縮する方向において、５０％以上が好ましく、８０％以上がより好ましく、１００％であることが最も好ましい。一方、成形体をコイル形状にすることで、熱による伸縮性を高めることができるが、必ずしも、コイル形状にしなくても、熱伸縮率が高い成形体とすることで、軽量で、かつ省スペース化を図ることができる。
In the molded body, there may be a part that does not have reversible thermal elasticity as long as the function as an actuator is not deteriorated. In this case, the portion of the molded product having reversible thermal expansion and contraction is preferably 50% or more, more preferably 80% or more, and most preferably 100% in the direction of thermal expansion and contraction of the molded product. On the other hand, by making the molded body into a coil shape, it is possible to increase the elasticity due to heat, but by making the molded body into a molded body with a high thermal expansion / contraction rate, it is lightweight and space-saving. Can be achieved.
本発明の実施形態の成形体は、－３０℃から２００℃の温度領域において、単位温度当たりの収縮率が０．０７％／℃以上であることが好ましい。
－３０℃から２００℃の温度領域において、単位温度当たりの収縮率が０．０７％／℃以上であれば、アクチュエータとしてアプリケーションの応用性が高く、優れたアクチュエータといえる。
収縮率が０．０７％／℃以上である動作温度領域の下限は、低いほど低温環境下でも動作が可能であり、アクチュエータとして使用することができるため、特に制限されないが、２０℃以上であれば室温付近で実現可能なアクチュエータとして好ましい。動作温度領域の下限が、０℃以上であれば、寒冷地でも実現可能なアクチュエータとして好ましく、－３０℃以上であれば、極寒地でも実用性のあるアクチュエータとして好ましい。 The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature in a temperature range of −30 ° C. to 200 ° C.
If the shrinkage rate per unit temperature is 0.07% / ° C. or higher in the temperature range of -30 ° C to 200 ° C, the application is highly applicable as an actuator, and it can be said that the actuator is excellent.
The lower limit of the operating temperature range in which the shrinkage rate is 0.07% / ° C or higher is not particularly limited as it can be operated even in a low temperature environment and can be used as an actuator, but it may be 20 ° C or higher. For example, it is preferable as an actuator that can be realized near room temperature. When the lower limit of the operating temperature region is 0 ° C. or higher, it is preferable as an actuator that can be realized even in a cold region, and when it is −30 ° C. or higher, it is preferable as an actuator that is practical even in an extremely cold region.
－３０℃から２００℃の温度領域において、単位温度当たりの収縮率が０．０７％／℃以上であれば、アクチュエータとしてアプリケーションの応用性が高く、優れたアクチュエータといえる。
収縮率が０．０７％／℃以上である動作温度領域の下限は、低いほど低温環境下でも動作が可能であり、アクチュエータとして使用することができるため、特に制限されないが、２０℃以上であれば室温付近で実現可能なアクチュエータとして好ましい。動作温度領域の下限が、０℃以上であれば、寒冷地でも実現可能なアクチュエータとして好ましく、－３０℃以上であれば、極寒地でも実用性のあるアクチュエータとして好ましい。 The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature in a temperature range of −30 ° C. to 200 ° C.
If the shrinkage rate per unit temperature is 0.07% / ° C. or higher in the temperature range of -30 ° C to 200 ° C, the application is highly applicable as an actuator, and it can be said that the actuator is excellent.
The lower limit of the operating temperature range in which the shrinkage rate is 0.07% / ° C or higher is not particularly limited as it can be operated even in a low temperature environment and can be used as an actuator, but it may be 20 ° C or higher. For example, it is preferable as an actuator that can be realized near room temperature. When the lower limit of the operating temperature region is 0 ° C. or higher, it is preferable as an actuator that can be realized even in a cold region, and when it is −30 ° C. or higher, it is preferable as an actuator that is practical even in an extremely cold region.
動作温度領域の上限は特に制限されないが、９０℃以下であれば、比較的加熱が容易で一般環境において実現可能なアクチュエータとして好ましく、１５０℃以下であれば、高温雰囲気で実現可能なアクチュエータとして好ましく、２００℃以下であれば、エンジン付近のような高温雰囲気で実現可能なアクチュエータとして好ましい。ただし、動作可能な温度範囲は高分子のガラス転移温度により任意調整可能であり、本発明は使用環境によって制限されるものではなく、所望の使用環境に応じて材料設計できる。
The upper limit of the operating temperature range is not particularly limited, but if it is 90 ° C. or lower, it is preferable as an actuator that can be relatively easily heated and can be realized in a general environment, and if it is 150 ° C. or lower, it is preferable as an actuator that can be realized in a high temperature atmosphere. , 200 ° C. or lower is preferable as an actuator that can be realized in a high temperature atmosphere such as near an engine. However, the operable temperature range can be arbitrarily adjusted by the glass transition temperature of the polymer, and the present invention is not limited by the usage environment, and the material can be designed according to the desired usage environment.
本発明の実施形態の成形体は、１～２０ＭＰａの引張荷重状態で、加熱による単位温度当たりの収縮率が０．０７％／℃以上であることが好ましい。
成形体の熱伸縮方向の１ＭＰａ以上の引張荷重状態で、加熱による単位温度当たりの収縮率が０．０７％／℃以上であると、少ない成形体の数や、より細い成形体でも収縮応力を発現することができ、アクチュエータとして有効である。前記観点から、加熱による単位温度当たりの収縮率が０．０７％／℃以上を満たす際の引張荷重状態は、３ＭＰａ以上の引張荷重状態であることがより好ましく、４ＭＰａ以上の引張荷重状態であることがさらに好ましい。
前記観点から、引張荷重状態の上限は特に制限がないが、１０ＭＰａの引張荷重状態で加熱した場合の単位温度当たりの収縮率が０．０７％／℃以上を満たすのであれば、アクチュエータとしてアプリケーションの応用性が高く、優れたアクチュエータといえる。したがって、収縮率が０．０７％／℃以上を満たす際の引張荷重状態は、１～２０ＭＰａもしくは１～１０ＭＰａの範囲に設定できる。 The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating under a tensile load of 1 to 20 MPa.
When the shrinkage rate per unit temperature due to heating is 0.07% / ° C or higher under a tensile load of 1 MPa or more in the thermal expansion / contraction direction of the molded body, shrinkage stress is applied even with a small number of molded bodies or a thinner molded body. It can be expressed and is effective as an actuator. From the above viewpoint, the tensile load state when the shrinkage rate per unit temperature due to heating satisfies 0.07% / ° C. or higher is more preferably a tensile load state of 3 MPa or more, and a tensile load state of 4 MPa or more. Is even more preferable.
From the above viewpoint, the upper limit of the tensile load state is not particularly limited, but if the shrinkage rate per unit temperature when heated under the tensile load state of 10 MPa satisfies 0.07% / ° C. or higher, the application can be used as an actuator. It is highly applicable and can be said to be an excellent actuator. Therefore, the tensile load state when the shrinkage rate satisfies 0.07% / ° C. or higher can be set in the range of 1 to 20 MPa or 1 to 10 MPa.
成形体の熱伸縮方向の１ＭＰａ以上の引張荷重状態で、加熱による単位温度当たりの収縮率が０．０７％／℃以上であると、少ない成形体の数や、より細い成形体でも収縮応力を発現することができ、アクチュエータとして有効である。前記観点から、加熱による単位温度当たりの収縮率が０．０７％／℃以上を満たす際の引張荷重状態は、３ＭＰａ以上の引張荷重状態であることがより好ましく、４ＭＰａ以上の引張荷重状態であることがさらに好ましい。
前記観点から、引張荷重状態の上限は特に制限がないが、１０ＭＰａの引張荷重状態で加熱した場合の単位温度当たりの収縮率が０．０７％／℃以上を満たすのであれば、アクチュエータとしてアプリケーションの応用性が高く、優れたアクチュエータといえる。したがって、収縮率が０．０７％／℃以上を満たす際の引張荷重状態は、１～２０ＭＰａもしくは１～１０ＭＰａの範囲に設定できる。 The molded product according to the embodiment of the present invention preferably has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating under a tensile load of 1 to 20 MPa.
When the shrinkage rate per unit temperature due to heating is 0.07% / ° C or higher under a tensile load of 1 MPa or more in the thermal expansion / contraction direction of the molded body, shrinkage stress is applied even with a small number of molded bodies or a thinner molded body. It can be expressed and is effective as an actuator. From the above viewpoint, the tensile load state when the shrinkage rate per unit temperature due to heating satisfies 0.07% / ° C. or higher is more preferably a tensile load state of 3 MPa or more, and a tensile load state of 4 MPa or more. Is even more preferable.
From the above viewpoint, the upper limit of the tensile load state is not particularly limited, but if the shrinkage rate per unit temperature when heated under the tensile load state of 10 MPa satisfies 0.07% / ° C. or higher, the application can be used as an actuator. It is highly applicable and can be said to be an excellent actuator. Therefore, the tensile load state when the shrinkage rate satisfies 0.07% / ° C. or higher can be set in the range of 1 to 20 MPa or 1 to 10 MPa.
本発明の実施形態の成形体は、５０℃の温度変化の加熱による収縮後に５０℃降温したときの復元率が、９０％以上であることが好ましい。
本発明の実施形態の成形体をアクチュエータとして使用する場合、収縮と伸縮が繰り返しできることが重要である。加熱して収縮させた後に収縮前の温度に降温したときの本発明の成形体の熱収縮方向の長さの復元率が９０％以上であれば、アクチュエータとして十分に使用できる。この観点から、前記復元率は、９５％以上がより好ましく、９７％以上がさらに好ましい。
また、前記復元率を維持する回数は、２回以上が好ましく、１０回以上がより好ましく、１００回以上がさらに好ましく、１０００回以上がもっとも好ましい。 The molded product according to the embodiment of the present invention preferably has a restoration rate of 90% or more when the temperature is lowered by 50 ° C. after shrinking by heating at a temperature change of 50 ° C.
When the molded product of the embodiment of the present invention is used as an actuator, it is important that it can repeatedly contract and contract. If the restoration rate of the length in the heat shrinkage direction of the molded product of the present invention when the temperature is lowered to the temperature before shrinkage after being heated and shrunk is 90% or more, it can be sufficiently used as an actuator. From this point of view, the restoration rate is more preferably 95% or more, further preferably 97% or more.
The number of times to maintain the restoration rate is preferably 2 times or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more.
本発明の実施形態の成形体をアクチュエータとして使用する場合、収縮と伸縮が繰り返しできることが重要である。加熱して収縮させた後に収縮前の温度に降温したときの本発明の成形体の熱収縮方向の長さの復元率が９０％以上であれば、アクチュエータとして十分に使用できる。この観点から、前記復元率は、９５％以上がより好ましく、９７％以上がさらに好ましい。
また、前記復元率を維持する回数は、２回以上が好ましく、１０回以上がより好ましく、１００回以上がさらに好ましく、１０００回以上がもっとも好ましい。 The molded product according to the embodiment of the present invention preferably has a restoration rate of 90% or more when the temperature is lowered by 50 ° C. after shrinking by heating at a temperature change of 50 ° C.
When the molded product of the embodiment of the present invention is used as an actuator, it is important that it can repeatedly contract and contract. If the restoration rate of the length in the heat shrinkage direction of the molded product of the present invention when the temperature is lowered to the temperature before shrinkage after being heated and shrunk is 90% or more, it can be sufficiently used as an actuator. From this point of view, the restoration rate is more preferably 95% or more, further preferably 97% or more.
The number of times to maintain the restoration rate is preferably 2 times or more, more preferably 10 times or more, further preferably 100 times or more, and most preferably 1000 times or more.
本発明の実施形態の成形体は、オレフィン系重合体からなることが好ましい。
屈曲性高分子であるポリオレフィン等のオレフィン系重合体は、絡み合い数および架橋数を増やすことが容易なため、単位温度当たりの熱収縮率が高い成形体を得ることができる。
オレフィン系重合体は、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体等のポリオレフィンをはじめ、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体、エチレン－エチルアクリレート共重合体等のエチレン系共重合体などのオレフィン共重合体、ポリビニリデンフルオライド等のフッ素系ポリマー、ポリ塩化ビニリデン等の塩素系ポリマーが挙げられる。
要求する可逆的熱伸縮性が得られれば、オレフィン系重合体以外の重合体及び添加剤を含むこともできる。 The molded product of the embodiment of the present invention is preferably made of an olefin polymer.
Since it is easy to increase the number of entanglements and the number of crosslinks of the olefin polymer such as polyolefin which is a flexible polymer, it is possible to obtain a molded product having a high heat shrinkage rate per unit temperature.
The olefin-based polymer includes polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer, as well as ethylene-based polymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-ethyl acrylate copolymer. Examples thereof include olefin polymers such as polymers, fluoropolymers such as polyvinylidene fluoride, and chlorine-based polymers such as polyvinylidene chloride.
Polymers and additives other than olefin-based polymers can be contained as long as the required reversible thermal stretchability can be obtained.
屈曲性高分子であるポリオレフィン等のオレフィン系重合体は、絡み合い数および架橋数を増やすことが容易なため、単位温度当たりの熱収縮率が高い成形体を得ることができる。
オレフィン系重合体は、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体等のポリオレフィンをはじめ、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体、エチレン－エチルアクリレート共重合体等のエチレン系共重合体などのオレフィン共重合体、ポリビニリデンフルオライド等のフッ素系ポリマー、ポリ塩化ビニリデン等の塩素系ポリマーが挙げられる。
要求する可逆的熱伸縮性が得られれば、オレフィン系重合体以外の重合体及び添加剤を含むこともできる。 The molded product of the embodiment of the present invention is preferably made of an olefin polymer.
Since it is easy to increase the number of entanglements and the number of crosslinks of the olefin polymer such as polyolefin which is a flexible polymer, it is possible to obtain a molded product having a high heat shrinkage rate per unit temperature.
The olefin-based polymer includes polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer, as well as ethylene-based polymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-ethyl acrylate copolymer. Examples thereof include olefin polymers such as polymers, fluoropolymers such as polyvinylidene fluoride, and chlorine-based polymers such as polyvinylidene chloride.
Polymers and additives other than olefin-based polymers can be contained as long as the required reversible thermal stretchability can be obtained.
本発明の実施形態の成形体は、ポリエチレンからなることが好ましい。
本発明の実施形態の成形体がポリエチレンからなることで、材料のポリエチレンが比較的安価で、紡糸性に優れ、架橋の導入も容易であるため、熱収縮率の高い成形体を低コストで得ることができる。 The molded product of the embodiment of the present invention is preferably made of polyethylene.
Since the molded product of the embodiment of the present invention is made of polyethylene, the polyethylene material is relatively inexpensive, has excellent spinnability, and is easy to introduce crosslinks, so that a molded product having a high heat shrinkage rate can be obtained at low cost. be able to.
本発明の実施形態の成形体がポリエチレンからなることで、材料のポリエチレンが比較的安価で、紡糸性に優れ、架橋の導入も容易であるため、熱収縮率の高い成形体を低コストで得ることができる。 The molded product of the embodiment of the present invention is preferably made of polyethylene.
Since the molded product of the embodiment of the present invention is made of polyethylene, the polyethylene material is relatively inexpensive, has excellent spinnability, and is easy to introduce crosslinks, so that a molded product having a high heat shrinkage rate can be obtained at low cost. be able to.
本発明の実施形態におけるシラン架橋性ポリエチレン組成物（シラン変性高分子としてシラン変性ポリエチレンを含む組成物）のＭＦＲ（１９０℃、荷重２．１６ｋｇ）は、紡糸性の観点から通常０．５～５０ｇ／１０分であり、０．５～４０ｇ／１０分であることが好ましく、０．５～３０ｇ／１０分であることがより好ましい。
The MFR (190 ° C., load 2.16 kg) of the silane crosslinkable polyethylene composition (composition containing silane-modified polyethylene as a silane-modified polymer) in the embodiment of the present invention is usually 0.5 to 50 g from the viewpoint of spinnability. It is / 10 minutes, preferably 0.5 to 40 g / 10 minutes, and more preferably 0.5 to 30 g / 10 minutes.
本発明の実施形態の成形体は、繊維状、板状、シート状もしくはフィルム状であることが好ましく、又はこれらから選ばれる１種以上の多層構造を有することが好ましい。
一方向に熱伸縮するものであれば、成形体の形状はどのようなものであっても良い。繊維状であれば、コイル形状に形成しやすく、収縮応力が高くでき、屈曲性を持たせることが可能である。板状であれば、熱伸縮する断面積を大きくとりやすく、圧縮荷重等の、応力がかかるところで使用でき、収縮応力も高いものが得られる。また、板状の場合は、細長い形状としてコイル形状にすればよい。シート状、フィルム状であれば、積層して多層体としたり、その形状を丸めて円筒構造としたりすることで、熱伸縮する断面積を大きくとりやすく、収縮力を高くすることができやすくなる。
さらに、アクチュエータとして使用する用途に応じて、同じ形状の成形体を複数使用して多層構造にしたり、異なる形状の成形体を組み合わせて多層構造にしたりすることもできる。 The molded product of the embodiment of the present invention is preferably in the form of fibers, plates, sheets or films, or preferably has one or more multilayer structures selected from these.
The shape of the molded body may be any shape as long as it is thermally expanded and contracted in one direction. If it is fibrous, it can be easily formed into a coil shape, the shrinkage stress can be increased, and the flexibility can be imparted. If it is plate-shaped, it is easy to take a large cross-sectional area that expands and contracts with heat, it can be used in places where stress is applied such as compressive load, and it can be obtained with high shrinkage stress. Further, in the case of a plate shape, a coil shape may be used as an elongated shape. If it is in the form of a sheet or film, it can be laminated to form a multilayer body, or the shape can be rounded to form a cylindrical structure, so that it is easy to take a large cross-sectional area that expands and contracts with heat, and it becomes easy to increase the shrinkage force. ..
Further, depending on the intended use as an actuator, a plurality of molded bodies having the same shape may be used to form a multi-layer structure, or molded bodies having different shapes may be combined to form a multi-layer structure.
一方向に熱伸縮するものであれば、成形体の形状はどのようなものであっても良い。繊維状であれば、コイル形状に形成しやすく、収縮応力が高くでき、屈曲性を持たせることが可能である。板状であれば、熱伸縮する断面積を大きくとりやすく、圧縮荷重等の、応力がかかるところで使用でき、収縮応力も高いものが得られる。また、板状の場合は、細長い形状としてコイル形状にすればよい。シート状、フィルム状であれば、積層して多層体としたり、その形状を丸めて円筒構造としたりすることで、熱伸縮する断面積を大きくとりやすく、収縮力を高くすることができやすくなる。
さらに、アクチュエータとして使用する用途に応じて、同じ形状の成形体を複数使用して多層構造にしたり、異なる形状の成形体を組み合わせて多層構造にしたりすることもできる。 The molded product of the embodiment of the present invention is preferably in the form of fibers, plates, sheets or films, or preferably has one or more multilayer structures selected from these.
The shape of the molded body may be any shape as long as it is thermally expanded and contracted in one direction. If it is fibrous, it can be easily formed into a coil shape, the shrinkage stress can be increased, and the flexibility can be imparted. If it is plate-shaped, it is easy to take a large cross-sectional area that expands and contracts with heat, it can be used in places where stress is applied such as compressive load, and it can be obtained with high shrinkage stress. Further, in the case of a plate shape, a coil shape may be used as an elongated shape. If it is in the form of a sheet or film, it can be laminated to form a multilayer body, or the shape can be rounded to form a cylindrical structure, so that it is easy to take a large cross-sectional area that expands and contracts with heat, and it becomes easy to increase the shrinkage force. ..
Further, depending on the intended use as an actuator, a plurality of molded bodies having the same shape may be used to form a multi-layer structure, or molded bodies having different shapes may be combined to form a multi-layer structure.
本発明の繊維状の成形体を製造する方法としては、従来公知の溶融紡糸、湿式紡糸、乾式紡糸、乾湿式等の種々の手法を採用することができる。架橋構造を形成する段階は特に制限されないが、未延伸糸を延伸配向し、結晶配向した延伸繊維を得た後に架橋処理を行うことで、紡糸の生産性を損なうことなく、繊維の力学物性と結晶配向を維持したまま架橋構造を形成することができるため、好ましい。
As a method for producing the fibrous molded product of the present invention, various conventionally known methods such as melt spinning, wet spinning, dry spinning, and dry / wet can be adopted. The stage of forming the crosslinked structure is not particularly limited, but by drawing-oriented the undrawn yarn and performing the cross-linking treatment after obtaining the crystal-oriented drawn fiber, the mechanical properties of the fiber can be obtained without impairing the productivity of the spinning yarn. It is preferable because a crosslinked structure can be formed while maintaining the crystal orientation.
本発明の実施形態の成形体は、繊維状である場合、繊維状成形体の単繊維繊度が５０～１００００ｄｔｅｘであることが好ましい。
単繊維繊度（ｄｔｅｘ）は繊維１本の１００００ｍ当りの重さ（ｇ）を意味する。
単繊維繊度の下限は、材料の強度や弾性率によるため、特に制限されないが、後加工の強度の点、およびコイル化した際のバネ指数を高める点から、単繊維繊度は５０ｄｔｅｘ以上が好ましく、１００ｄｔｅｘ以上がより好ましく、２００ｄｔｅｘ以上がさらに好ましい。
単繊維繊度の上限は、材料の柔軟性によるため、特に制限されないが、柔軟性、後加工のしやすさの点から、単繊維繊度は１００００ｄｔｅｘ以下が好ましく、５０００ｄｔｅｘ以下がより好ましく、１０００ｄｔｅｘ以下がさらに好ましい。 When the molded product of the embodiment of the present invention is fibrous, it is preferable that the single fiber fineness of the fibrous molded product is 50 to 10000 dtex.
The single fiber fineness (dtex) means the weight (g) per 10,000 m of one fiber.
The lower limit of the single fiber fineness is not particularly limited because it depends on the strength and elastic modulus of the material, but the single fiber fineness is preferably 50 dtex or more from the viewpoint of the strength of post-processing and the increase of the spring index when coiled. 100 dtex or more is more preferable, and 200 dtex or more is further preferable.
The upper limit of the single fiber fineness is not particularly limited because it depends on the flexibility of the material, but the single fiber fineness is preferably 10,000 dtex or less, more preferably 5000 dtex or less, and 1000 dtex or less from the viewpoint of flexibility and ease of post-processing. More preferred.
単繊維繊度（ｄｔｅｘ）は繊維１本の１００００ｍ当りの重さ（ｇ）を意味する。
単繊維繊度の下限は、材料の強度や弾性率によるため、特に制限されないが、後加工の強度の点、およびコイル化した際のバネ指数を高める点から、単繊維繊度は５０ｄｔｅｘ以上が好ましく、１００ｄｔｅｘ以上がより好ましく、２００ｄｔｅｘ以上がさらに好ましい。
単繊維繊度の上限は、材料の柔軟性によるため、特に制限されないが、柔軟性、後加工のしやすさの点から、単繊維繊度は１００００ｄｔｅｘ以下が好ましく、５０００ｄｔｅｘ以下がより好ましく、１０００ｄｔｅｘ以下がさらに好ましい。 When the molded product of the embodiment of the present invention is fibrous, it is preferable that the single fiber fineness of the fibrous molded product is 50 to 10000 dtex.
The single fiber fineness (dtex) means the weight (g) per 10,000 m of one fiber.
The lower limit of the single fiber fineness is not particularly limited because it depends on the strength and elastic modulus of the material, but the single fiber fineness is preferably 50 dtex or more from the viewpoint of the strength of post-processing and the increase of the spring index when coiled. 100 dtex or more is more preferable, and 200 dtex or more is further preferable.
The upper limit of the single fiber fineness is not particularly limited because it depends on the flexibility of the material, but the single fiber fineness is preferably 10,000 dtex or less, more preferably 5000 dtex or less, and 1000 dtex or less from the viewpoint of flexibility and ease of post-processing. More preferred.
本発明の実施形態の成形体は、繊維状である場合、繊維状成形体の単繊維の直径が８０～１２００μｍであることが好ましい。
単繊維の直径の下限は、材料の強度や弾性率等によるため、特に制限されないが、コイル形状とするための加撚や、製織などの後加工の強度の点、およびコイル化した際のバネ指数を高める点から、単繊維の直径は８０μｍ以上が好ましく、１２０μｍ以上がより好ましく、１７０μｍ以上がさらに好ましい。
単繊維の直径の上限は、材料の柔軟性等によるため、特に制限されないが、単繊維の直径が小さいと、柔軟性があり、後加工しやすくなるため、単繊維の直径は１２００μｍ以下が好ましく、８４０μｍ以下がより好ましく、３８０μｍ以下がさらに好ましい。 When the molded product of the embodiment of the present invention is fibrous, it is preferable that the diameter of the single fiber of the fibrous molded product is 80 to 1200 μm.
The lower limit of the diameter of the single fiber is not particularly limited because it depends on the strength of the material, the elastic modulus, etc. From the viewpoint of increasing the index, the diameter of the single fiber is preferably 80 μm or more, more preferably 120 μm or more, still more preferably 170 μm or more.
The upper limit of the diameter of the single fiber is not particularly limited because it depends on the flexibility of the material, but if the diameter of the single fiber is small, it is flexible and easy to post-process, so the diameter of the single fiber is preferably 1200 μm or less. , 840 μm or less is more preferable, and 380 μm or less is further preferable.
単繊維の直径の下限は、材料の強度や弾性率等によるため、特に制限されないが、コイル形状とするための加撚や、製織などの後加工の強度の点、およびコイル化した際のバネ指数を高める点から、単繊維の直径は８０μｍ以上が好ましく、１２０μｍ以上がより好ましく、１７０μｍ以上がさらに好ましい。
単繊維の直径の上限は、材料の柔軟性等によるため、特に制限されないが、単繊維の直径が小さいと、柔軟性があり、後加工しやすくなるため、単繊維の直径は１２００μｍ以下が好ましく、８４０μｍ以下がより好ましく、３８０μｍ以下がさらに好ましい。 When the molded product of the embodiment of the present invention is fibrous, it is preferable that the diameter of the single fiber of the fibrous molded product is 80 to 1200 μm.
The lower limit of the diameter of the single fiber is not particularly limited because it depends on the strength of the material, the elastic modulus, etc. From the viewpoint of increasing the index, the diameter of the single fiber is preferably 80 μm or more, more preferably 120 μm or more, still more preferably 170 μm or more.
The upper limit of the diameter of the single fiber is not particularly limited because it depends on the flexibility of the material, but if the diameter of the single fiber is small, it is flexible and easy to post-process, so the diameter of the single fiber is preferably 1200 μm or less. , 840 μm or less is more preferable, and 380 μm or less is further preferable.
本発明の実施形態の成形体は、コイル形状に形成されていることが好ましい。
本発明の実施形態のコイル化された繊維状の成形体は、例えば、以下のように製造することができる。まず、シラン変性高分子組成物を溶融紡糸し、２～２０倍の延伸を行う。さらに、架橋処理を、好ましくは１２時間以上の静置により行い、得られたシラン架橋ポリエチレン又はシラン架橋ポリエチレン組成物の繊維を、３～２０ＭＰａの張力を掛けながら加撚してコイル化することにより、コイル化された繊維を製造することができる。 The molded body of the embodiment of the present invention is preferably formed in a coil shape.
The coiled fibrous molded product of the embodiment of the present invention can be manufactured, for example, as follows. First, the silane-modified polymer composition is melt-spun and stretched 2 to 20 times. Further, the cross-linking treatment is preferably carried out by allowing it to stand for 12 hours or more, and the obtained fiber of the silane cross-linked polyethylene or the silane cross-linked polyethylene composition is twisted and coiled while applying a tension of 3 to 20 MPa. , Coiled fibers can be produced.
本発明の実施形態のコイル化された繊維状の成形体は、例えば、以下のように製造することができる。まず、シラン変性高分子組成物を溶融紡糸し、２～２０倍の延伸を行う。さらに、架橋処理を、好ましくは１２時間以上の静置により行い、得られたシラン架橋ポリエチレン又はシラン架橋ポリエチレン組成物の繊維を、３～２０ＭＰａの張力を掛けながら加撚してコイル化することにより、コイル化された繊維を製造することができる。 The molded body of the embodiment of the present invention is preferably formed in a coil shape.
The coiled fibrous molded product of the embodiment of the present invention can be manufactured, for example, as follows. First, the silane-modified polymer composition is melt-spun and stretched 2 to 20 times. Further, the cross-linking treatment is preferably carried out by allowing it to stand for 12 hours or more, and the obtained fiber of the silane cross-linked polyethylene or the silane cross-linked polyethylene composition is twisted and coiled while applying a tension of 3 to 20 MPa. , Coiled fibers can be produced.
３ＭＰａ以上の張力を掛けながら加撚してコイル化することで、コイル形状が良好となり、２０ＭＰａ以下、好ましくは８ＭＰａ以下の張力にすることで、熱収縮時のコイルの破断を少なくすることができる。これらの観点から、コイル化時の張力は３．５～７ＭＰａがより好ましく、４～６ＭＰａがさらに好ましい。
By twisting and twisting while applying a tension of 3 MPa or more to form a coil, the coil shape becomes good, and by setting the tension to 20 MPa or less, preferably 8 MPa or less, it is possible to reduce the breakage of the coil during heat shrinkage. .. From these viewpoints, the tension at the time of coiling is more preferably 3.5 to 7 MPa, further preferably 4 to 6 MPa.
また、架橋処理については、好ましくは１２時間以上の静置をすることにより架橋処理を行うことで、架橋が十分に行われ、可逆的伸縮性が良好となる。この観点から、架橋処理を行う時間は１６時間以上がより好ましく、２０時間以上がさらに好ましい。また、３６時間あれば、架橋が十分行われて、これ以上架橋が進むことは少ないと考えられるので、架橋処理を行う時間の上限は３６時間以下に設定できる。
As for the cross-linking treatment, the cross-linking treatment is preferably carried out by allowing it to stand for 12 hours or more, so that the cross-linking is sufficiently performed and the reversible elasticity is improved. From this viewpoint, the time for performing the crosslinking treatment is more preferably 16 hours or more, further preferably 20 hours or more. Further, if it is 36 hours, it is considered that the crosslinking is sufficiently performed and the crosslinking is unlikely to proceed any further. Therefore, the upper limit of the time for performing the crosslinking treatment can be set to 36 hours or less.
本発明の実施形態の成形体は、以下の条件（１）～（３）をすべて満たすことが好ましい。
（１）繊維軸に対して垂直方向から測定したX線回折パターンについて、２θ＝１０°から３０°の区間に１つ以上のピークがある。
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上である。
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下である。 It is preferable that the molded product of the embodiment of the present invention satisfies all of the following conditions (1) to (3).
(1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the peak with the highest intensity, or the intensity of the peak with the highest intensity is more than double the intensity of the peak with the next highest intensity.
(3) The degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material.
（１）繊維軸に対して垂直方向から測定したX線回折パターンについて、２θ＝１０°から３０°の区間に１つ以上のピークがある。
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上である。
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下である。 It is preferable that the molded product of the embodiment of the present invention satisfies all of the following conditions (1) to (3).
(1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the peak with the highest intensity, or the intensity of the peak with the highest intensity is more than double the intensity of the peak with the next highest intensity.
(3) The degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material.
（１）繊維軸に対して垂直方向から測定したX線回折パターンについて、２θ＝１０°から３０°の区間に１つ以上のピークがあり、
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上であり、
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下であれば、
コイルを形成する繊維が結晶配向しており、アクチュエータ性能が向上するため好ましい。 (1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there are one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the highest intensity peak, or the intensity of the highest intensity peak is more than double the intensity of the next highest intensity peak.
(3) If the fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material,
It is preferable because the fibers forming the coil are crystal-oriented and the actuator performance is improved.
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上であり、
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下であれば、
コイルを形成する繊維が結晶配向しており、アクチュエータ性能が向上するため好ましい。 (1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there are one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the highest intensity peak, or the intensity of the highest intensity peak is more than double the intensity of the next highest intensity peak.
(3) If the fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material,
It is preferable because the fibers forming the coil are crystal-oriented and the actuator performance is improved.
本発明の実施形態の成形体は、バネ指数Ｄ／ｄが０．５以上であり、前記コイル形状の平均直径Ｄが１００～２０００μｍであることが好ましい。
The molded body of the embodiment of the present invention preferably has a spring index D / d of 0.5 or more and an average diameter D of the coil shape of 100 to 2000 μm.
本発明の実施形態の成形体は、繊維状であり、バネ指数Ｄ／ｄが０．５以上であることが好ましい。ここで、Ｄはコイル平均直径（コイル平均径）（μｍ）を表し、ｄはコイルを構成する単繊維の直径（μｍ）を表す。図２及び図３において、コイル平均直径Ｄ及び単繊維直径ｄの位置を示している。なお、図３におけるＤ’はコイル外径を示している。
バネ指数が０．５以上であれば、コイルの単位長さあたりの熱収縮率を高くすることができる。この観点から、バネ指数は、０．６以上がより好ましく、０．７以上がさらに好ましい。また、バネ指数が低くなるほど、コイルの単位長さあたりの加熱によるコイル軸方向に収縮する力を高くできるため、バネ指数は、１０．０以下が好ましく、６．０以下がより好ましく、３．０以下がさらに好ましく、１．５以下が最も好ましい。 The molded product according to the embodiment of the present invention is preferably fibrous and has a spring index D / d of 0.5 or more. Here, D represents the coil average diameter (coil average diameter) (μm), and d represents the diameter (μm) of the single fiber constituting the coil. 2 and 3 show the positions of the coil average diameter D and the single fiber diameter d. Note that D'in FIG. 3 indicates the outer diameter of the coil.
When the spring index is 0.5 or more, the heat shrinkage rate per unit length of the coil can be increased. From this viewpoint, the spring index is more preferably 0.6 or more, and further preferably 0.7 or more. Further, as the spring index becomes lower, the force of contraction in the coil axial direction due to heating per unit length of the coil can be increased. Therefore, the spring index is preferably 10.0 or less, more preferably 6.0 or less. 0 or less is more preferable, and 1.5 or less is most preferable.
バネ指数が０．５以上であれば、コイルの単位長さあたりの熱収縮率を高くすることができる。この観点から、バネ指数は、０．６以上がより好ましく、０．７以上がさらに好ましい。また、バネ指数が低くなるほど、コイルの単位長さあたりの加熱によるコイル軸方向に収縮する力を高くできるため、バネ指数は、１０．０以下が好ましく、６．０以下がより好ましく、３．０以下がさらに好ましく、１．５以下が最も好ましい。 The molded product according to the embodiment of the present invention is preferably fibrous and has a spring index D / d of 0.5 or more. Here, D represents the coil average diameter (coil average diameter) (μm), and d represents the diameter (μm) of the single fiber constituting the coil. 2 and 3 show the positions of the coil average diameter D and the single fiber diameter d. Note that D'in FIG. 3 indicates the outer diameter of the coil.
When the spring index is 0.5 or more, the heat shrinkage rate per unit length of the coil can be increased. From this viewpoint, the spring index is more preferably 0.6 or more, and further preferably 0.7 or more. Further, as the spring index becomes lower, the force of contraction in the coil axial direction due to heating per unit length of the coil can be increased. Therefore, the spring index is preferably 10.0 or less, more preferably 6.0 or less. 0 or less is more preferable, and 1.5 or less is most preferable.
前記コイル形状の平均直径Ｄが１００μｍ以上であれば、剛性があり、アクチュエーターとして装置に組み込む際に扱いやすくなり、好ましい。また２０００μｍ以下であれば、柔軟性が高くなり、好ましい。
これらの観点から、前記コイル形状の平均直径Ｄは１２０～１５００μｍがより好ましく、１４０～１０００μｍがさらに好ましく、１６０～５００μｍが最も好ましい。 When the average diameter D of the coil shape is 100 μm or more, it is rigid and easy to handle when incorporated into an apparatus as an actuator, which is preferable. Further, when it is 2000 μm or less, the flexibility is high, which is preferable.
From these viewpoints, the average diameter D of the coil shape is more preferably 120 to 1500 μm, further preferably 140 to 1000 μm, and most preferably 160 to 500 μm.
これらの観点から、前記コイル形状の平均直径Ｄは１２０～１５００μｍがより好ましく、１４０～１０００μｍがさらに好ましく、１６０～５００μｍが最も好ましい。 When the average diameter D of the coil shape is 100 μm or more, it is rigid and easy to handle when incorporated into an apparatus as an actuator, which is preferable. Further, when it is 2000 μm or less, the flexibility is high, which is preferable.
From these viewpoints, the average diameter D of the coil shape is more preferably 120 to 1500 μm, further preferably 140 to 1000 μm, and most preferably 160 to 500 μm.
本発明の実施形態の成形体は、密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレン２０～８０質量％と、密度が０．８６０～０．８８０ｇ／ｃｍ３である直鎖状低密度ポリエチレン２０～８０質量％と、を含有する混合物を含むことが好ましい。このような成形体を得るためには、製造時の前記変性前組成物が、変性前の高分子として上記混合物を含むことが好ましい。
密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレンを含むことで、製造時の組成物の延伸性が向上し、力学物性が高くなる。その結果、コイル化時の破断を抑制することができ、かつ延伸配向するため、コイル形状の成形体の熱収縮率を高くすることができる。 The molded body of the embodiment of the present invention is selected from linear low-density polyethylene having a density of 0.881 to 0.941 g / cm 3 and high-density polyethylene having a density of 0.942 to 0.970 g / cm 3 . It is preferable to contain a mixture containing 20 to 80% by mass of one or more polyethylenes to be made and 20 to 80% by mass of linear low density polyethylene having a density of 0.860 to 0.880 g / cm 3 . .. In order to obtain such a molded product, it is preferable that the pre-modification composition at the time of production contains the above mixture as the polymer before modification.
Containing one or more polyethylene selected from linear low density polyethylene with a density of 0.881 to 0.941 g / cm 3 and high density polyethylene with a density of 0.942 to 0.970 g / cm 3 . Therefore, the stretchability of the composition at the time of production is improved, and the mechanical properties are improved. As a result, breakage at the time of coiling can be suppressed, and since the drawing orientation is achieved, the heat shrinkage rate of the coil-shaped molded body can be increased.
密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレンを含むことで、製造時の組成物の延伸性が向上し、力学物性が高くなる。その結果、コイル化時の破断を抑制することができ、かつ延伸配向するため、コイル形状の成形体の熱収縮率を高くすることができる。 The molded body of the embodiment of the present invention is selected from linear low-density polyethylene having a density of 0.881 to 0.941 g / cm 3 and high-density polyethylene having a density of 0.942 to 0.970 g / cm 3 . It is preferable to contain a mixture containing 20 to 80% by mass of one or more polyethylenes to be made and 20 to 80% by mass of linear low density polyethylene having a density of 0.860 to 0.880 g / cm 3 . .. In order to obtain such a molded product, it is preferable that the pre-modification composition at the time of production contains the above mixture as the polymer before modification.
Containing one or more polyethylene selected from linear low density polyethylene with a density of 0.881 to 0.941 g / cm 3 and high density polyethylene with a density of 0.942 to 0.970 g / cm 3 . Therefore, the stretchability of the composition at the time of production is improved, and the mechanical properties are improved. As a result, breakage at the time of coiling can be suppressed, and since the drawing orientation is achieved, the heat shrinkage rate of the coil-shaped molded body can be increased.
これらの観点から、密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレンの含有量は、前記混合物中、２０質量％以上が好ましく、３０質量％以上が好ましく、５０質量％以上がさらに好ましい。また、前記含有量が８０質量％以下であることで、溶融紡糸時の溶融張力が安定し、成形体の生産性を高くすることができる。この観点から、前記含有量は、前記混合物中、７０質量％以下がより好ましい。密度はＡＳＴＭ Ｄ７９２により測定することができる。
From these points of view, one or more selected from linear low density polyethylene having a density of 0.881 to 0.941 g / cm 3 and high density polyethylene having a density of 0.942 to 0.970 g / cm 3 . The content of polyethylene in the above mixture is preferably 20% by mass or more, preferably 30% by mass or more, and even more preferably 50% by mass or more. Further, when the content is 80% by mass or less, the melt tension at the time of melt spinning is stable, and the productivity of the molded product can be increased. From this viewpoint, the content is more preferably 70% by mass or less in the mixture. Density can be measured by ASTM D792.
前記直鎖状低密度ポリエチレンは、メタロセン触媒を用いて重合することが好ましい。メタロセン触媒を用いることで、直線状の高分子が得られやすく、その結果、延伸時の延伸性が向上し、熱収縮率を高くしやすい。
The linear low-density polyethylene is preferably polymerized using a metallocene catalyst. By using a metallocene catalyst, it is easy to obtain a linear polymer, and as a result, the stretchability at the time of stretching is improved, and the heat shrinkage rate is easily increased.
本発明の実施形態の成形体は、前記混合物の密度が０．８６０～０．９４０ｇ／ｃｍ３であることが好ましい。
密度が低いほど、軽量で、かつ、加熱時の熱収縮に寄与できる非晶が多く、良好な熱収縮効果を発現するため、密度の下限は特に制限されない。ただし、密度が０．８６０ｇ／ｃｍ３以上であれば、十分な力学物性を有し、コイル加工時の破断を抑えることができる。前記観点から、密度は０．８７０ｇ／ｃｍ３以上がより好ましく、０．８８０ｇ／ｃｍ３以上がさらに好ましく、０．８９０ｇ／ｃｍ３以上が最も好ましい。また、密度が高いほど力学物性が向上し、コイル加工時の破断を抑制し、生産性が上がるため、密度の上限は特に制限されない。ただし、密度が０．９４０ｇ／ｃｍ３以下であれば、加熱時の熱収縮に寄与できる非晶が十分で、良好な熱収縮効果を発現することができる。前記観点から、密度は０．９３０ｇ／ｃｍ３以下がより好ましく、０．９２０ｇ／ｃｍ３以下がさらに好ましい。密度はＡＳＴＭ Ｄ７９２により測定することができる。 In the molded product of the embodiment of the present invention, the density of the mixture is preferably 0.860 to 0.940 g / cm 3 .
The lower the density, the lighter the weight, the more amorphous that can contribute to the heat shrinkage during heating, and the better the heat shrinkage effect is exhibited. Therefore, the lower limit of the density is not particularly limited. However, when the density is 0.860 g / cm 3 or more, it has sufficient mechanical properties and can suppress breakage during coil processing. From the above viewpoint, the density is more preferably 0.870 g / cm 3 or more, further preferably 0.880 g / cm 3 or more, and most preferably 0.890 g / cm 3 or more. Further, the higher the density, the better the mechanical characteristics, the suppression of breakage during coil processing, and the higher productivity, so that the upper limit of the density is not particularly limited. However, when the density is 0.940 g / cm 3 or less, amorphous materials that can contribute to heat shrinkage during heating are sufficient, and a good heat shrinkage effect can be exhibited. From the above viewpoint, the density is more preferably 0.930 g / cm 3 or less, and further preferably 0.920 g / cm 3 or less. Density can be measured by ASTM D792.
密度が低いほど、軽量で、かつ、加熱時の熱収縮に寄与できる非晶が多く、良好な熱収縮効果を発現するため、密度の下限は特に制限されない。ただし、密度が０．８６０ｇ／ｃｍ３以上であれば、十分な力学物性を有し、コイル加工時の破断を抑えることができる。前記観点から、密度は０．８７０ｇ／ｃｍ３以上がより好ましく、０．８８０ｇ／ｃｍ３以上がさらに好ましく、０．８９０ｇ／ｃｍ３以上が最も好ましい。また、密度が高いほど力学物性が向上し、コイル加工時の破断を抑制し、生産性が上がるため、密度の上限は特に制限されない。ただし、密度が０．９４０ｇ／ｃｍ３以下であれば、加熱時の熱収縮に寄与できる非晶が十分で、良好な熱収縮効果を発現することができる。前記観点から、密度は０．９３０ｇ／ｃｍ３以下がより好ましく、０．９２０ｇ／ｃｍ３以下がさらに好ましい。密度はＡＳＴＭ Ｄ７９２により測定することができる。 In the molded product of the embodiment of the present invention, the density of the mixture is preferably 0.860 to 0.940 g / cm 3 .
The lower the density, the lighter the weight, the more amorphous that can contribute to the heat shrinkage during heating, and the better the heat shrinkage effect is exhibited. Therefore, the lower limit of the density is not particularly limited. However, when the density is 0.860 g / cm 3 or more, it has sufficient mechanical properties and can suppress breakage during coil processing. From the above viewpoint, the density is more preferably 0.870 g / cm 3 or more, further preferably 0.880 g / cm 3 or more, and most preferably 0.890 g / cm 3 or more. Further, the higher the density, the better the mechanical characteristics, the suppression of breakage during coil processing, and the higher productivity, so that the upper limit of the density is not particularly limited. However, when the density is 0.940 g / cm 3 or less, amorphous materials that can contribute to heat shrinkage during heating are sufficient, and a good heat shrinkage effect can be exhibited. From the above viewpoint, the density is more preferably 0.930 g / cm 3 or less, and further preferably 0.920 g / cm 3 or less. Density can be measured by ASTM D792.
本発明の実施形態の成形体は、撚数が１～３０回／ｍｍであるであることが好ましい。
撚数とは、コイルの軸方向において、１ｍｍ当たりに成形体が捩れる回数である。撚数が高くなるほど、コイルの単位長さあたりの熱収縮率を高くすることができるため、撚数の上限は特に制限されない。ただし、加撚に伴うコイルの破断を抑制する観点から、撚数は３０回／ｍｍ以下が好ましく、２０回／ｍｍ以下がより好ましく、１５回／ｍｍ以下がさらに好ましく、１０回／ｍｍ以下が最も好ましい。
また、撚数が低くなるほど、加撚に伴うコイルの破断が抑えられ、生産性を上げることができるため、撚数の下限は特に制限されない。ただし、熱収縮率を高くする観点から、撚数は１回／ｍｍ以上が好ましく、３回／ｍｍ以上がより好ましく、５回／ｍｍ以上がさらに好ましく、７回／ｍｍ以上が最も好ましい。 The molded product according to the embodiment of the present invention preferably has a twist number of 1 to 30 times / mm.
The number of twists is the number of times the molded product is twisted per 1 mm in the axial direction of the coil. As the number of twists increases, the heat shrinkage rate per unit length of the coil can be increased, so that the upper limit of the number of twists is not particularly limited. However, from the viewpoint of suppressing the breaking of the coil due to twisting, the number of twists is preferably 30 times / mm or less, more preferably 20 times / mm or less, further preferably 15 times / mm or less, and 10 times / mm or less. Most preferred.
Further, as the number of twists is lower, the breakage of the coil due to twisting is suppressed and the productivity can be increased, so that the lower limit of the number of twists is not particularly limited. However, from the viewpoint of increasing the heat shrinkage rate, the number of twists is preferably 1 time / mm or more, more preferably 3 times / mm or more, further preferably 5 times / mm or more, and most preferably 7 times / mm or more.
撚数とは、コイルの軸方向において、１ｍｍ当たりに成形体が捩れる回数である。撚数が高くなるほど、コイルの単位長さあたりの熱収縮率を高くすることができるため、撚数の上限は特に制限されない。ただし、加撚に伴うコイルの破断を抑制する観点から、撚数は３０回／ｍｍ以下が好ましく、２０回／ｍｍ以下がより好ましく、１５回／ｍｍ以下がさらに好ましく、１０回／ｍｍ以下が最も好ましい。
また、撚数が低くなるほど、加撚に伴うコイルの破断が抑えられ、生産性を上げることができるため、撚数の下限は特に制限されない。ただし、熱収縮率を高くする観点から、撚数は１回／ｍｍ以上が好ましく、３回／ｍｍ以上がより好ましく、５回／ｍｍ以上がさらに好ましく、７回／ｍｍ以上が最も好ましい。 The molded product according to the embodiment of the present invention preferably has a twist number of 1 to 30 times / mm.
The number of twists is the number of times the molded product is twisted per 1 mm in the axial direction of the coil. As the number of twists increases, the heat shrinkage rate per unit length of the coil can be increased, so that the upper limit of the number of twists is not particularly limited. However, from the viewpoint of suppressing the breaking of the coil due to twisting, the number of twists is preferably 30 times / mm or less, more preferably 20 times / mm or less, further preferably 15 times / mm or less, and 10 times / mm or less. Most preferred.
Further, as the number of twists is lower, the breakage of the coil due to twisting is suppressed and the productivity can be increased, so that the lower limit of the number of twists is not particularly limited. However, from the viewpoint of increasing the heat shrinkage rate, the number of twists is preferably 1 time / mm or more, more preferably 3 times / mm or more, further preferably 5 times / mm or more, and most preferably 7 times / mm or more.
本発明の実施形態の成形体は、可逆的熱伸縮性を有する成形体であって、可逆的熱伸縮性を有さない部分を部分的に有することが好ましい。
本発明の実施形態の成形体は、前記実施形態の成形体を部分的に有することができ、すなわち熱収縮しない部分を部分的に有することができる。例えば、図１に示すように、繊維状成形体中央部を含む主繊維部分ａ（前記実施形態の繊維の部分）と、その両側に、繊維端を含む端部ｂを有する形態をとることができる。ａは、加熱による単位温度当たりの熱収縮率が例えば０．０７％／℃以上の高い熱収縮性を有する部分、Ｌａは主繊維部分ａの長さ、ｂは、単位温度当たりの熱収縮率が例えば０．０７％／℃未満の熱収縮性が低い（もしくは熱伸縮性が無い）部分、Ｌｂは端部ｂの長さを示す。
本実施形態の成形体をアクチュエータに使用する場合、両端部を固定するため、固定部は熱伸縮性が低いもしくは熱伸縮しないことが好ましい。
繊維軸方向（繊維長方向）に沿った全体の長さ（図１では主繊維部分ａの長さＬａと一方の端部ｂの長さＬｂと他方の端部ｂの長さＬｂとの合計）に対する、高い熱収縮性を有する部分の長さ（図１ではＬａ）の割合は、良好な熱収縮性を得るために５０％以上が好ましく、８０％以上がより好ましく、両端部の固定が緩むことなく固定する点から９８％以下であることが好ましい。 It is preferable that the molded product according to the embodiment of the present invention is a molded product having reversible thermal elasticity and partially has a portion that does not have reversible thermal elasticity.
The molded product of the embodiment of the present invention can partially have the molded product of the above-described embodiment, that is, can partially have a portion that does not shrink heat. For example, as shown in FIG. 1, the main fiber portion a including the central portion of the fibrous molded body (the fibrous portion of the embodiment) and the end portions b including the fiber ends on both sides thereof may be provided. can. a is a portion having a high heat shrinkage rate per unit temperature due to heating, for example, 0.07% / ° C. or higher, La is the length of the main fiber portion a, and b is a heat shrinkage rate per unit temperature. However, for example, a portion having a low thermal contractility (or no thermal elasticity) of less than 0.07% / ° C., Lb indicates the length of the end portion b.
When the molded product of the present embodiment is used for an actuator, since both ends are fixed, it is preferable that the fixed portion has low thermal elasticity or does not thermally expand or contract.
The total length along the fiber axis direction (fiber length direction) (in FIG. 1, the sum of the length La of the main fiber portion a, the length Lb of one end b, and the length Lb of the other end b). ), The ratio of the length of the portion having high heat shrinkage (La in FIG. 1) is preferably 50% or more, more preferably 80% or more in order to obtain good heat shrinkage, and fixing of both ends is performed. It is preferably 98% or less from the point of fixing without loosening.
本発明の実施形態の成形体は、前記実施形態の成形体を部分的に有することができ、すなわち熱収縮しない部分を部分的に有することができる。例えば、図１に示すように、繊維状成形体中央部を含む主繊維部分ａ（前記実施形態の繊維の部分）と、その両側に、繊維端を含む端部ｂを有する形態をとることができる。ａは、加熱による単位温度当たりの熱収縮率が例えば０．０７％／℃以上の高い熱収縮性を有する部分、Ｌａは主繊維部分ａの長さ、ｂは、単位温度当たりの熱収縮率が例えば０．０７％／℃未満の熱収縮性が低い（もしくは熱伸縮性が無い）部分、Ｌｂは端部ｂの長さを示す。
本実施形態の成形体をアクチュエータに使用する場合、両端部を固定するため、固定部は熱伸縮性が低いもしくは熱伸縮しないことが好ましい。
繊維軸方向（繊維長方向）に沿った全体の長さ（図１では主繊維部分ａの長さＬａと一方の端部ｂの長さＬｂと他方の端部ｂの長さＬｂとの合計）に対する、高い熱収縮性を有する部分の長さ（図１ではＬａ）の割合は、良好な熱収縮性を得るために５０％以上が好ましく、８０％以上がより好ましく、両端部の固定が緩むことなく固定する点から９８％以下であることが好ましい。 It is preferable that the molded product according to the embodiment of the present invention is a molded product having reversible thermal elasticity and partially has a portion that does not have reversible thermal elasticity.
The molded product of the embodiment of the present invention can partially have the molded product of the above-described embodiment, that is, can partially have a portion that does not shrink heat. For example, as shown in FIG. 1, the main fiber portion a including the central portion of the fibrous molded body (the fibrous portion of the embodiment) and the end portions b including the fiber ends on both sides thereof may be provided. can. a is a portion having a high heat shrinkage rate per unit temperature due to heating, for example, 0.07% / ° C. or higher, La is the length of the main fiber portion a, and b is a heat shrinkage rate per unit temperature. However, for example, a portion having a low thermal contractility (or no thermal elasticity) of less than 0.07% / ° C., Lb indicates the length of the end portion b.
When the molded product of the present embodiment is used for an actuator, since both ends are fixed, it is preferable that the fixed portion has low thermal elasticity or does not thermally expand or contract.
The total length along the fiber axis direction (fiber length direction) (in FIG. 1, the sum of the length La of the main fiber portion a, the length Lb of one end b, and the length Lb of the other end b). ), The ratio of the length of the portion having high heat shrinkage (La in FIG. 1) is preferably 50% or more, more preferably 80% or more in order to obtain good heat shrinkage, and fixing of both ends is performed. It is preferably 98% or less from the point of fixing without loosening.
前記の熱伸縮性（熱収縮性）が低いもしくは熱伸縮しない部分を形成する方法としては、例えば、架橋する時に繊維の両端部を架橋反応が起きにくい或いは起きない状態（シラン架橋の場合、例えば水含有雰囲気中に曝さない状態）にすることで熱伸縮性が低いもしくは熱伸縮しない部分を形成することができる。
As a method for forming a portion having low thermal elasticity (heat shrinkage) or not thermally expanding or contracting, for example, a state in which a cross-linking reaction is unlikely to occur or does not occur at both ends of the fiber during cross-linking (in the case of silane cross-linking, for example). By setting the condition so that it is not exposed to a water-containing atmosphere), it is possible to form a portion having low thermal elasticity or no thermal expansion and contraction.
（繊維製品）
本発明の実施形態の繊維製品は、前記実施形態の成形体を含む繊維製品であり、本発明の実施形態の繊維製品は、織物、編物、不織布、又は紐であることが好ましい。 (Fiber products)
The textile product of the embodiment of the present invention is a textile product containing the molded product of the embodiment, and the textile product of the embodiment of the present invention is preferably a woven fabric, a knitted fabric, a non-woven fabric, or a string.
本発明の実施形態の繊維製品は、前記実施形態の成形体を含む繊維製品であり、本発明の実施形態の繊維製品は、織物、編物、不織布、又は紐であることが好ましい。 (Fiber products)
The textile product of the embodiment of the present invention is a textile product containing the molded product of the embodiment, and the textile product of the embodiment of the present invention is preferably a woven fabric, a knitted fabric, a non-woven fabric, or a string.
本発明の実施形態の繊維製品は、前記繊維製品が織物であって、経糸または緯糸の一方が前記成形体を含み、他方が前記成形体を含まず且つ絶縁被膜で覆われた電熱線を含むことが好ましい。
In the textile product of the embodiment of the present invention, the textile product is a woven fabric, one of the warp and weft contains the molded body, and the other contains a heating wire that does not contain the molded body and is covered with an insulating film. Is preferable.
本発明の実施形態の織物は、経糸または緯糸の一方が可逆的熱伸縮性を有する繊維Ａであり、他方が可逆的熱伸縮性を有さず、かつ絶縁被膜で覆われた電熱線を含む。ここで、可逆的熱伸縮性を有するとは、加熱による収縮と、冷却による伸長とをおおよそ一定の変位で繰り返す性質を有することを意味する。ただし、本発明の技術的範囲は、加熱する温度範囲や繰り返し動作に伴う劣化現象による特性変化において制約を受けるものではない。可逆的熱伸縮性を有する繊維Ａが織物の経糸または緯糸の一方に配置されることで、該織物は一方向に伸縮可能となる。また、本発明の実施形態では、可逆的熱伸縮性を有する繊維Ａを複数本並べて、織物を構成する。複数の繊維Ａが並んでいることにより、伸縮の力を大きくすることができる。また、多方向に絶縁被膜で覆われた電熱線を配置することで、前記繊維Ａに効率良く熱を伝えることができ、余分な繊維を配置する必要がないため、軽量化が実現できる。
The woven fabric of the embodiment of the present invention contains a heating wire in which one of the warp and weft is a fiber A having reversible thermal elasticity and the other has no reversible thermal elasticity and is covered with an insulating film. .. Here, having a reversible thermal elasticity means having a property of repeating shrinkage due to heating and expansion due to cooling with a substantially constant displacement. However, the technical scope of the present invention is not limited by the heating temperature range or the characteristic change due to the deterioration phenomenon due to the repeated operation. By arranging the fiber A having reversible thermal elasticity on one of the warp and weft of the woven fabric, the woven fabric can be expanded and contracted in one direction. Further, in the embodiment of the present invention, a plurality of fibers A having reversible thermal elasticity are arranged side by side to form a woven fabric. By arranging a plurality of fibers A side by side, the force of expansion and contraction can be increased. Further, by arranging the heating wires covered with the insulating film in multiple directions, heat can be efficiently transferred to the fibers A, and since it is not necessary to arrange extra fibers, weight reduction can be realized.
可逆的熱伸縮性を有する好ましい態様は、復元率９０％以上の伸縮を１回以上できることが好ましく、５回以上できることがより好ましく、１０回以上できることがさらに好ましい。可逆的熱伸縮性を有するより好ましい態様は、復元率９５％以上の伸縮を１回以上できることが好ましく、５回以上できることがより好ましく、１０回以上できることがさらに好ましく、１００回以上できることが特に好ましい。可逆的熱伸縮性を有するさらに好ましい態様は、復元率９７％以上の伸縮を１回以上できることが好ましく、５回以上できることがより好ましく、１０回以上できることがさらに好ましく、１００回以上できることが特に好ましい。
A preferred embodiment having reversible thermal elasticity is preferably to be able to expand and contract with a restoration rate of 90% or more once or more, more preferably 5 times or more, and even more preferably 10 times or more. In a more preferable embodiment having reversible thermal elasticity, it is preferable to be able to expand and contract with a restoration rate of 95% or more once, more preferably 5 times or more, further preferably 10 times or more, and particularly preferably 100 times or more. .. A more preferable embodiment having reversible thermal elasticity is that the expansion and contraction with a restoration rate of 97% or more is preferably possible once or more, more preferably 5 times or more, further preferably 10 times or more, and particularly preferably 100 times or more. ..
可逆的熱伸縮性を有する繊維Ａとしては、特に限定されるものではないが、例えば、ナイロン繊維、ポリエステル繊維、アラミド繊維、ポリ塩化ビニル繊維、テフロン(登録商標)繊維、ビニロン繊維、ポリウレタン繊維、ポリ乳酸繊維、アクリル繊維、ポリオレフィン繊維、シラン架橋ポリエチレン繊維等が挙げられる。これらの中でも、可逆的熱伸縮性の観点から、ナイロン繊維、シラン架橋ポリエチレン繊維が好ましい。
The fiber A having reversible thermal elasticity is not particularly limited, and for example, nylon fiber, polyester fiber, aramid fiber, polyvinyl chloride fiber, Teflon (registered trademark) fiber, vinylon fiber, polyurethane fiber, and the like. Examples thereof include polylactic acid fiber, acrylic fiber, polyolefin fiber, and silane crosslinked polyethylene fiber. Among these, nylon fiber and silane cross-linked polyethylene fiber are preferable from the viewpoint of reversible thermal elasticity.
本発明の実施形態において、電熱線とは、発熱素線に絶縁被膜を被覆したものをいう。発熱素線の材質や寸法に特に制限はないが、抵抗値やコストの観点から、ニッケルクロム合金が好ましい。なお、電熱線の柔軟性や電熱線の直径を調整するために、発熱素線は巻芯に巻いて使用してもよい。この場合、巻芯としては、耐熱性や絶縁性、耐擦過性の観点から、ポリアリレート繊維やアラミド繊維が好適である。
In the embodiment of the present invention, the heating wire means a heating element wire coated with an insulating film. The material and dimensions of the heating element are not particularly limited, but nickel-chromium alloy is preferable from the viewpoint of resistance value and cost. In addition, in order to adjust the flexibility of the heating wire and the diameter of the heating wire, the heating element may be wound around the winding core and used. In this case, polyarylate fiber or aramid fiber is suitable as the winding core from the viewpoint of heat resistance, insulation, and scratch resistance.
前記電熱線が絶縁被膜で覆われていることで、通電加熱の際に誤ってショートする恐れがなく、人が接触しても感電の恐れがない。また、織物をアクチュエータとして使用する際には、冷却のために水等を使用する場合もあるが、感電や漏電の恐れもなくなる。絶縁被膜の材質は、絶縁性が良好な材料であれば特に制限されるものではないが、最も汎用的で安価な材料として塩化ビニルが好ましい。さらに、絶縁被膜は、耐熱性と、アクチュエータの伸縮運動に耐え得る耐摩耗性とを備えていることがより好ましく、例として、ポリテトラフルオロエチレンやテトラフルオロエチレンとパーフルオロアルコキシエチレンとの共重合体、エチレン－テトラフルオロエチレン共重合体、ポリビニリデンフルオライド等のフッ素系樹脂、ホルマール、ポリウレタン、ポリエステル、ポリアミドイミド、エナメル、架橋ポリエチレン、塩化ビニル樹脂、シリコーン系樹脂等が挙げられる。
Since the heating wire is covered with an insulating film, there is no risk of accidental short circuit during energization heating, and there is no risk of electric shock even if a person comes into contact with it. Further, when the woven fabric is used as an actuator, water or the like may be used for cooling, but there is no risk of electric shock or electric leakage. The material of the insulating coating is not particularly limited as long as it has good insulating properties, but vinyl chloride is preferable as the most versatile and inexpensive material. Further, it is more preferable that the insulating coating has heat resistance and abrasion resistance capable of withstanding the expansion and contraction movement of the actuator, and as an example, polytetrafluoroethylene or tetrafluoroethylene and a copolymer of perfluoroalkoxyethylene Examples thereof include a coalescence, an ethylene-tetrafluoroethylene copolymer, a fluororesin such as polyvinylidenefluoride, formal, polyurethane, polyester, polyamideimide, enamel, crosslinked polyethylene, vinyl chloride resin, and silicone resin.
電熱線を含む経糸または緯糸は、電熱線以外にも可逆的熱伸縮性を有さない他の糸を含むこともできる。可逆的熱伸縮性を有さない他の糸としては、化学繊維、天然繊維のどちらも使用できるが、電熱線の破断防止の点からは、強度の高い糸が好ましく、ポリエステル繊維を含む糸が好ましい。また、耐熱性などの点からは羊毛、綿が好ましい。
The warp or weft including the heating wire may include other yarns having no reversible thermal elasticity other than the heating wire. As other yarns that do not have reversible thermal elasticity, either chemical fibers or natural fibers can be used, but from the viewpoint of preventing breakage of the heating wire, high-strength yarns are preferable, and yarns containing polyester fibers are preferable. preferable. Further, wool and cotton are preferable from the viewpoint of heat resistance and the like.
本発明の実施形態の織物は、織物の組織が、平織、綾織、カラミ織および朱子織のいずれか、またはこれらの組織の組み合わせであることが好ましい。
織物の平面性や対称性や耐摩擦性を重視する場合は平織が好ましく、コイル形状の繊維の曲げ柔軟性や意匠性等の観点からは、綾織または朱子織が好ましい。繊維、またはコイル形状の繊維の伸縮を良好に発現させる観点からは、カラミ織が好ましい。 In the woven fabric of the embodiment of the present invention, it is preferable that the woven fabric has a plain weave, a twill weave, a kalami weave, a satin weave, or a combination of these weaves.
Plain weave is preferable when flatness, symmetry, and abrasion resistance of the woven fabric are important, and twill weave or satin weave is preferable from the viewpoint of bending flexibility and designability of coil-shaped fibers. From the viewpoint of satisfactorily exhibiting the expansion and contraction of the fiber or the coil-shaped fiber, the Karami weave is preferable.
織物の平面性や対称性や耐摩擦性を重視する場合は平織が好ましく、コイル形状の繊維の曲げ柔軟性や意匠性等の観点からは、綾織または朱子織が好ましい。繊維、またはコイル形状の繊維の伸縮を良好に発現させる観点からは、カラミ織が好ましい。 In the woven fabric of the embodiment of the present invention, it is preferable that the woven fabric has a plain weave, a twill weave, a kalami weave, a satin weave, or a combination of these weaves.
Plain weave is preferable when flatness, symmetry, and abrasion resistance of the woven fabric are important, and twill weave or satin weave is preferable from the viewpoint of bending flexibility and designability of coil-shaped fibers. From the viewpoint of satisfactorily exhibiting the expansion and contraction of the fiber or the coil-shaped fiber, the Karami weave is preferable.
本発明の実施形態の織物は、前記電熱線が、連続した１本の電熱線であることが好ましい。
図７は、経糸として繊維Ａ（１）を使用し、緯糸として連続した１本の電熱線２を使用した織物の一例を示す模式図である。図７に示すように、連続した１本の電熱線２をループで折り返して使用することで、長尺の電熱線をカットすることなく、より簡便に織物を製造できる。極端な例としては、１本の電熱線を１枚の織物の全てに使用できる。すなわち、１枚の織物内で、電熱線を直列回路にしているとみなすことができる。電熱線を１本の直列回路のように配置して織物を製造することで、通電の回路が簡単になり織物を軽量化しやすい。また、電熱線を緯糸として使用することで、１本の直列配置にしやすくなる。 In the woven fabric of the embodiment of the present invention, it is preferable that the heating wire is a continuous heating wire.
FIG. 7 is a schematic view showing an example of a woven fabric in which the fiber A (1) is used as a warp and acontinuous heating wire 2 is used as a weft. As shown in FIG. 7, by folding and using one continuous heating wire 2 in a loop, a woven fabric can be manufactured more easily without cutting a long heating wire. As an extreme example, one heating wire can be used for all of one woven fabric. That is, it can be considered that the heating wires are made into a series circuit in one woven fabric. By arranging the heating wires like a single series circuit to manufacture the woven fabric, the circuit of energization becomes simple and the weight of the woven fabric can be easily reduced. Further, by using the heating wire as a warp and weft, it becomes easy to arrange one in series.
図７は、経糸として繊維Ａ（１）を使用し、緯糸として連続した１本の電熱線２を使用した織物の一例を示す模式図である。図７に示すように、連続した１本の電熱線２をループで折り返して使用することで、長尺の電熱線をカットすることなく、より簡便に織物を製造できる。極端な例としては、１本の電熱線を１枚の織物の全てに使用できる。すなわち、１枚の織物内で、電熱線を直列回路にしているとみなすことができる。電熱線を１本の直列回路のように配置して織物を製造することで、通電の回路が簡単になり織物を軽量化しやすい。また、電熱線を緯糸として使用することで、１本の直列配置にしやすくなる。 In the woven fabric of the embodiment of the present invention, it is preferable that the heating wire is a continuous heating wire.
FIG. 7 is a schematic view showing an example of a woven fabric in which the fiber A (1) is used as a warp and a
また、本発明の実施形態の織物は、前記電熱線が、複数本の電熱線から構成されていてもよい。
図８は、経糸として繊維Ａ（１）を使用し、緯糸として複数本の電熱線２を使用した織物の一例を示す模式図である。電熱線が複数本の電熱線からなる織物をアクチュエータとして使用する場合、例えば繰り返し摩擦等により万が一、電熱線の破断等のトラブルが発生しても、１本の経糸もしくは緯糸の電熱線が破断するのみであり、織物単位で機能しなくなることを防ぐことができる。 Further, in the woven fabric of the embodiment of the present invention, the heating wire may be composed of a plurality of heating wires.
FIG. 8 is a schematic view showing an example of a woven fabric in which the fiber A (1) is used as a warp and a plurality ofheating wires 2 are used as a weft. When a woven fabric consisting of multiple heating wires is used as an actuator, for example, even if a trouble such as breakage of the heating wire occurs due to repeated friction, the heating wire of one warp or weft breaks. It is only possible to prevent the fabric from failing.
図８は、経糸として繊維Ａ（１）を使用し、緯糸として複数本の電熱線２を使用した織物の一例を示す模式図である。電熱線が複数本の電熱線からなる織物をアクチュエータとして使用する場合、例えば繰り返し摩擦等により万が一、電熱線の破断等のトラブルが発生しても、１本の経糸もしくは緯糸の電熱線が破断するのみであり、織物単位で機能しなくなることを防ぐことができる。 Further, in the woven fabric of the embodiment of the present invention, the heating wire may be composed of a plurality of heating wires.
FIG. 8 is a schematic view showing an example of a woven fabric in which the fiber A (1) is used as a warp and a plurality of
本発明の実施形態の繊維製品において、前記電熱線の直径が２０～２０００μｍであることが好ましい。
In the textile product of the embodiment of the present invention, the diameter of the heating wire is preferably 20 to 2000 μm.
本発明の実施形態の繊維製品において、前記繊維Ａがコイル形状であることが好ましい。
本発明の実施形態の繊維製品において、コイル形状とは、繊維材料に撚りをかけ続けた際に形成されるコイル形状をいう。コイル形状としては、芯棒等を使用せずに、単純に撚りをかけ続けることにより自然にコイルを形成させたオーバーツイスト型と、コイル形状が形成され始めた際に当箇所へ芯棒となるものを挿入、もしくは、初めから繊維材料を芯棒に巻き付けてコイル形状を形成させたマンドレル型がある。いずれにおいても、加熱することで収縮し、冷却することで伸長するものであり、本発明の実施形態においては、所望とする発生応力と熱収縮率に応じて両者を使い分けることができる。なお、コイル形状の繊維Ａは、所望のコイル形状の外径や熱収縮率が得られるように、荷重の大きさや、撚りの回数および速度、温度条件等を適宜調整することにより作製することができる。 In the textile product of the embodiment of the present invention, it is preferable that the fiber A has a coil shape.
In the textile product of the embodiment of the present invention, the coil shape means the coil shape formed when the fiber material is continuously twisted. As the coil shape, there is an over-twist type in which the coil is naturally formed by simply continuing twisting without using a core rod, etc., and when the coil shape begins to be formed, it becomes a core rod at this point. There is a mandrel type in which a coil is formed by inserting something or winding a fiber material around a core rod from the beginning. In either case, the material shrinks when heated and expands when cooled, and in the embodiment of the present invention, both can be used properly according to the desired generated stress and heat shrinkage rate. The coil-shaped fiber A can be produced by appropriately adjusting the size of the load, the number and speed of twisting, the temperature conditions, etc. so that the outer diameter and heat shrinkage of the desired coil shape can be obtained. can.
本発明の実施形態の繊維製品において、コイル形状とは、繊維材料に撚りをかけ続けた際に形成されるコイル形状をいう。コイル形状としては、芯棒等を使用せずに、単純に撚りをかけ続けることにより自然にコイルを形成させたオーバーツイスト型と、コイル形状が形成され始めた際に当箇所へ芯棒となるものを挿入、もしくは、初めから繊維材料を芯棒に巻き付けてコイル形状を形成させたマンドレル型がある。いずれにおいても、加熱することで収縮し、冷却することで伸長するものであり、本発明の実施形態においては、所望とする発生応力と熱収縮率に応じて両者を使い分けることができる。なお、コイル形状の繊維Ａは、所望のコイル形状の外径や熱収縮率が得られるように、荷重の大きさや、撚りの回数および速度、温度条件等を適宜調整することにより作製することができる。 In the textile product of the embodiment of the present invention, it is preferable that the fiber A has a coil shape.
In the textile product of the embodiment of the present invention, the coil shape means the coil shape formed when the fiber material is continuously twisted. As the coil shape, there is an over-twist type in which the coil is naturally formed by simply continuing twisting without using a core rod, etc., and when the coil shape begins to be formed, it becomes a core rod at this point. There is a mandrel type in which a coil is formed by inserting something or winding a fiber material around a core rod from the beginning. In either case, the material shrinks when heated and expands when cooled, and in the embodiment of the present invention, both can be used properly according to the desired generated stress and heat shrinkage rate. The coil-shaped fiber A can be produced by appropriately adjusting the size of the load, the number and speed of twisting, the temperature conditions, etc. so that the outer diameter and heat shrinkage of the desired coil shape can be obtained. can.
前記コイル形状の繊維Ａにおいて、コイル形状の外径Ｄ’は１００～２０００μｍであることが好ましい。
なお、本発明におけるコイル形状の外径Ｄ’とは、図３、６に示すとおり、コイルそのものの外径を意味する。コイル形状の外径Ｄ’は、織物における経糸もしくは緯糸の糸直径とみなすことができるため、織物の立体構造に大きく寄与する。以上の観点から、コイル形状の外径Ｄ’は１００～２０００μｍであることが好ましい。コイル形状の外径Ｄ’が１００μｍ以上であれば、コイルを製造する際にコイルが破断しにくく、容易にコイルを製造できる。また、コイル形状の外径Ｄ’が２０００μｍ以下であれば、１枚の織物が必要以上に厚くなることなく、平面状の織物を製造できる。前記観点から、コイル形状の外径Ｄ’は、より好ましくは１５０～１５００μｍ、さらに好ましくは２００～１０００μｍ、特に好ましくは２５０～９００μｍ、最も好ましくは３００～８００μｍである。コイル形状の外径Ｄ’の測定方法は、精密な測定ができる手段であれば特に限定されないが、光学顕微鏡やマイクロスコープによる測定が寸法精度上好ましい。 In the coil-shaped fiber A, the outer diameter D'of the coil shape is preferably 100 to 2000 μm.
The outer diameter D'of the coil shape in the present invention means the outer diameter of the coil itself, as shown in FIGS. 3 and 6. Since the outer diameter D'of the coil shape can be regarded as the thread diameter of the warp or weft in the woven fabric, it greatly contributes to the three-dimensional structure of the woven fabric. From the above viewpoint, the outer diameter D'of the coil shape is preferably 100 to 2000 μm. When the outer diameter D'of the coil shape is 100 μm or more, the coil is less likely to break when the coil is manufactured, and the coil can be easily manufactured. Further, if the outer diameter D'of the coil shape is 2000 μm or less, a flat woven fabric can be manufactured without making one woven fabric unnecessarily thick. From the above viewpoint, the outer diameter D'of the coil shape is more preferably 150 to 1500 μm, further preferably 200 to 1000 μm, particularly preferably 250 to 900 μm, and most preferably 300 to 800 μm. The method for measuring the outer diameter D'of the coil shape is not particularly limited as long as it is a means capable of precise measurement, but measurement with an optical microscope or a microscope is preferable in terms of dimensional accuracy.
なお、本発明におけるコイル形状の外径Ｄ’とは、図３、６に示すとおり、コイルそのものの外径を意味する。コイル形状の外径Ｄ’は、織物における経糸もしくは緯糸の糸直径とみなすことができるため、織物の立体構造に大きく寄与する。以上の観点から、コイル形状の外径Ｄ’は１００～２０００μｍであることが好ましい。コイル形状の外径Ｄ’が１００μｍ以上であれば、コイルを製造する際にコイルが破断しにくく、容易にコイルを製造できる。また、コイル形状の外径Ｄ’が２０００μｍ以下であれば、１枚の織物が必要以上に厚くなることなく、平面状の織物を製造できる。前記観点から、コイル形状の外径Ｄ’は、より好ましくは１５０～１５００μｍ、さらに好ましくは２００～１０００μｍ、特に好ましくは２５０～９００μｍ、最も好ましくは３００～８００μｍである。コイル形状の外径Ｄ’の測定方法は、精密な測定ができる手段であれば特に限定されないが、光学顕微鏡やマイクロスコープによる測定が寸法精度上好ましい。 In the coil-shaped fiber A, the outer diameter D'of the coil shape is preferably 100 to 2000 μm.
The outer diameter D'of the coil shape in the present invention means the outer diameter of the coil itself, as shown in FIGS. 3 and 6. Since the outer diameter D'of the coil shape can be regarded as the thread diameter of the warp or weft in the woven fabric, it greatly contributes to the three-dimensional structure of the woven fabric. From the above viewpoint, the outer diameter D'of the coil shape is preferably 100 to 2000 μm. When the outer diameter D'of the coil shape is 100 μm or more, the coil is less likely to break when the coil is manufactured, and the coil can be easily manufactured. Further, if the outer diameter D'of the coil shape is 2000 μm or less, a flat woven fabric can be manufactured without making one woven fabric unnecessarily thick. From the above viewpoint, the outer diameter D'of the coil shape is more preferably 150 to 1500 μm, further preferably 200 to 1000 μm, particularly preferably 250 to 900 μm, and most preferably 300 to 800 μm. The method for measuring the outer diameter D'of the coil shape is not particularly limited as long as it is a means capable of precise measurement, but measurement with an optical microscope or a microscope is preferable in terms of dimensional accuracy.
また、前記電熱線の直径は２０～２０００μｍであることが好ましい。本発明における電熱線の直径とは、絶縁被膜を含む線の外径を意味する。電熱線の直径は、織物における経糸もしくは緯糸の糸直径とみなすことができるため、織物の立体構造に大きく寄与する。電熱線の直径が小さいほど、織り込んだ際の非加熱部との接触面積が増え、通電加熱によって生じた熱量を良好に非加熱部へ伝えることができる。そのため、電熱線の直径の下限は特に制限されないが、電熱線の直径が２０μｍ以上であれば、擦過に強く、繰り返し耐久性の高い織物を製造できる。また、電熱線の直径が２０００μｍ以下であれば、１枚の織物が必要以上に厚くなることなく、平面状の織物を製造できる。前記観点から、電熱線の直径は、より好ましくは３０～１５００μｍ、さらに好ましくは４０～１５００μｍ、特に好ましくは５０～１３００μｍ、最も好ましくは１００～１０００μｍである。電熱線の直径の測定方法は、コイル形状の外径と同様、光学顕微鏡やマイクロスコープによる測定が寸法精度上好ましい。
Further, the diameter of the heating wire is preferably 20 to 2000 μm. The diameter of the heating wire in the present invention means the outer diameter of the wire including the insulating coating. Since the diameter of the heating wire can be regarded as the diameter of the warp or weft in the woven fabric, it greatly contributes to the three-dimensional structure of the woven fabric. The smaller the diameter of the heating wire, the larger the contact area with the non-heated portion when weaving, and the amount of heat generated by energization heating can be satisfactorily transferred to the non-heated portion. Therefore, the lower limit of the diameter of the heating wire is not particularly limited, but if the diameter of the heating wire is 20 μm or more, it is possible to produce a woven fabric that is resistant to scratching and has high repeatability. Further, if the diameter of the heating wire is 2000 μm or less, a flat woven fabric can be manufactured without making one woven fabric unnecessarily thick. From the above viewpoint, the diameter of the heating wire is more preferably 30 to 1500 μm, further preferably 40 to 1500 μm, particularly preferably 50 to 1300 μm, and most preferably 100 to 1000 μm. As a method for measuring the diameter of the heating wire, it is preferable to measure with an optical microscope or a microscope in terms of dimensional accuracy, as in the case of the outer diameter of the coil shape.
本発明の実施形態の織物は、可逆的熱伸縮性を有し、熱収縮率が３％以上であることが好ましい。
織物の熱収縮率が３％以上であれば、アクチュエータとして利用しやすくなる。熱収縮率が大きいほど、使用用途が広がるため好ましい。この観点から、前記熱収縮率は４％以上がより好ましく、５％以上がさらに好ましい。また、前記熱収縮率は、３０％以下であることが好ましい。前記熱収縮率が３０％以下であれば、織物の収縮前の形態が維持しやすくなる。この観点から、熱収縮率は２０％以下がより好ましく、１５％以下がさらに好ましい。
なお、本発明の実施形態において、織物の熱収縮率は、可逆的熱伸縮性を有する繊維Ａの熱収縮率とほぼ等しいものと考えることができる。ただし、織物を形成する際に、コイル形状の繊維Ａが蛇行して配置されることにより、織物の熱収縮率が少し高くなる可能性も考えられる。いずれにせよ、織物の熱収縮率が３％以上であるか、上記範囲内にあるか、織物を構成する可逆的熱伸縮性を有する繊維Ａの熱収縮率が３％以上であるか、上記範囲内にあることが望ましい。 The woven fabric of the embodiment of the present invention preferably has reversible thermal elasticity and a thermal shrinkage rate of 3% or more.
If the heat shrinkage rate of the woven fabric is 3% or more, it can be easily used as an actuator. The larger the heat shrinkage rate, the wider the range of uses, which is preferable. From this viewpoint, the heat shrinkage rate is more preferably 4% or more, further preferably 5% or more. Further, the heat shrinkage rate is preferably 30% or less. When the heat shrinkage rate is 30% or less, the shape of the woven fabric before shrinkage can be easily maintained. From this viewpoint, the heat shrinkage rate is more preferably 20% or less, still more preferably 15% or less.
In the embodiment of the present invention, the heat shrinkage rate of the woven fabric can be considered to be substantially equal to the heat shrinkage rate of the fiber A having reversible heat stretchability. However, when the woven fabric is formed, the coil-shaped fibers A may be arranged in a meandering manner, so that the heat shrinkage rate of the woven fabric may be slightly increased. In any case, whether the heat shrinkage rate of the woven fabric is 3% or more, is within the above range, or the heat shrinkage rate of the fiber A having reversible heat elasticity constituting the woven fabric is 3% or more, as described above. It is desirable to be within the range.
織物の熱収縮率が３％以上であれば、アクチュエータとして利用しやすくなる。熱収縮率が大きいほど、使用用途が広がるため好ましい。この観点から、前記熱収縮率は４％以上がより好ましく、５％以上がさらに好ましい。また、前記熱収縮率は、３０％以下であることが好ましい。前記熱収縮率が３０％以下であれば、織物の収縮前の形態が維持しやすくなる。この観点から、熱収縮率は２０％以下がより好ましく、１５％以下がさらに好ましい。
なお、本発明の実施形態において、織物の熱収縮率は、可逆的熱伸縮性を有する繊維Ａの熱収縮率とほぼ等しいものと考えることができる。ただし、織物を形成する際に、コイル形状の繊維Ａが蛇行して配置されることにより、織物の熱収縮率が少し高くなる可能性も考えられる。いずれにせよ、織物の熱収縮率が３％以上であるか、上記範囲内にあるか、織物を構成する可逆的熱伸縮性を有する繊維Ａの熱収縮率が３％以上であるか、上記範囲内にあることが望ましい。 The woven fabric of the embodiment of the present invention preferably has reversible thermal elasticity and a thermal shrinkage rate of 3% or more.
If the heat shrinkage rate of the woven fabric is 3% or more, it can be easily used as an actuator. The larger the heat shrinkage rate, the wider the range of uses, which is preferable. From this viewpoint, the heat shrinkage rate is more preferably 4% or more, further preferably 5% or more. Further, the heat shrinkage rate is preferably 30% or less. When the heat shrinkage rate is 30% or less, the shape of the woven fabric before shrinkage can be easily maintained. From this viewpoint, the heat shrinkage rate is more preferably 20% or less, still more preferably 15% or less.
In the embodiment of the present invention, the heat shrinkage rate of the woven fabric can be considered to be substantially equal to the heat shrinkage rate of the fiber A having reversible heat stretchability. However, when the woven fabric is formed, the coil-shaped fibers A may be arranged in a meandering manner, so that the heat shrinkage rate of the woven fabric may be slightly increased. In any case, whether the heat shrinkage rate of the woven fabric is 3% or more, is within the above range, or the heat shrinkage rate of the fiber A having reversible heat elasticity constituting the woven fabric is 3% or more, as described above. It is desirable to be within the range.
熱収縮させる温度は５０～１５０℃の範囲が好ましい。低温で収縮させるほど効率が良く、５０℃以上であれば、外気温との温度の差の影響が少なく、熱収縮の制御がしやすい。熱収縮するスピードの観点から、熱収縮させる温度は高い方が好ましく、６０℃以上がより好ましく、７０℃以上がさらに好ましい。また、熱収縮させる温度が１５０℃以下であれば、温度上昇までの時間を短縮でき速やかに収縮させることができる。この観点から、熱収縮させる温度は１２０℃以下がより好ましく、１００℃以下がさらに好ましい。
The temperature for heat shrinkage is preferably in the range of 50 to 150 ° C. The more it shrinks at a low temperature, the more efficient it is, and if it is 50 ° C. or higher, the influence of the temperature difference from the outside air temperature is small, and it is easy to control the heat shrinkage. From the viewpoint of the speed of heat shrinkage, the temperature for heat shrinkage is preferably high, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher. Further, when the heat shrinkage temperature is 150 ° C. or lower, the time until the temperature rise can be shortened and the shrinkage can be performed quickly. From this point of view, the heat shrinkage temperature is more preferably 120 ° C. or lower, further preferably 100 ° C. or lower.
本発明の実施形態の繊維製品は、一辺の長さが５０～１０００ｍｍ、他方の辺の長さが５～２００ｍｍであることが好ましい。長辺と短辺からなる矩形あるいは長尺形状とすることができ、各辺が同じ長さの正方形であってよい。
本発明の実施形態の繊維製品が織物である場合は、長辺の長さが５０～１０００ｍｍ、短辺の長さが５～２００ｍｍであることが好ましい。
本発明の実施形態の織物の長辺の長さは、アシストスーツへの応用を検討する場合には、５０～１０００ｍｍであればよい。長辺の長さは、織物の使用箇所や使用方法、使用者の体格、コイル形状の繊維のアクチュエータとしての伸縮長等に応じて適宜選択される。例えば身長が１７０ｃｍ、体重が６０ｋｇの標準的な体格に対しては、腰補助用アシストスーツの場合は長辺の長さが８０～５００ｍｍであることが好ましい。 The textile product of the embodiment of the present invention preferably has a side length of 50 to 1000 mm and a side length of 5 to 200 mm. It can be a rectangle or a long shape consisting of a long side and a short side, and each side may be a square having the same length.
When the textile product of the embodiment of the present invention is a woven fabric, it is preferable that the length of the long side is 50 to 1000 mm and the length of the short side is 5 to 200 mm.
The length of the long side of the woven fabric of the embodiment of the present invention may be 50 to 1000 mm when considering application to an assist suit. The length of the long side is appropriately selected according to the place and method of use of the woven fabric, the physique of the user, the expansion and contraction length of the coil-shaped fiber as an actuator, and the like. For example, for a standard physique having a height of 170 cm and a weight of 60 kg, it is preferable that the length of the long side is 80 to 500 mm in the case of the waist assist assist suit.
本発明の実施形態の繊維製品が織物である場合は、長辺の長さが５０～１０００ｍｍ、短辺の長さが５～２００ｍｍであることが好ましい。
本発明の実施形態の織物の長辺の長さは、アシストスーツへの応用を検討する場合には、５０～１０００ｍｍであればよい。長辺の長さは、織物の使用箇所や使用方法、使用者の体格、コイル形状の繊維のアクチュエータとしての伸縮長等に応じて適宜選択される。例えば身長が１７０ｃｍ、体重が６０ｋｇの標準的な体格に対しては、腰補助用アシストスーツの場合は長辺の長さが８０～５００ｍｍであることが好ましい。 The textile product of the embodiment of the present invention preferably has a side length of 50 to 1000 mm and a side length of 5 to 200 mm. It can be a rectangle or a long shape consisting of a long side and a short side, and each side may be a square having the same length.
When the textile product of the embodiment of the present invention is a woven fabric, it is preferable that the length of the long side is 50 to 1000 mm and the length of the short side is 5 to 200 mm.
The length of the long side of the woven fabric of the embodiment of the present invention may be 50 to 1000 mm when considering application to an assist suit. The length of the long side is appropriately selected according to the place and method of use of the woven fabric, the physique of the user, the expansion and contraction length of the coil-shaped fiber as an actuator, and the like. For example, for a standard physique having a height of 170 cm and a weight of 60 kg, it is preferable that the length of the long side is 80 to 500 mm in the case of the waist assist assist suit.
本発明の実施形態の織物の短辺の長さは、アシストスーツへの応用を検討する場合には、５～２００ｍｍであればよい。短辺の長さは、モジュールとしての必要発生応力と、モジュールの寸法等に応じて適宜選択される。例えば、背中側に背負うシステムのアシストスーツにおいて、左右に分けて２つのモジュールとして使用する場合、短辺の長さが２００ｍｍ以下であれば、装着感を損なうことなく使用することができる。
The length of the short side of the woven fabric according to the embodiment of the present invention may be 5 to 200 mm when considering application to an assist suit. The length of the short side is appropriately selected according to the required stress generated as the module, the dimensions of the module, and the like. For example, in an assist suit of a system carried on the back side, when it is used as two modules divided into left and right, if the length of the short side is 200 mm or less, it can be used without impairing the wearing feeling.
本発明の実施形態のアクチュエータは、前記実施形態の成形体が並行配列および／または直列配列されている。
本発明の実施形態の成形体を並行に配列することによって、収縮力を大きくすることができ、また、直列に配列することによって、収縮変位を大きくすることができる。
前記成形体が繊維状成形体である場合、並行配列および／または直列配列するために織物や編物などの生地としてもよい。
本発明の実施形態のアクチュエータは、少なくとも本発明の実施形態の成形体と、加熱手段を含む構成を有することがきる。このアクチュエータはさらに冷却手段を含むこともできる。 In the actuator of the embodiment of the present invention, the compacts of the embodiment are arranged in parallel and / or in series.
By arranging the molded bodies of the embodiment of the present invention in parallel, the contraction force can be increased, and by arranging them in series, the contraction displacement can be increased.
When the molded product is a fibrous molded product, it may be used as a fabric such as a woven fabric or a knitted fabric for parallel arrangement and / or serial arrangement.
The actuator of the embodiment of the present invention can have at least a structure including a molded body of the embodiment of the present invention and heating means. The actuator may further include cooling means.
本発明の実施形態の成形体を並行に配列することによって、収縮力を大きくすることができ、また、直列に配列することによって、収縮変位を大きくすることができる。
前記成形体が繊維状成形体である場合、並行配列および／または直列配列するために織物や編物などの生地としてもよい。
本発明の実施形態のアクチュエータは、少なくとも本発明の実施形態の成形体と、加熱手段を含む構成を有することがきる。このアクチュエータはさらに冷却手段を含むこともできる。 In the actuator of the embodiment of the present invention, the compacts of the embodiment are arranged in parallel and / or in series.
By arranging the molded bodies of the embodiment of the present invention in parallel, the contraction force can be increased, and by arranging them in series, the contraction displacement can be increased.
When the molded product is a fibrous molded product, it may be used as a fabric such as a woven fabric or a knitted fabric for parallel arrangement and / or serial arrangement.
The actuator of the embodiment of the present invention can have at least a structure including a molded body of the embodiment of the present invention and heating means. The actuator may further include cooling means.
前記加熱手段は特に限定されないが、例えば、温風による直接加熱の他、金属被覆や電熱線の複合により、電場によって加熱することもできる。また、冷却手段は必ずしも必須ではないが、ファンによる空冷やペルチェ素子を組み合わせることで、効率的に冷却することができる。
The heating means is not particularly limited, but for example, in addition to direct heating with warm air, heating can also be performed by an electric field by combining a metal coating or a heating wire. Further, although the cooling means is not always essential, efficient cooling can be achieved by combining air cooling with a fan or a Pelche element.
（アクチュエータモジュール）
本発明の実施形態のアクチュエータモジュールは、前記実施形態の繊維製品が２～３０枚積層した積層物を含む。 (Actuator module)
The actuator module of the embodiment of the present invention includes a laminate in which 2 to 30 textile products of the above embodiment are laminated.
本発明の実施形態のアクチュエータモジュールは、前記実施形態の繊維製品が２～３０枚積層した積層物を含む。 (Actuator module)
The actuator module of the embodiment of the present invention includes a laminate in which 2 to 30 textile products of the above embodiment are laminated.
本発明の実施形態のアクチュエータモジュールは、前記織物が２～３０枚積層した積層物を含むことが好ましい。
本発明においては、熱収縮方向が同じ方向になるように前記織物を積層することによって、厚み方向へも、コイル形状の繊維の数を増やし、伸縮力を増やすことができる。また、織物を積層することで、電熱線を発熱させた際に、周囲の空気等への熱のロスを減らし、効率的に、コイル形状の繊維を加熱することができるようになる。
例えば、平織の織物を同じ位置で厚み方向が増すように１０枚積層した場合、図９に示すように、コイル形状の繊維１が、その織物を構成する電熱線２および２’だけでなく、周囲の織物における電熱線とも接触して加熱される。そのため、加熱時の熱エネルギーのロスをより低減して、効率的にアクチュエータとして動作させることが可能となる。織物の積層枚数は、必要とされる発生応力に応じて決定することができる。織物の積層枚数が多いほどモジュールの大きさに対する表面積の割合が減るため、効率よくコイル形状の繊維を加熱することができる。 The actuator module according to the embodiment of the present invention preferably includes a laminate in which 2 to 30 sheets of the above-mentioned fabric are laminated.
In the present invention, by laminating the woven fabrics so that the heat shrinkage directions are the same, the number of coil-shaped fibers can be increased and the stretching force can be increased also in the thickness direction. Further, by laminating the woven fabrics, when the heating wire is heated, the heat loss to the surrounding air or the like is reduced, and the coil-shaped fibers can be efficiently heated.
For example, when 10 plain weave fabrics are laminated at the same position so as to increase in the thickness direction, as shown in FIG. 9, the coil-shapedfibers 1 are not only the heating wires 2 and 2'constituting the fabric, but also the heating wires 2 and 2'. It is also heated in contact with the heating wire in the surrounding woven fabric. Therefore, it is possible to further reduce the loss of heat energy during heating and efficiently operate the actuator. The number of laminated fabrics can be determined according to the required generated stress. As the number of laminated fabrics increases, the ratio of the surface area to the size of the module decreases, so that the coil-shaped fibers can be heated efficiently.
本発明においては、熱収縮方向が同じ方向になるように前記織物を積層することによって、厚み方向へも、コイル形状の繊維の数を増やし、伸縮力を増やすことができる。また、織物を積層することで、電熱線を発熱させた際に、周囲の空気等への熱のロスを減らし、効率的に、コイル形状の繊維を加熱することができるようになる。
例えば、平織の織物を同じ位置で厚み方向が増すように１０枚積層した場合、図９に示すように、コイル形状の繊維１が、その織物を構成する電熱線２および２’だけでなく、周囲の織物における電熱線とも接触して加熱される。そのため、加熱時の熱エネルギーのロスをより低減して、効率的にアクチュエータとして動作させることが可能となる。織物の積層枚数は、必要とされる発生応力に応じて決定することができる。織物の積層枚数が多いほどモジュールの大きさに対する表面積の割合が減るため、効率よくコイル形状の繊維を加熱することができる。 The actuator module according to the embodiment of the present invention preferably includes a laminate in which 2 to 30 sheets of the above-mentioned fabric are laminated.
In the present invention, by laminating the woven fabrics so that the heat shrinkage directions are the same, the number of coil-shaped fibers can be increased and the stretching force can be increased also in the thickness direction. Further, by laminating the woven fabrics, when the heating wire is heated, the heat loss to the surrounding air or the like is reduced, and the coil-shaped fibers can be efficiently heated.
For example, when 10 plain weave fabrics are laminated at the same position so as to increase in the thickness direction, as shown in FIG. 9, the coil-shaped
本発明の実施形態において、前記織物の積層物は、電源や冷却ユニット等を付帯することでアクチュエータモジュールとすることができる。電源は、必要な電力が供給可能なものであれば特に制限されることはなく、固定式や携帯式といった様態にも特に制限はない。また、冷却ユニットとしては、冷風による空冷や液体による冷却が挙げられる。また、特にコントロールが必要でなければ自然冷却でも構わない。迅速な冷却が必要な場合は、液体による冷却が有用である。その場合、本発明の実施形態の織物は電熱線が絶縁被膜を有しているため、水等の電気を通しやすい液体でも利用することができる。また、当然さらなる安全性を確保するために、絶縁性の液体を使用しても構わない。絶縁性の液体としては、例えばシリコーンオイルやパーフルオロポリエーテルなどが挙げられる。パーフルオロポリエーテルは一般的に冷媒としても知られるため、本発明の実施形態の積層物には好適である。また、加熱と冷却の両者を効率よく使用するためにペルチェ素子の利用が有効である。
In the embodiment of the present invention, the laminate of the woven fabric can be made into an actuator module by attaching a power supply, a cooling unit, or the like. The power source is not particularly limited as long as it can supply the required power, and there is no particular limitation on the fixed type or the portable type. Further, examples of the cooling unit include air cooling with cold air and cooling with a liquid. In addition, natural cooling may be used unless special control is required. Liquid cooling is useful when rapid cooling is required. In that case, since the woven fabric of the embodiment of the present invention has an insulating coating on the heating wire, it can be used even with a liquid such as water that easily conducts electricity. In addition, of course, an insulating liquid may be used to ensure further safety. Examples of the insulating liquid include silicone oil and perfluoropolyether. Since perfluoropolyether is also generally known as a refrigerant, it is suitable for the laminate of the embodiment of the present invention. Further, it is effective to use a Pelche element in order to efficiently use both heating and cooling.
（アクチュエータ）
本発明の実施形態のアクチュエータは、前記実施形態の成形体を含むアクチュエータ、あるいは、前記実施形態の成形体を並行及び／又は直列に配列して形成されるアクチュエータである。
本発明の実施形態のアクチュエータは、ソフトアクチュエータと呼ばれることもあり、素材自体が伸縮性を有するものである。
本実施形態のアクチュエータは、少なくとも、前記成形体と、加熱器を含む構成を有することができる。さらに、冷却器を有することもできる。
前記成形体を並行に配列することによって、収縮力を大きくすることができる。また、直列に配列することによって、収縮変位を大きくすることができる。
本発明の実施形態のアクチュエータを加熱する方法は特に限定されないが、例えば、温風による直接加熱の他、金属被覆や電熱線の複合により、電場によって加熱することもできる。好ましくは、絶縁被膜した電熱線を用いることにより、感電防止や耐久性を付与する事ができる。また、冷却は必ずしも必須ではないが、ファンによる空冷やペルチェ素子を組み合わせることで、効率的に冷却することができる。
本発明の実施形態のアクチュエータの用途として、好ましくは、高い収縮の発生力と高い伸縮変位が要求されるパワーアシストスーツ、ロボットのアーム、ロボットのハンド、その他ロボットの駆動部に利用する事ができる。
また、軽量性や静音性が要求される車載用センサーの駆動部、車載用ルーバーの駆動部、車載用座席の駆動部、車載用カメラの駆動部、その他車載用デバイスの駆動部に利用する事ができる。
また、軽量性と高い収縮の発生力が要求される内視鏡や止血バンドなどの医療用デバイス、カメラレンズの駆動部などの家電製品、ドローンのジンバルなどの航空機部品、工業用内視鏡の駆動部、ベッドの駆動部、室内空調用ルーバーの駆動部、空調用センサー/カメラ駆動部、インナー/アウターウェアなどの繊維製品、介護用マットに利用する事ができる。
また、温度変化で駆動する事が要求されるサーモスタットとして混合バルブ、シャワー湯温調整、火傷防止装置に利用する事ができる。 (Actuator)
The actuator of the embodiment of the present invention is an actuator including the molded body of the embodiment, or an actuator formed by arranging the molded bodies of the embodiment in parallel and / or in series.
The actuator of the embodiment of the present invention is sometimes called a soft actuator, and the material itself has elasticity.
The actuator of the present embodiment can have at least a configuration including the molded body and a heater. In addition, it can also have a cooler.
By arranging the molded bodies in parallel, the contraction force can be increased. Further, by arranging them in series, the contraction displacement can be increased.
The method for heating the actuator according to the embodiment of the present invention is not particularly limited, but for example, in addition to direct heating with warm air, heating by an electric field can also be performed by combining a metal coating or a heating wire. Preferably, by using a heating wire having an insulating coating, it is possible to prevent electric shock and impart durability. Further, although cooling is not always essential, efficient cooling can be achieved by combining air cooling with a fan or a Pelche element.
As an application of the actuator of the embodiment of the present invention, it can be preferably used for a power assist suit, a robot arm, a robot hand, and other robot driving parts that require a high contraction generating force and a high expansion / contraction displacement. ..
In addition, it should be used for the drive unit of in-vehicle sensors, the drive unit of in-vehicle louvers, the drive unit of in-vehicle seats, the drive unit of in-vehicle cameras, and the drive unit of other in-vehicle devices, which are required to be lightweight and quiet. Can be done.
In addition, medical devices such as endoscopes and hemostatic bands that are required to be lightweight and generate high contraction, home appliances such as camera lens drives, aircraft parts such as drone gimbals, and industrial endoscopes. It can be used for drive units, bed drives, indoor air-conditioning louver drives, air-conditioning sensors / camera drives, textile products such as inner / outer wear, and nursing mats.
It can also be used as a thermostat that is required to be driven by temperature changes, such as a mixing valve, shower hot water temperature adjustment, and burn prevention device.
本発明の実施形態のアクチュエータは、前記実施形態の成形体を含むアクチュエータ、あるいは、前記実施形態の成形体を並行及び／又は直列に配列して形成されるアクチュエータである。
本発明の実施形態のアクチュエータは、ソフトアクチュエータと呼ばれることもあり、素材自体が伸縮性を有するものである。
本実施形態のアクチュエータは、少なくとも、前記成形体と、加熱器を含む構成を有することができる。さらに、冷却器を有することもできる。
前記成形体を並行に配列することによって、収縮力を大きくすることができる。また、直列に配列することによって、収縮変位を大きくすることができる。
本発明の実施形態のアクチュエータを加熱する方法は特に限定されないが、例えば、温風による直接加熱の他、金属被覆や電熱線の複合により、電場によって加熱することもできる。好ましくは、絶縁被膜した電熱線を用いることにより、感電防止や耐久性を付与する事ができる。また、冷却は必ずしも必須ではないが、ファンによる空冷やペルチェ素子を組み合わせることで、効率的に冷却することができる。
本発明の実施形態のアクチュエータの用途として、好ましくは、高い収縮の発生力と高い伸縮変位が要求されるパワーアシストスーツ、ロボットのアーム、ロボットのハンド、その他ロボットの駆動部に利用する事ができる。
また、軽量性や静音性が要求される車載用センサーの駆動部、車載用ルーバーの駆動部、車載用座席の駆動部、車載用カメラの駆動部、その他車載用デバイスの駆動部に利用する事ができる。
また、軽量性と高い収縮の発生力が要求される内視鏡や止血バンドなどの医療用デバイス、カメラレンズの駆動部などの家電製品、ドローンのジンバルなどの航空機部品、工業用内視鏡の駆動部、ベッドの駆動部、室内空調用ルーバーの駆動部、空調用センサー/カメラ駆動部、インナー/アウターウェアなどの繊維製品、介護用マットに利用する事ができる。
また、温度変化で駆動する事が要求されるサーモスタットとして混合バルブ、シャワー湯温調整、火傷防止装置に利用する事ができる。 (Actuator)
The actuator of the embodiment of the present invention is an actuator including the molded body of the embodiment, or an actuator formed by arranging the molded bodies of the embodiment in parallel and / or in series.
The actuator of the embodiment of the present invention is sometimes called a soft actuator, and the material itself has elasticity.
The actuator of the present embodiment can have at least a configuration including the molded body and a heater. In addition, it can also have a cooler.
By arranging the molded bodies in parallel, the contraction force can be increased. Further, by arranging them in series, the contraction displacement can be increased.
The method for heating the actuator according to the embodiment of the present invention is not particularly limited, but for example, in addition to direct heating with warm air, heating by an electric field can also be performed by combining a metal coating or a heating wire. Preferably, by using a heating wire having an insulating coating, it is possible to prevent electric shock and impart durability. Further, although cooling is not always essential, efficient cooling can be achieved by combining air cooling with a fan or a Pelche element.
As an application of the actuator of the embodiment of the present invention, it can be preferably used for a power assist suit, a robot arm, a robot hand, and other robot driving parts that require a high contraction generating force and a high expansion / contraction displacement. ..
In addition, it should be used for the drive unit of in-vehicle sensors, the drive unit of in-vehicle louvers, the drive unit of in-vehicle seats, the drive unit of in-vehicle cameras, and the drive unit of other in-vehicle devices, which are required to be lightweight and quiet. Can be done.
In addition, medical devices such as endoscopes and hemostatic bands that are required to be lightweight and generate high contraction, home appliances such as camera lens drives, aircraft parts such as drone gimbals, and industrial endoscopes. It can be used for drive units, bed drives, indoor air-conditioning louver drives, air-conditioning sensors / camera drives, textile products such as inner / outer wear, and nursing mats.
It can also be used as a thermostat that is required to be driven by temperature changes, such as a mixing valve, shower hot water temperature adjustment, and burn prevention device.
（アシストスーツ）
本発明の実施形態のアシストスーツは、前記実施形態のアクチュエータモジュールを駆動部として備える。
前記織物および前記アクチュエータモジュールは、様々な用途で利用可能であるが、コイル形状の繊維の質量当たりの発生応力が高いという特長から、特にアシストスーツへの利用が好適である。アシストスーツとは、医療・介護分野や物流・荷役など重量物を扱う分野で、人間の力に加えて補助的に作用するための外骨格型もしくは衣類型の装置である。アシストスーツは、駆動部としてのアクチュエータモジュールに加え、人体に装着するためのベルトやサポータ等を含むことができる。また、アシストスーツは、動作幅や動作方向を操作するためにギヤ等を具備することができ、必要に応じてリンク機構等の機械機構を含むことができる。目的に応じて、腰補助用や歩行補助用や腕補助用等、様々なタイプのアシストスーツが挙げられる。前記織物および前記アクチュエータモジュールは、これら種々のアシストスーツの構成要素として、いずれのタイプにも適用可能である。 (Assist suit)
The assist suit of the embodiment of the present invention includes the actuator module of the embodiment as a drive unit.
Although the woven fabric and the actuator module can be used for various purposes, they are particularly suitable for use in assist suits because of the high stress generated per mass of coil-shaped fibers. An assist suit is an exoskeleton-type or clothing-type device that acts as an auxiliary in addition to human power in fields such as medical / nursing care and logistics / cargo handling. The assist suit can include a belt, a supporter, and the like to be attached to the human body in addition to the actuator module as a drive unit. Further, the assist suit may be provided with a gear or the like for manipulating the operating width and the operating direction, and may include a mechanical mechanism such as a link mechanism, if necessary. Depending on the purpose, various types of assist suits such as waist assist, walking assist, and arm assist can be mentioned. The fabric and the actuator module are applicable to any type as components of these various assist suits.
本発明の実施形態のアシストスーツは、前記実施形態のアクチュエータモジュールを駆動部として備える。
前記織物および前記アクチュエータモジュールは、様々な用途で利用可能であるが、コイル形状の繊維の質量当たりの発生応力が高いという特長から、特にアシストスーツへの利用が好適である。アシストスーツとは、医療・介護分野や物流・荷役など重量物を扱う分野で、人間の力に加えて補助的に作用するための外骨格型もしくは衣類型の装置である。アシストスーツは、駆動部としてのアクチュエータモジュールに加え、人体に装着するためのベルトやサポータ等を含むことができる。また、アシストスーツは、動作幅や動作方向を操作するためにギヤ等を具備することができ、必要に応じてリンク機構等の機械機構を含むことができる。目的に応じて、腰補助用や歩行補助用や腕補助用等、様々なタイプのアシストスーツが挙げられる。前記織物および前記アクチュエータモジュールは、これら種々のアシストスーツの構成要素として、いずれのタイプにも適用可能である。 (Assist suit)
The assist suit of the embodiment of the present invention includes the actuator module of the embodiment as a drive unit.
Although the woven fabric and the actuator module can be used for various purposes, they are particularly suitable for use in assist suits because of the high stress generated per mass of coil-shaped fibers. An assist suit is an exoskeleton-type or clothing-type device that acts as an auxiliary in addition to human power in fields such as medical / nursing care and logistics / cargo handling. The assist suit can include a belt, a supporter, and the like to be attached to the human body in addition to the actuator module as a drive unit. Further, the assist suit may be provided with a gear or the like for manipulating the operating width and the operating direction, and may include a mechanical mechanism such as a link mechanism, if necessary. Depending on the purpose, various types of assist suits such as waist assist, walking assist, and arm assist can be mentioned. The fabric and the actuator module are applicable to any type as components of these various assist suits.
（熱収縮率、復元率の測定方法）
実施例および比較例の成形体は、熱機械分析装置（日立ハイテクサイエンス社製、型式：ＴＭＡ６１００）を使用し、次のようにして熱収縮率および復元率を測定した。
まず、成形体試料に、直径から算出した断面積をもとに、引張応力が１、３、５、１０MPaとなるように荷重をかけ、約５ｍｍの間隔で２か所に印をつける。
次に、前記引張荷重をかけた状態で、３５℃から８５℃まで昇温し、３５℃まで降温する。３５℃に降温した状態で、先に成形体試料に付けた２か所の印の間の距離（Ｌ１）を測定する。次いで、３５℃から８５℃まで再度昇温し、成形体試料に付けた２か所の印の間の距離（Ｌ２）を測定する。
距離Ｌ１及びＬ２から、以下の式により熱収縮率を求める。
熱収縮率（％）＝（Ｌ１－Ｌ２）×１００／Ｌ１
単位温度当たりの熱収縮率（％／℃）＝（Ｌ１－Ｌ２）×１００／Ｌ１／５０
続いて、３５℃まで降温し、成形体に付けた２か所の印の間の距離（Ｌ３）を測定し、さらに同様にして昇温と降温を９回繰り返した後、成形体に付けた２か所の印の間の距離（Ｌ３）を測定する。
距離Ｌ１及びＬ３から、以下の式により復元率を求める。
復元率（％）＝１００－｜初期試長変化率｜
初期試長変化率＝（Ｌ３－Ｌ１）×１００／Ｌ１
表１では、昇温と降温の繰り返しが１回のものを「復元率１」、繰り返しが１０回のものを「復元率１０」とした。
また、引張応力（Ｐａ）は、熱収縮率を測定するときに成形体試料に掛ける荷重Ｆ（Ｎ）と成形体断面積Ａ（ｍｍ２）から下記式より求めた。
引張応力（Ｐａ）＝Ｆ／Ａ (Measurement method of heat shrinkage rate and restoration rate)
As the molded products of Examples and Comparative Examples, a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Corporation, model: TMA6100) was used, and the heat shrinkage rate and the restoration rate were measured as follows.
First, a load is applied to the molded product sample so that the tensile stress is 1, 3, 5, 10 MPa based on the cross-sectional area calculated from the diameter, and marks are made at two places at intervals of about 5 mm.
Next, with the tensile load applied, the temperature is raised from 35 ° C to 85 ° C and then lowered to 35 ° C. With the temperature lowered to 35 ° C., the distance (L1) between the two marks previously attached to the molded product sample is measured. Then, the temperature is raised again from 35 ° C. to 85 ° C., and the distance (L2) between the two marks attached to the molded product sample is measured.
From the distances L1 and L2, the heat shrinkage rate is obtained by the following formula.
Heat shrinkage rate (%) = (L1-L2) x 100 / L1
Heat shrinkage rate per unit temperature (% / ° C) = (L1-L2) x 100 / L1 / 50
Subsequently, the temperature was lowered to 35 ° C., the distance (L3) between the two marks attached to the molded body was measured, and the temperature was raised and lowered 9 times in the same manner, and then attached to the molded body. Measure the distance (L3) between the two marks.
From the distances L1 and L3, the restoration rate is calculated by the following formula.
Restoration rate (%) = 100- ｜ Initial test length change rate ｜
Initial trial length change rate = (L3-L1) x 100 / L1
In Table 1, the one in which the temperature rise and fall are repeated once is referred to as “restoration rate 1”, and the one in which the temperature is repeatedly raised and lowered 10 times is referred to as “restoration rate 10”.
Further, the tensile stress (Pa) was obtained from the following formula from the load F (N) applied to the molded body sample and the molded body cross-sectional area A (mm 2 ) when measuring the heat shrinkage rate.
Tensile stress (Pa) = F / A
実施例および比較例の成形体は、熱機械分析装置（日立ハイテクサイエンス社製、型式：ＴＭＡ６１００）を使用し、次のようにして熱収縮率および復元率を測定した。
まず、成形体試料に、直径から算出した断面積をもとに、引張応力が１、３、５、１０MPaとなるように荷重をかけ、約５ｍｍの間隔で２か所に印をつける。
次に、前記引張荷重をかけた状態で、３５℃から８５℃まで昇温し、３５℃まで降温する。３５℃に降温した状態で、先に成形体試料に付けた２か所の印の間の距離（Ｌ１）を測定する。次いで、３５℃から８５℃まで再度昇温し、成形体試料に付けた２か所の印の間の距離（Ｌ２）を測定する。
距離Ｌ１及びＬ２から、以下の式により熱収縮率を求める。
熱収縮率（％）＝（Ｌ１－Ｌ２）×１００／Ｌ１
単位温度当たりの熱収縮率（％／℃）＝（Ｌ１－Ｌ２）×１００／Ｌ１／５０
続いて、３５℃まで降温し、成形体に付けた２か所の印の間の距離（Ｌ３）を測定し、さらに同様にして昇温と降温を９回繰り返した後、成形体に付けた２か所の印の間の距離（Ｌ３）を測定する。
距離Ｌ１及びＬ３から、以下の式により復元率を求める。
復元率（％）＝１００－｜初期試長変化率｜
初期試長変化率＝（Ｌ３－Ｌ１）×１００／Ｌ１
表１では、昇温と降温の繰り返しが１回のものを「復元率１」、繰り返しが１０回のものを「復元率１０」とした。
また、引張応力（Ｐａ）は、熱収縮率を測定するときに成形体試料に掛ける荷重Ｆ（Ｎ）と成形体断面積Ａ（ｍｍ２）から下記式より求めた。
引張応力（Ｐａ）＝Ｆ／Ａ (Measurement method of heat shrinkage rate and restoration rate)
As the molded products of Examples and Comparative Examples, a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Corporation, model: TMA6100) was used, and the heat shrinkage rate and the restoration rate were measured as follows.
First, a load is applied to the molded product sample so that the tensile stress is 1, 3, 5, 10 MPa based on the cross-sectional area calculated from the diameter, and marks are made at two places at intervals of about 5 mm.
Next, with the tensile load applied, the temperature is raised from 35 ° C to 85 ° C and then lowered to 35 ° C. With the temperature lowered to 35 ° C., the distance (L1) between the two marks previously attached to the molded product sample is measured. Then, the temperature is raised again from 35 ° C. to 85 ° C., and the distance (L2) between the two marks attached to the molded product sample is measured.
From the distances L1 and L2, the heat shrinkage rate is obtained by the following formula.
Heat shrinkage rate (%) = (L1-L2) x 100 / L1
Heat shrinkage rate per unit temperature (% / ° C) = (L1-L2) x 100 / L1 / 50
Subsequently, the temperature was lowered to 35 ° C., the distance (L3) between the two marks attached to the molded body was measured, and the temperature was raised and lowered 9 times in the same manner, and then attached to the molded body. Measure the distance (L3) between the two marks.
From the distances L1 and L3, the restoration rate is calculated by the following formula.
Restoration rate (%) = 100- ｜ Initial test length change rate ｜
Initial trial length change rate = (L3-L1) x 100 / L1
In Table 1, the one in which the temperature rise and fall are repeated once is referred to as “
Further, the tensile stress (Pa) was obtained from the following formula from the load F (N) applied to the molded body sample and the molded body cross-sectional area A (mm 2 ) when measuring the heat shrinkage rate.
Tensile stress (Pa) = F / A
（単繊維繊度の測定方法）
１ｍあたりの繊維の質量Ｗ（ｇ）を測定して、１００００倍することで、単繊維繊度（ｄｔｅｘ）算出した。
単繊維繊度（ｄｔｅｘ）＝Ｗ×１００００ (Measuring method of single fiber fineness)
The mass W (g) of the fiber per 1 m was measured and multiplied by 10,000 to calculate the single fiber fineness (dtex).
Single fiber fineness (dtex) = W × 10000
１ｍあたりの繊維の質量Ｗ（ｇ）を測定して、１００００倍することで、単繊維繊度（ｄｔｅｘ）算出した。
単繊維繊度（ｄｔｅｘ）＝Ｗ×１００００ (Measuring method of single fiber fineness)
The mass W (g) of the fiber per 1 m was measured and multiplied by 10,000 to calculate the single fiber fineness (dtex).
Single fiber fineness (dtex) = W × 10000
（単繊維の直径の測定方法）
単繊維の直径を超高速・高精度寸法測定器（キーエンス社製、型式：ＬＳ－９００６）で測定した。 (Measuring method of single fiber diameter)
The diameter of the single fiber was measured with an ultra-high speed and high precision dimensional measuring instrument (manufactured by KEYENCE, model: LS-9006).
単繊維の直径を超高速・高精度寸法測定器（キーエンス社製、型式：ＬＳ－９００６）で測定した。 (Measuring method of single fiber diameter)
The diameter of the single fiber was measured with an ultra-high speed and high precision dimensional measuring instrument (manufactured by KEYENCE, model: LS-9006).
（ゲル分率の測定方法）
ゲル分率は、以下の方法で測定した。このゲル分率は架橋度を表すものであり、数値が高いほど架橋度が高いことを示す。
まず、測定を行う繊維試料の質量（Ｍ１）を測定する。次に、前記繊維試料に対して、キシレンを使用して、キシレン沸点にて１０時間ソックスレー抽出を行い、その後残った繊維試料を乾燥し、繊維試料の質量（Ｍ２）を測定する。Ｍ１及びＭ２から、以下の式によりゲル分率を求める。
ゲル分率（％）＝Ｍ２／Ｍ１×１００
上記の測定方法は、繊維試料を溶剤（キシレン）で溶かした時に、溶かされずに残存する部分をゲル（架橋部分はゲルとして残る）とし、このゲル部分の質量と溶剤で溶かす前の繊維試料の質量との比（百分率）を「ゲル分率」として、架橋の進行の程度を評価する。 (Measuring method of gel fraction)
The gel fraction was measured by the following method. This gel fraction represents the degree of cross-linking, and the higher the value, the higher the degree of cross-linking.
First, the mass (M1) of the fiber sample to be measured is measured. Next, the fiber sample is subjected to Soxhlet extraction at the boiling point of xylene for 10 hours using xylene, and then the remaining fiber sample is dried and the mass (M2) of the fiber sample is measured. From M1 and M2, the gel fraction is calculated by the following formula.
Gel fraction (%) = M2 / M1 × 100
In the above measurement method, when the fiber sample is melted with a solvent (xylene), the part that remains undissolved is made into a gel (the crosslinked part remains as a gel), and the mass of this gel part and the fiber sample before being melted with the solvent. The degree of progress of cross-linking is evaluated by using the ratio (percentage) with the mass as the "gel fraction".
ゲル分率は、以下の方法で測定した。このゲル分率は架橋度を表すものであり、数値が高いほど架橋度が高いことを示す。
まず、測定を行う繊維試料の質量（Ｍ１）を測定する。次に、前記繊維試料に対して、キシレンを使用して、キシレン沸点にて１０時間ソックスレー抽出を行い、その後残った繊維試料を乾燥し、繊維試料の質量（Ｍ２）を測定する。Ｍ１及びＭ２から、以下の式によりゲル分率を求める。
ゲル分率（％）＝Ｍ２／Ｍ１×１００
上記の測定方法は、繊維試料を溶剤（キシレン）で溶かした時に、溶かされずに残存する部分をゲル（架橋部分はゲルとして残る）とし、このゲル部分の質量と溶剤で溶かす前の繊維試料の質量との比（百分率）を「ゲル分率」として、架橋の進行の程度を評価する。 (Measuring method of gel fraction)
The gel fraction was measured by the following method. This gel fraction represents the degree of cross-linking, and the higher the value, the higher the degree of cross-linking.
First, the mass (M1) of the fiber sample to be measured is measured. Next, the fiber sample is subjected to Soxhlet extraction at the boiling point of xylene for 10 hours using xylene, and then the remaining fiber sample is dried and the mass (M2) of the fiber sample is measured. From M1 and M2, the gel fraction is calculated by the following formula.
Gel fraction (%) = M2 / M1 × 100
In the above measurement method, when the fiber sample is melted with a solvent (xylene), the part that remains undissolved is made into a gel (the crosslinked part remains as a gel), and the mass of this gel part and the fiber sample before being melted with the solvent. The degree of progress of cross-linking is evaluated by using the ratio (percentage) with the mass as the "gel fraction".
（結晶化度の測定方法）
繊維の結晶化度の測定は、Ｘ線発生装置（リガク社製、ｕｌｔｒａＸ１８、波長λ＝１．５４Å）を用いて行った。
延伸糸を約５ｃｍになるように切断して、繊維が重ならないように１軸方向に整列させてサンプルホルダーにとりつけた。
管電圧は４０ｋＶ、管電流は２００ｍＡ、照射時間は１２０分で、イメージングプレートに露光した。
得られた２次元回折像について、β=０゜～３６０゜までを積分した後、バックグランドを差し引いて、最終的な１次元プロファイルとした。
１次元プロファイルから結晶ピークと非晶ピークに分離するにあたり、結晶ピークは文献で公知の回折角にピークを設置して、非晶ピークはプロファイルとの差分を補完するようにピークを設置して、波形分離解析ソフトＦｉｔｙｋ（オープンソースソフトウェア）をもちいてフィッティングを行った。結晶ピーク積分強度の和をすべてのピーク積分強度で除すことで、結晶化度を算出した。なお、フィッティングしたピーク関数は、ガウス関数とローレンツ関数の重ね合わせである疑似フォークト関数を用い、ガウス関数とローレンツ関数の比を１：１に固定した。 (Measuring method of crystallinity)
The crystallinity of the fiber was measured using an X-ray generator (Rigaku, ultraX18, wavelength λ = 1.54 Å).
The drawn yarn was cut to a length of about 5 cm, aligned in the uniaxial direction so that the fibers did not overlap, and attached to the sample holder.
The tube voltage was 40 kV, the tube current was 200 mA, the irradiation time was 120 minutes, and the imaging plate was exposed.
The obtained two-dimensional diffraction image was integrated from β = 0 ° to 360 °, and then the background was subtracted to obtain the final one-dimensional profile.
In separating the one-dimensional profile into a crystal peak and an amorphous peak, the crystal peak is set at a diffraction angle known in the literature, and the amorphous peak is set so as to complement the difference from the profile. Fitting was performed using the waveform separation analysis software Fitik (open source software). The crystallinity was calculated by dividing the sum of the crystal peak integrated intensities by all the peak integrated intensities. As the fitted peak function, a pseudo Voigt function, which is a superposition of the Gaussian function and the Lorentz function, was used, and the ratio of the Gaussian function and the Lorentz function was fixed at 1: 1.
繊維の結晶化度の測定は、Ｘ線発生装置（リガク社製、ｕｌｔｒａＸ１８、波長λ＝１．５４Å）を用いて行った。
延伸糸を約５ｃｍになるように切断して、繊維が重ならないように１軸方向に整列させてサンプルホルダーにとりつけた。
管電圧は４０ｋＶ、管電流は２００ｍＡ、照射時間は１２０分で、イメージングプレートに露光した。
得られた２次元回折像について、β=０゜～３６０゜までを積分した後、バックグランドを差し引いて、最終的な１次元プロファイルとした。
１次元プロファイルから結晶ピークと非晶ピークに分離するにあたり、結晶ピークは文献で公知の回折角にピークを設置して、非晶ピークはプロファイルとの差分を補完するようにピークを設置して、波形分離解析ソフトＦｉｔｙｋ（オープンソースソフトウェア）をもちいてフィッティングを行った。結晶ピーク積分強度の和をすべてのピーク積分強度で除すことで、結晶化度を算出した。なお、フィッティングしたピーク関数は、ガウス関数とローレンツ関数の重ね合わせである疑似フォークト関数を用い、ガウス関数とローレンツ関数の比を１：１に固定した。 (Measuring method of crystallinity)
The crystallinity of the fiber was measured using an X-ray generator (Rigaku, ultraX18, wavelength λ = 1.54 Å).
The drawn yarn was cut to a length of about 5 cm, aligned in the uniaxial direction so that the fibers did not overlap, and attached to the sample holder.
The tube voltage was 40 kV, the tube current was 200 mA, the irradiation time was 120 minutes, and the imaging plate was exposed.
The obtained two-dimensional diffraction image was integrated from β = 0 ° to 360 °, and then the background was subtracted to obtain the final one-dimensional profile.
In separating the one-dimensional profile into a crystal peak and an amorphous peak, the crystal peak is set at a diffraction angle known in the literature, and the amorphous peak is set so as to complement the difference from the profile. Fitting was performed using the waveform separation analysis software Fitik (open source software). The crystallinity was calculated by dividing the sum of the crystal peak integrated intensities by all the peak integrated intensities. As the fitted peak function, a pseudo Voigt function, which is a superposition of the Gaussian function and the Lorentz function, was used, and the ratio of the Gaussian function and the Lorentz function was fixed at 1: 1.
（結晶配向度の測定方法）
繊維の結晶配向度の測定は、試料水平型強力Ｘ線回折装置（リガク社製、ＲＩＮＴ－ＴＴＲIII、波長λ＝１．５４Å）を用いて行った。
繊維を約５ｃｍになるように切断して、繊維が重ならないように１軸方向に整列させて、サンプルホルダーに取り付けた。
管電圧は５０ｋＶ、管電流は３００ｍＡ、走査間範囲５～４０゜、スキャンスピード１０゜／分で測定を実施して、結晶ピークを見つけた後、最大強度の結晶ピークの角度に検出器を固定して、入射Ｘ線と反射Ｘ線のなす角を２等分する面上で、サンプルホルダーを回転させながら回折強度を測定した。
その時のサンプルホルダーの回転角をβとする。結晶ピークを見つけた時のサンプルホルダーの回転角をβ＝１８０゜として、サンプルホルダーを回転させて得られた回折強度プロファイルのβ＝９０゜、２７０゜の強度を０として、ベースラインを設定する。ベースラインを差し引いて得られたプロファイルから、β＝１８０°のピークの半値幅αを読み取り、下記式により結晶配向度を算出した。
結晶配向度＝（１８０－α）×１００／１８０ (Measuring method of crystal orientation)
The crystal orientation of the fibers was measured using a sample horizontal strong X-ray diffractometer (Rigaku, RINT-TTRIII, wavelength λ = 1.54 Å).
The fibers were cut to about 5 cm, aligned in the uniaxial direction so that the fibers did not overlap, and attached to the sample holder.
The tube voltage is 50 kV, the tube current is 300 mA, the scanning range is 5 to 40 °, and the scan speed is 10 ° / min. After finding the crystal peak, the detector is fixed at the angle of the maximum intensity crystal peak. Then, the diffraction intensity was measured while rotating the sample holder on the surface that divides the angle formed by the incident X-ray and the reflected X-ray into two equal parts.
Let β be the rotation angle of the sample holder at that time. Set the baseline by setting the rotation angle of the sample holder when the crystal peak is found to β = 180 ° and setting the intensity of β = 90 ° and 270 ° of the diffraction intensity profile obtained by rotating the sample holder to 0. .. From the profile obtained by subtracting the baseline, the half width α of the peak at β = 180 ° was read, and the degree of crystal orientation was calculated by the following formula.
Crystal orientation = (180-α) × 100/180
繊維の結晶配向度の測定は、試料水平型強力Ｘ線回折装置（リガク社製、ＲＩＮＴ－ＴＴＲIII、波長λ＝１．５４Å）を用いて行った。
繊維を約５ｃｍになるように切断して、繊維が重ならないように１軸方向に整列させて、サンプルホルダーに取り付けた。
管電圧は５０ｋＶ、管電流は３００ｍＡ、走査間範囲５～４０゜、スキャンスピード１０゜／分で測定を実施して、結晶ピークを見つけた後、最大強度の結晶ピークの角度に検出器を固定して、入射Ｘ線と反射Ｘ線のなす角を２等分する面上で、サンプルホルダーを回転させながら回折強度を測定した。
その時のサンプルホルダーの回転角をβとする。結晶ピークを見つけた時のサンプルホルダーの回転角をβ＝１８０゜として、サンプルホルダーを回転させて得られた回折強度プロファイルのβ＝９０゜、２７０゜の強度を０として、ベースラインを設定する。ベースラインを差し引いて得られたプロファイルから、β＝１８０°のピークの半値幅αを読み取り、下記式により結晶配向度を算出した。
結晶配向度＝（１８０－α）×１００／１８０ (Measuring method of crystal orientation)
The crystal orientation of the fibers was measured using a sample horizontal strong X-ray diffractometer (Rigaku, RINT-TTRIII, wavelength λ = 1.54 Å).
The fibers were cut to about 5 cm, aligned in the uniaxial direction so that the fibers did not overlap, and attached to the sample holder.
The tube voltage is 50 kV, the tube current is 300 mA, the scanning range is 5 to 40 °, and the scan speed is 10 ° / min. After finding the crystal peak, the detector is fixed at the angle of the maximum intensity crystal peak. Then, the diffraction intensity was measured while rotating the sample holder on the surface that divides the angle formed by the incident X-ray and the reflected X-ray into two equal parts.
Let β be the rotation angle of the sample holder at that time. Set the baseline by setting the rotation angle of the sample holder when the crystal peak is found to β = 180 ° and setting the intensity of β = 90 ° and 270 ° of the diffraction intensity profile obtained by rotating the sample holder to 0. .. From the profile obtained by subtracting the baseline, the half width α of the peak at β = 180 ° was read, and the degree of crystal orientation was calculated by the following formula.
Crystal orientation = (180-α) × 100/180
（密度の測定方法）
繊維の密度は、ＪＩＳ Ｋ ７１１２に基づく密度勾配管法により測定した。 (Density measurement method)
The fiber density was measured by the density gradient tube method based on JIS K 7112.
繊維の密度は、ＪＩＳ Ｋ ７１１２に基づく密度勾配管法により測定した。 (Density measurement method)
The fiber density was measured by the density gradient tube method based on JIS K 7112.
（コイル形状の外径Ｄ’、コイル形状の繊維の長さ、単繊維直径ｄ、および電熱線の直径の測定）
コイル形状の繊維について、コイル形状の外径Ｄ’、コイル形状の繊維の長さ、単繊維直径ｄ、および電熱線の直径は、デジタルマイクロスコープ（商品名：ＤＳＸ５００、オリンパス社製）を用いて測定した。 (Measurement of coil-shaped outer diameter D', coil-shaped fiber length, single fiber diameter d, and heating wire diameter)
For coil-shaped fibers, the coil-shaped outer diameter D', coil-shaped fiber length, single fiber diameter d, and heating wire diameter are determined using a digital microscope (trade name: DSX500, manufactured by Olympus Corporation). It was measured.
コイル形状の繊維について、コイル形状の外径Ｄ’、コイル形状の繊維の長さ、単繊維直径ｄ、および電熱線の直径は、デジタルマイクロスコープ（商品名：ＤＳＸ５００、オリンパス社製）を用いて測定した。 (Measurement of coil-shaped outer diameter D', coil-shaped fiber length, single fiber diameter d, and heating wire diameter)
For coil-shaped fibers, the coil-shaped outer diameter D', coil-shaped fiber length, single fiber diameter d, and heating wire diameter are determined using a digital microscope (trade name: DSX500, manufactured by Olympus Corporation). It was measured.
（バネ指数の測定方法）
バネ指数Ｄ／ｄは、コイル平均直径Ｄ（μｍ）及び単繊維直径ｄ（μｍ）を用いて算出した。
コイル平均直径Ｄは、コイル外径Ｄ’（μｍ）及び単繊維直径ｄ（μｍ）を測定し、Ｄ＝Ｄ’－ｄより算出した。 (Measurement method of spring index)
The spring index D / d was calculated using the coil average diameter D (μm) and the single fiber diameter d (μm).
The coil average diameter D was calculated from D = D'-d by measuring the coil outer diameter D'(μm) and the single fiber diameter d (μm).
バネ指数Ｄ／ｄは、コイル平均直径Ｄ（μｍ）及び単繊維直径ｄ（μｍ）を用いて算出した。
コイル平均直径Ｄは、コイル外径Ｄ’（μｍ）及び単繊維直径ｄ（μｍ）を測定し、Ｄ＝Ｄ’－ｄより算出した。 (Measurement method of spring index)
The spring index D / d was calculated using the coil average diameter D (μm) and the single fiber diameter d (μm).
The coil average diameter D was calculated from D = D'-d by measuring the coil outer diameter D'(μm) and the single fiber diameter d (μm).
（実施例１）
シラン架橋性ポリエチレン樹脂（三菱ケミカル社製、製品名「リンクロン」ＭＦ９００Ｎ、密度ρ＝０．９０ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））と、シラノール縮合触媒マスターバッチ（三菱ケミカル社製、ＬＺ０８２）を、シラン架橋性ポリエチレン樹脂１００質量部に対して前記触媒マスターバッチ５質量部の比率で溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．２５ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６７ｇ／分の吐出量で吐出し、６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Example 1)
Silane crosslinkable polyethylene resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" MF900N, density ρ = 0.90 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)), A silanol condensation catalyst masterbatch (manufactured by Mitsubishi Chemical Co., Ltd., LZ082) was charged into an extruder of a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of a silane crosslinkable polyethylene resin, and melted at 220 ° C. After kneading, the resin at 220 ° C. is discharged from a spinning nozzle having a discharge hole diameter of 1.25 mmφ and a discharge hole number of 1 hole at a discharge rate of 0.67 g / min, and is wound around a bobbin at a take-up speed of 6 m / min. An undrawn yarn was obtained.
シラン架橋性ポリエチレン樹脂（三菱ケミカル社製、製品名「リンクロン」ＭＦ９００Ｎ、密度ρ＝０．９０ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））と、シラノール縮合触媒マスターバッチ（三菱ケミカル社製、ＬＺ０８２）を、シラン架橋性ポリエチレン樹脂１００質量部に対して前記触媒マスターバッチ５質量部の比率で溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．２５ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６７ｇ／分の吐出量で吐出し、６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Example 1)
Silane crosslinkable polyethylene resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" MF900N, density ρ = 0.90 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)), A silanol condensation catalyst masterbatch (manufactured by Mitsubishi Chemical Co., Ltd., LZ082) was charged into an extruder of a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of a silane crosslinkable polyethylene resin, and melted at 220 ° C. After kneading, the resin at 220 ° C. is discharged from a spinning nozzle having a discharge hole diameter of 1.25 mmφ and a discharge hole number of 1 hole at a discharge rate of 0.67 g / min, and is wound around a bobbin at a take-up speed of 6 m / min. An undrawn yarn was obtained.
得られた未延伸糸を、１段目の延伸を糸温度が５０℃、延伸倍率が３．５倍で熱板延伸を行った。連続して２段目の延伸を糸温度が５５℃、延伸倍率が１．２倍で熱板延伸を行った。続いて、糸温度が７０℃、延伸倍率１．０倍で熱アニール処理を行った。
The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 50 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 55 ° C. and a drawing ratio of 1.2 times. Subsequently, the heat annealing treatment was performed at a yarn temperature of 70 ° C. and a draw ratio of 1.0 times.
次いで、アニール処理された繊維を、定長緊張下にて、９０℃の温水に２４時間浸して架橋処理を行い、架橋構造を有する繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。なお、熱収縮率を測定する引張応力は５ＭＰａとして測定した。
比較例と比較し、同じ引張応力でも収縮率が高く、収縮力が高いことが分かる。 Next, the annealed fiber was immersed in warm water at 90 ° C. for 24 hours under constant length tension to carry out a cross-linking treatment, and a fiber having a cross-linked structure was obtained.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
Compared with the comparative example, it can be seen that the shrinkage rate is high and the shrinkage force is high even with the same tensile stress.
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。なお、熱収縮率を測定する引張応力は５ＭＰａとして測定した。
比較例と比較し、同じ引張応力でも収縮率が高く、収縮力が高いことが分かる。 Next, the annealed fiber was immersed in warm water at 90 ° C. for 24 hours under constant length tension to carry out a cross-linking treatment, and a fiber having a cross-linked structure was obtained.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
Compared with the comparative example, it can be seen that the shrinkage rate is high and the shrinkage force is high even with the same tensile stress.
（実施例２）
シラン架橋性ポリエチレンを密度が異なるシラン架橋性ポリエチレン樹脂（三菱ケミカル社製、製品名「リンクロン」ＳＬ８００Ｎ、密度ρ＝０．８８ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））へ代えた以外は、実施例１と同様にして架橋繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。なお、熱収縮率を測定する引張応力は５ＭＰａとして測定した。 (Example 2)
Silane cross-linking polyethylene resin with different densities of silane cross-linking polyethylene resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" SL800N, density ρ = 0.88 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C,load 2. Crosslinked fibers were obtained in the same manner as in Example 1 except that they were replaced with 16 kg, 10 minutes)).
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
シラン架橋性ポリエチレンを密度が異なるシラン架橋性ポリエチレン樹脂（三菱ケミカル社製、製品名「リンクロン」ＳＬ８００Ｎ、密度ρ＝０．８８ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））へ代えた以外は、実施例１と同様にして架橋繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。なお、熱収縮率を測定する引張応力は５ＭＰａとして測定した。 (Example 2)
Silane cross-linking polyethylene resin with different densities of silane cross-linking polyethylene resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" SL800N, density ρ = 0.88 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C,
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
（実施例３）
シラン架橋性ポリエチレン樹脂（三菱ケミカル社製、製品名「リンクロン」ＭＦ９００Ｎ、密度ρ＝０．９０ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））と、シラノール縮合触媒マスターバッチ（三菱ケミカル社製、ＬＺ０８２）を、シラン架橋性ポリエチレン樹脂１００質量部に対して前記触媒マスターバッチ５質量部の比率で溶融紡糸装置に投入し、最大２１０℃で溶融混練し、吐出孔径が１．６ｍｍφ、吐出孔数が１ホールの紡糸ノズルから１．５６ｇ／分の吐出量で吐出し、１４．４ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。
得られた未延伸糸を、糸温度が８０℃、延伸倍率が５．９０倍で一段目の乾熱延伸を行った。連続して、糸温度が９５℃、延伸倍率が１．０７倍で二段目の乾熱延伸を行った。次いで、糸温度が１０３℃、延伸倍率０．９５倍で緩和しながら熱アニール処理を行い、総延伸倍率６．００倍の繊維を得た。
得られた繊維をボビンに巻き取られた形態のまま高温恒湿機にて最大温度８５℃、湿度８５％ＲＨの条件に到達するよう昇降温を繰り返しながら４８時間架橋処理を行い、シラン架橋構造を有する繊維（直径：０．２ｍｍ）を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。なお、熱収縮率を測定する引張応力は５ＭＰａとして測定した。 (Example 3)
Silane crosslinkable polyethylene resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" MF900N, density ρ = 0.90 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)), A silanol condensation catalyst masterbatch (manufactured by Mitsubishi Chemical Co., Ltd., LZ082) was put into a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of a silane crosslinkable polyethylene resin, and melt-kneaded at a maximum of 210 ° C. A spinning nozzle with a discharge hole diameter of 1.6 mmφ and a number of discharge holes of 1 hole discharges at a discharge rate of 1.56 g / min and is wound around a bobbin at a take-up speed of 14.4 m / min to obtain undrawn yarn. rice field.
The obtained undrawn yarn was subjected to the first dry heat drawing at a yarn temperature of 80 ° C. and a draw ratio of 5.90 times. The second stage dry heat drawing was continuously performed at a yarn temperature of 95 ° C. and a draw ratio of 1.07 times. Next, a thermal annealing treatment was performed while relaxing at a yarn temperature of 103 ° C. and a draw ratio of 0.95 times to obtain a fiber having a total draw ratio of 6.00 times.
The obtained fiber was subjected to a cross-linking treatment for 48 hours while repeatedly raising and lowering the temperature so as to reach the conditions of a maximum temperature of 85 ° C. and a humidity of 85% RH in a high-temperature and humidity chamber while the obtained fiber was wound around a bobbin, and a silane cross-linking structure was performed. (Diameter: 0.2 mm) was obtained.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
シラン架橋性ポリエチレン樹脂（三菱ケミカル社製、製品名「リンクロン」ＭＦ９００Ｎ、密度ρ＝０．９０ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））と、シラノール縮合触媒マスターバッチ（三菱ケミカル社製、ＬＺ０８２）を、シラン架橋性ポリエチレン樹脂１００質量部に対して前記触媒マスターバッチ５質量部の比率で溶融紡糸装置に投入し、最大２１０℃で溶融混練し、吐出孔径が１．６ｍｍφ、吐出孔数が１ホールの紡糸ノズルから１．５６ｇ／分の吐出量で吐出し、１４．４ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。
得られた未延伸糸を、糸温度が８０℃、延伸倍率が５．９０倍で一段目の乾熱延伸を行った。連続して、糸温度が９５℃、延伸倍率が１．０７倍で二段目の乾熱延伸を行った。次いで、糸温度が１０３℃、延伸倍率０．９５倍で緩和しながら熱アニール処理を行い、総延伸倍率６．００倍の繊維を得た。
得られた繊維をボビンに巻き取られた形態のまま高温恒湿機にて最大温度８５℃、湿度８５％ＲＨの条件に到達するよう昇降温を繰り返しながら４８時間架橋処理を行い、シラン架橋構造を有する繊維（直径：０．２ｍｍ）を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。なお、熱収縮率を測定する引張応力は５ＭＰａとして測定した。 (Example 3)
Silane crosslinkable polyethylene resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" MF900N, density ρ = 0.90 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)), A silanol condensation catalyst masterbatch (manufactured by Mitsubishi Chemical Co., Ltd., LZ082) was put into a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of a silane crosslinkable polyethylene resin, and melt-kneaded at a maximum of 210 ° C. A spinning nozzle with a discharge hole diameter of 1.6 mmφ and a number of discharge holes of 1 hole discharges at a discharge rate of 1.56 g / min and is wound around a bobbin at a take-up speed of 14.4 m / min to obtain undrawn yarn. rice field.
The obtained undrawn yarn was subjected to the first dry heat drawing at a yarn temperature of 80 ° C. and a draw ratio of 5.90 times. The second stage dry heat drawing was continuously performed at a yarn temperature of 95 ° C. and a draw ratio of 1.07 times. Next, a thermal annealing treatment was performed while relaxing at a yarn temperature of 103 ° C. and a draw ratio of 0.95 times to obtain a fiber having a total draw ratio of 6.00 times.
The obtained fiber was subjected to a cross-linking treatment for 48 hours while repeatedly raising and lowering the temperature so as to reach the conditions of a maximum temperature of 85 ° C. and a humidity of 85% RH in a high-temperature and humidity chamber while the obtained fiber was wound around a bobbin, and a silane cross-linking structure was performed. (Diameter: 0.2 mm) was obtained.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1. The tensile stress for measuring the heat shrinkage was measured as 5 MPa.
（実施例４）
実施例３で得られた繊維について熱収縮率を測定する引張応力を３ＭＰａとして熱収縮率を測定した。 (Example 4)
The heat shrinkage of the fibers obtained in Example 3 was measured with a tensile stress of 3 MPa for measuring the heat shrinkage.
実施例３で得られた繊維について熱収縮率を測定する引張応力を３ＭＰａとして熱収縮率を測定した。 (Example 4)
The heat shrinkage of the fibers obtained in Example 3 was measured with a tensile stress of 3 MPa for measuring the heat shrinkage.
（実施例５）
実施例３で得られた繊維について熱収縮率を測定する引張応力を１ＭＰａとして熱収縮率を測定した。 (Example 5)
The heat shrinkage of the fibers obtained in Example 3 was measured with a tensile stress of 1 MPa for measuring the heat shrinkage.
実施例３で得られた繊維について熱収縮率を測定する引張応力を１ＭＰａとして熱収縮率を測定した。 (Example 5)
The heat shrinkage of the fibers obtained in Example 3 was measured with a tensile stress of 1 MPa for measuring the heat shrinkage.
（比較例１）
直鎖状低密度ポリエチレン（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製、品番４２８０７８、密度ρ＝０．９２ｇ／ｃｍ３、ＭＦＲ＝１．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．０ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出し、８．０ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 1)
Melt spinning of linear low density polyethylene (manufactured by SIGMA-ALDRICH, product number 428878, density ρ = 0.92 g / cm 3 , MFR = 1.0 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) It is put into the extruder of the device, melt-kneaded at 220 ° C, and the resin at 220 ° C is discharged from a spinning nozzle having a discharge hole diameter of 1.0 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 0.0 m / min.
直鎖状低密度ポリエチレン（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製、品番４２８０７８、密度ρ＝０．９２ｇ／ｃｍ３、ＭＦＲ＝１．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．０ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出し、８．０ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 1)
Melt spinning of linear low density polyethylene (manufactured by SIGMA-ALDRICH, product number 428878, density ρ = 0.92 g / cm 3 , MFR = 1.0 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) It is put into the extruder of the device, melt-kneaded at 220 ° C, and the resin at 220 ° C is discharged from a spinning nozzle having a discharge hole diameter of 1.0 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 0.0 m / min.
得られた未延伸糸を、１段目の延伸を糸温度が８０℃、延伸倍率が３．５倍で熱板延伸を行った。連続して２段目の延伸を糸温度が９０℃、延伸倍率が１．１倍で熱板延伸を行った。続いて、糸温度が１１０℃、延伸倍率１．０倍で熱アニール処理を行い、架橋を有さない繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 90 ° C. and a drawing ratio of 1.1 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 110 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinks.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 90 ° C. and a drawing ratio of 1.1 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 110 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinks.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
（比較例２）
直鎖状低密度ポリエチレン（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製、品番４２８０７８、密度ρ＝０．９２ｇ／ｃｍ３、ＭＦＲ＝１．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．０ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出し、２．０ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 2)
Melt spinning of linear low density polyethylene (manufactured by SIGMA-ALDRICH, product number 428878, density ρ = 0.92 g / cm 3 , MFR = 1.0 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) It is put into the extruder of the device, melt-kneaded at 220 ° C, and the resin at 220 ° C is discharged from a spinning nozzle with a discharge hole diameter of 1.0 mmφ and a discharge hole number of 1 hole at a discharge rate of 0.63 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 0.0 m / min.
直鎖状低密度ポリエチレン（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製、品番４２８０７８、密度ρ＝０．９２ｇ／ｃｍ３、ＭＦＲ＝１．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．０ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出し、２．０ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 2)
Melt spinning of linear low density polyethylene (manufactured by SIGMA-ALDRICH, product number 428878, density ρ = 0.92 g / cm 3 , MFR = 1.0 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) It is put into the extruder of the device, melt-kneaded at 220 ° C, and the resin at 220 ° C is discharged from a spinning nozzle with a discharge hole diameter of 1.0 mmφ and a discharge hole number of 1 hole at a discharge rate of 0.63 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 0.0 m / min.
得られた未延伸糸を、１段目の延伸を糸温度が８０℃、延伸倍率が９．４倍で熱板延伸を行った。連続して２段目の延伸を糸温度が１００℃、延伸倍率が１．１倍で熱板延伸を行った。続いて、糸温度が１１０℃、延伸倍率１．０倍で熱アニール処理を行い、架橋構造を有さない繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 9.4 times in the first step. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 100 ° C. and a drawing ratio of 1.1 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 110 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 9.4 times in the first step. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 100 ° C. and a drawing ratio of 1.1 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 110 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
（比較例３）
低密度ポリエチレン（日本ポリエチレン社製、製品名：ノバテックＬＣ５２２、密度ρ＝０．９３ｇ／ｃｍ３、ＭＦＲ＝４．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、１９０℃で溶融混練し、１９０℃の樹脂を吐出孔径が１．０ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出し、１．６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 3)
Low-density polyethylene (manufactured by Nippon Polyethylene, product name: Novatec LC522, density ρ = 0.93 g / cm 3 , MFR = 4.0 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) 1. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 6 m / min.
低密度ポリエチレン（日本ポリエチレン社製、製品名：ノバテックＬＣ５２２、密度ρ＝０．９３ｇ／ｃｍ３、ＭＦＲ＝４．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、１９０℃で溶融混練し、１９０℃の樹脂を吐出孔径が１．０ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出し、１．６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 3)
Low-density polyethylene (manufactured by Nippon Polyethylene, product name: Novatec LC522, density ρ = 0.93 g / cm 3 , MFR = 4.0 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) 1. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 6 m / min.
得られた未延伸糸を、１段目の延伸を糸温度が８０℃、延伸倍率が３．５倍で熱板延伸を行った。連続して２段目の延伸を糸温度が８５℃、延伸倍率が１．１倍で熱板延伸を行った。続いて、糸温度が１００℃、延伸倍率１．０倍で熱アニール処理を行い、架橋構造を有さない繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 85 ° C. and a drawing ratio of 1.1 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 100 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 80 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 85 ° C. and a drawing ratio of 1.1 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 100 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
（比較例４）
シラン架橋性ポリエチレン（三菱ケミカル社製、製品名「リンクロン」ＳＬ８００Ｎ、密度ρ＝０．８８ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．２５ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３／分の吐出量で吐出し、６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 4)
Melt spinning of silane crosslinkable polyethylene (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" SL800N, density ρ = 0.88 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) It is put into the extruder of the device, melt-kneaded at 220 ° C, and the resin at 220 ° C is discharged from a spinning nozzle with a discharge hole diameter of 1.25 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 / min, 6 m. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of / min.
シラン架橋性ポリエチレン（三菱ケミカル社製、製品名「リンクロン」ＳＬ８００Ｎ、密度ρ＝０．８８ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．２５ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３／分の吐出量で吐出し、６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 4)
Melt spinning of silane crosslinkable polyethylene (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" SL800N, density ρ = 0.88 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) It is put into the extruder of the device, melt-kneaded at 220 ° C, and the resin at 220 ° C is discharged from a spinning nozzle with a discharge hole diameter of 1.25 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 / min, 6 m. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of / min.
得られた未延伸糸を、１段目の延伸を糸温度が５０℃、延伸倍率が３．５倍で熱板延伸を行った。連続して２段目の延伸を糸温度が５５℃、延伸倍率が１．２倍で熱板延伸を行った。続いて、糸温度が７０℃、延伸倍率１．０倍で熱アニール処理を行い、架橋構造を有さない繊維を得た。
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 50 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 55 ° C. and a drawing ratio of 1.2 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 70 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
得られた繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。これらの結果を表１に示す。 The obtained undrawn yarn was drawn on a hot plate at a yarn temperature of 50 ° C. and a draw ratio of 3.5 times for the first-stage drawing. The second-stage drawing was continuously performed by hot plate drawing at a yarn temperature of 55 ° C. and a drawing ratio of 1.2 times. Subsequently, thermal annealing treatment was performed at a yarn temperature of 70 ° C. and a draw ratio of 1.0 times to obtain fibers having no crosslinked structure.
Measurements were performed to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage, and restoration rate of the obtained fibers. These results are shown in Table 1.
（比較例５）
シラン架橋性ポリエチレン（三菱ケミカル社製、製品名「リンクロン」ＳＬ８００Ｎ、密度ρ＝０．８８ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））と、シラノール縮合触媒マスターバッチ（三菱ケミカル社製、ＬＺ０８２）を、シラン架橋性ポリエチレン１００質量部に対して前記触媒マスターバッチ５部質量部の比率で溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．２５ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出した。６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 5)
Silan crosslinkable polyethylene (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" SL800N, density ρ = 0.88 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) and silanol. A condensation catalyst masterbatch (LZ082 manufactured by Mitsubishi Chemical Co., Ltd.) was put into an extruder of a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of silane crosslinkable polyethylene, and melt-kneaded at 220 ° C. Then, the resin at 220 ° C. was discharged from a spinning nozzle having a discharge hole diameter of 1.25 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 6 m / min.
シラン架橋性ポリエチレン（三菱ケミカル社製、製品名「リンクロン」ＳＬ８００Ｎ、密度ρ＝０．８８ｇ／ｃｍ３、ＭＦＲ＝１ｇ／１０分（１９０℃、荷重２．１６ｋｇ、１０分））と、シラノール縮合触媒マスターバッチ（三菱ケミカル社製、ＬＺ０８２）を、シラン架橋性ポリエチレン１００質量部に対して前記触媒マスターバッチ５部質量部の比率で溶融紡糸装置の押出機に投入し、２２０℃で溶融混練し、２２０℃の樹脂を吐出孔径が１．２５ｍｍφ、吐出孔数が１ホールの紡糸ノズルから０．６３ｇ／分の吐出量で吐出した。６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。 (Comparative Example 5)
Silan crosslinkable polyethylene (manufactured by Mitsubishi Chemical Co., Ltd., product name "Linkron" SL800N, density ρ = 0.88 g / cm 3 , MFR = 1 g / 10 minutes (190 ° C, load 2.16 kg, 10 minutes)) and silanol. A condensation catalyst masterbatch (LZ082 manufactured by Mitsubishi Chemical Co., Ltd.) was put into an extruder of a melt spinning apparatus at a ratio of 5 parts by mass of the catalyst masterbatch to 100 parts by mass of silane crosslinkable polyethylene, and melt-kneaded at 220 ° C. Then, the resin at 220 ° C. was discharged from a spinning nozzle having a discharge hole diameter of 1.25 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 6 m / min.
得られた未延伸糸を、定長緊張下にて、９０℃の温水に２４時間浸して架橋処理を行い、架橋構造を有する繊維を得た。
得られた架橋繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。熱収縮率を測定しようとしたところ、熱で伸びて破断してしまい測定できなかった。これは結晶配向度が低いことが原因の１つと考えられる。これらの結果を表１に示す。 The obtained undrawn yarn was immersed in warm water at 90 ° C. for 24 hours under constant length tension to carry out a cross-linking treatment to obtain a fiber having a cross-linked structure.
Measurements were carried out to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage rate, and restoration rate of the obtained crosslinked fiber. When I tried to measure the heat shrinkage rate, it stretched due to heat and broke, so I could not measure it. This is considered to be one of the causes due to the low degree of crystal orientation. These results are shown in Table 1.
得られた架橋繊維の単繊維繊度、直径、結晶化度、結晶配向度、ゲル分率、熱収縮率、復元率を求めるための測定を行った。熱収縮率を測定しようとしたところ、熱で伸びて破断してしまい測定できなかった。これは結晶配向度が低いことが原因の１つと考えられる。これらの結果を表１に示す。 The obtained undrawn yarn was immersed in warm water at 90 ° C. for 24 hours under constant length tension to carry out a cross-linking treatment to obtain a fiber having a cross-linked structure.
Measurements were carried out to determine the single fiber fineness, diameter, crystallinity, crystal orientation, gel fraction, heat shrinkage rate, and restoration rate of the obtained crosslinked fiber. When I tried to measure the heat shrinkage rate, it stretched due to heat and broke, so I could not measure it. This is considered to be one of the causes due to the low degree of crystal orientation. These results are shown in Table 1.
（実施例６）
直鎖状低密度ポリエチレン１（日本ポリエチレン社製、商品名：ＮＦ４６４Ｎ、ＭＦＲ＝２．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ）、密度＝０．９１８ｇ／ｃｍ３）と直鎖状低密度ポリエチレン２（ダウケミカル社製、商品名：Ｅｎｇａｇｅ８２００、ＭＦＲ＝５．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ）、密度＝０．８７０ｇ／ｃｍ３）を６０：４０の質量割合で混合して、変性前組成物（密度＝０．８９９ｇ／ｃｍ３）とした。
この変性前組成物１００質量部に対して、ジ－ｔ－ブチルパーオキサイド０．０４質量部とビニルトリメトキシシラン２．０質量部とを添加、混合した。その後、混合物を、単軸押出機（Ｄ＝５０ｍｍφ、Ｌ／Ｄ＝３２）を用いて、温度２２０℃、スクリュー回転数５０ｒｐｍ、押出量２０ｋｇ／ｈの条件で溶融混練紐状に押し出し、冷却した後カッティングし、シラン架橋性ポリエチレン組成物を得た。
得られたシラン架橋性ポリエチレン組成物のＭＦＲ（１９０℃、荷重２．１６ｋｇ、１０分）及び密度を測定したところ、ＭＦＲ＝１ｇ／１０分、密度＝０．９０２ｇ／ｃｍ３であった。 (Example 6)
Linear low density polyethylene 1 (manufactured by Nippon Polyethylene, trade name: NF464N, MFR = 2.0 g / 10 minutes (190 ° C, load 2.16 kg), density = 0.918 g / cm 3 ) and linear low density Density polyethylene 2 (manufactured by Dow Chemical Co., Ltd., trade name: Energy8200, MFR = 5.0 g / 10 minutes (190 ° C., load 2.16 kg), density = 0.870 g / cm 3 ) is mixed at a mass ratio of 60:40. The composition was prepared as a pre-modification composition (density = 0.899 g / cm 3 ).
0.04 part by mass of di-t-butyl peroxide and 2.0 parts by mass of vinyltrimethoxysilane were added to and mixed with 100 parts by mass of this pre-denaturation composition. Then, the mixture was extruded into a melt-kneaded string using a single-screw extruder (D = 50 mmφ, L / D = 32) under the conditions of a temperature of 220 ° C., a screw rotation speed of 50 rpm, and an extrusion rate of 20 kg / h, and cooled. After cutting, a silane crosslinkable polyethylene composition was obtained.
The MFR (190 ° C., load 2.16 kg, 10 minutes) and density of the obtained silane crosslinkable polyethylene composition were measured and found to be MFR = 1 g / 10 min and density = 0.902 g / cm 3 .
直鎖状低密度ポリエチレン１（日本ポリエチレン社製、商品名：ＮＦ４６４Ｎ、ＭＦＲ＝２．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ）、密度＝０．９１８ｇ／ｃｍ３）と直鎖状低密度ポリエチレン２（ダウケミカル社製、商品名：Ｅｎｇａｇｅ８２００、ＭＦＲ＝５．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ）、密度＝０．８７０ｇ／ｃｍ３）を６０：４０の質量割合で混合して、変性前組成物（密度＝０．８９９ｇ／ｃｍ３）とした。
この変性前組成物１００質量部に対して、ジ－ｔ－ブチルパーオキサイド０．０４質量部とビニルトリメトキシシラン２．０質量部とを添加、混合した。その後、混合物を、単軸押出機（Ｄ＝５０ｍｍφ、Ｌ／Ｄ＝３２）を用いて、温度２２０℃、スクリュー回転数５０ｒｐｍ、押出量２０ｋｇ／ｈの条件で溶融混練紐状に押し出し、冷却した後カッティングし、シラン架橋性ポリエチレン組成物を得た。
得られたシラン架橋性ポリエチレン組成物のＭＦＲ（１９０℃、荷重２．１６ｋｇ、１０分）及び密度を測定したところ、ＭＦＲ＝１ｇ／１０分、密度＝０．９０２ｇ／ｃｍ３であった。 (Example 6)
Linear low density polyethylene 1 (manufactured by Nippon Polyethylene, trade name: NF464N, MFR = 2.0 g / 10 minutes (190 ° C, load 2.16 kg), density = 0.918 g / cm 3 ) and linear low density Density polyethylene 2 (manufactured by Dow Chemical Co., Ltd., trade name: Energy8200, MFR = 5.0 g / 10 minutes (190 ° C., load 2.16 kg), density = 0.870 g / cm 3 ) is mixed at a mass ratio of 60:40. The composition was prepared as a pre-modification composition (density = 0.899 g / cm 3 ).
0.04 part by mass of di-t-butyl peroxide and 2.0 parts by mass of vinyltrimethoxysilane were added to and mixed with 100 parts by mass of this pre-denaturation composition. Then, the mixture was extruded into a melt-kneaded string using a single-screw extruder (D = 50 mmφ, L / D = 32) under the conditions of a temperature of 220 ° C., a screw rotation speed of 50 rpm, and an extrusion rate of 20 kg / h, and cooled. After cutting, a silane crosslinkable polyethylene composition was obtained.
The MFR (190 ° C., load 2.16 kg, 10 minutes) and density of the obtained silane crosslinkable polyethylene composition were measured and found to be MFR = 1 g / 10 min and density = 0.902 g / cm 3 .
このシラン架橋性ポリエチレン組成物１００質量部と、シラノール縮合触媒を含むマスターバッチ（三菱ケミカル社製、ＬＺ０８２）５質量部とを、溶融紡糸装置に投入し、２２０℃で溶融混練した。次いで、２２０℃の樹脂を、吐出孔径：１．２５ｍｍφ、吐出孔数：１ホールの紡糸ノズルから０．６７ｇ／分の吐出量で吐出した。６ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。
得られた未延伸糸について、１段目の延伸として、糸温度：９０℃、延伸倍率：５．６倍の条件で熱板延伸を行った。連続して２段目の延伸として、糸温度：９５℃、延伸倍率：１．１倍の条件で熱板延伸を行った。さらに、３段目は、糸温度：１０５℃、延伸倍率：１．０倍の条件で熱アニール処理を行った。さらに、定長緊張下にて、恒温恒湿器にて８５℃、８５％ＲＨの環境下で２４時間静置して架橋処理を行いシラン架橋ポリエチレン組成物よりなる繊維を得た。得られた繊維について、結晶化度及び結晶配向度を測定した。結果を表２に示す。 100 parts by mass of this silane crosslinkable polyethylene composition and 5 parts by mass of a masterbatch (manufactured by Mitsubishi Chemical Corporation, LZ082) containing a silanol condensation catalyst were put into a melt spinning apparatus and melt-kneaded at 220 ° C. Next, the resin at 220 ° C. was discharged from a spinning nozzle having a discharge hole diameter of 1.25 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.67 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 6 m / min.
The obtained undrawn yarn was drawn on a hot plate under the conditions of a yarn temperature of 90 ° C. and a draw ratio of 5.6 times as the first drawing. As the second-stage stretching, the hot plate was continuously stretched under the conditions of a yarn temperature of 95 ° C. and a draw ratio of 1.1 times. Further, the third stage was subjected to thermal annealing treatment under the conditions of a yarn temperature of 105 ° C. and a draw ratio of 1.0 times. Further, it was allowed to stand for 24 hours in an environment of 85 ° C. and 85% RH under constant length tension and subjected to cross-linking treatment to obtain a fiber made of a silane cross-linked polyethylene composition. The degree of crystallinity and the degree of crystal orientation of the obtained fibers were measured. The results are shown in Table 2.
得られた未延伸糸について、１段目の延伸として、糸温度：９０℃、延伸倍率：５．６倍の条件で熱板延伸を行った。連続して２段目の延伸として、糸温度：９５℃、延伸倍率：１．１倍の条件で熱板延伸を行った。さらに、３段目は、糸温度：１０５℃、延伸倍率：１．０倍の条件で熱アニール処理を行った。さらに、定長緊張下にて、恒温恒湿器にて８５℃、８５％ＲＨの環境下で２４時間静置して架橋処理を行いシラン架橋ポリエチレン組成物よりなる繊維を得た。得られた繊維について、結晶化度及び結晶配向度を測定した。結果を表２に示す。 100 parts by mass of this silane crosslinkable polyethylene composition and 5 parts by mass of a masterbatch (manufactured by Mitsubishi Chemical Corporation, LZ082) containing a silanol condensation catalyst were put into a melt spinning apparatus and melt-kneaded at 220 ° C. Next, the resin at 220 ° C. was discharged from a spinning nozzle having a discharge hole diameter of 1.25 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.67 g / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 6 m / min.
The obtained undrawn yarn was drawn on a hot plate under the conditions of a yarn temperature of 90 ° C. and a draw ratio of 5.6 times as the first drawing. As the second-stage stretching, the hot plate was continuously stretched under the conditions of a yarn temperature of 95 ° C. and a draw ratio of 1.1 times. Further, the third stage was subjected to thermal annealing treatment under the conditions of a yarn temperature of 105 ° C. and a draw ratio of 1.0 times. Further, it was allowed to stand for 24 hours in an environment of 85 ° C. and 85% RH under constant length tension and subjected to cross-linking treatment to obtain a fiber made of a silane cross-linked polyethylene composition. The degree of crystallinity and the degree of crystal orientation of the obtained fibers were measured. The results are shown in Table 2.
得られた繊維を２０ｃｍの長さに切断し、上端を回転軸に固定して、下端に１２ｇのおもりを取り付けることで、５ＭＰａの張力をかけた。続いて、コイル形状になるまで繊維長手方向の回転軸で加撚操作を行い、コイル形状の繊維を作製した。同様の方法で、コイル形状の繊維をもう一本作製した後、２本のコイル形状の繊維に５ＭＰａの張力をかけながら撚りのトルクが無くなるまで逆撚りをかけ、合撚した。
得られたコイル形状の繊維について、単繊維直径ｄ及びコイル外径Ｄ’をデジタルマイクロスコープにて観測し、コイル平均直径Ｄ及びバネ指数Ｄ／ｄを算出した。また、得られた繊維の密度、ゲル分率を測定し、熱伸縮評価を行った。これらの結果を表２に示す。 The obtained fiber was cut to a length of 20 cm, the upper end was fixed to a rotating shaft, and a 12 g weight was attached to the lower end to apply a tension of 5 MPa. Subsequently, a twisting operation was performed on the rotation axis in the longitudinal direction of the fiber until the fiber became a coil shape, and a coil-shaped fiber was produced. After producing another coil-shaped fiber by the same method, the two coil-shaped fibers were reverse-twisted and twisted together while applying a tension of 5 MPa until the twisting torque disappeared.
For the obtained coil-shaped fibers, the single fiber diameter d and the coil outer diameter D'were observed with a digital microscope, and the coil average diameter D and the spring index D / d were calculated. In addition, the density and gel fraction of the obtained fibers were measured, and thermal expansion and contraction evaluation was performed. These results are shown in Table 2.
得られたコイル形状の繊維について、単繊維直径ｄ及びコイル外径Ｄ’をデジタルマイクロスコープにて観測し、コイル平均直径Ｄ及びバネ指数Ｄ／ｄを算出した。また、得られた繊維の密度、ゲル分率を測定し、熱伸縮評価を行った。これらの結果を表２に示す。 The obtained fiber was cut to a length of 20 cm, the upper end was fixed to a rotating shaft, and a 12 g weight was attached to the lower end to apply a tension of 5 MPa. Subsequently, a twisting operation was performed on the rotation axis in the longitudinal direction of the fiber until the fiber became a coil shape, and a coil-shaped fiber was produced. After producing another coil-shaped fiber by the same method, the two coil-shaped fibers were reverse-twisted and twisted together while applying a tension of 5 MPa until the twisting torque disappeared.
For the obtained coil-shaped fibers, the single fiber diameter d and the coil outer diameter D'were observed with a digital microscope, and the coil average diameter D and the spring index D / d were calculated. In addition, the density and gel fraction of the obtained fibers were measured, and thermal expansion and contraction evaluation was performed. These results are shown in Table 2.
（比較例６）
直鎖状低密度ポリエチレン３（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製、商品名：４２８０７８、ＭＦＲ＝１．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ）、密度＝０．９２０ｇ／ｃｍ３）を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練した。次いで、２２０℃の樹脂を吐出孔径：１．０ｍｍφ、吐出孔数：１ホールの紡糸ノズルから、０．６３ｍｌ／分の吐出量で吐出した。２．０ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。
得られた未延伸糸について、１段目の延伸として、糸温度：９０℃、延伸倍率：９．４倍の条件で熱板延伸を行った。連続して２段目の延伸として、糸温度：１００℃、延伸倍率：１．１倍の条件で熱板延伸を行った。さらに、３段目は、糸温度：１１０℃、延伸倍率：１．０倍の条件で熱アニール処理を行った。
得られた繊維について、結晶化度及び結晶配向度を測定した。結果を表２に示す。 (Comparative Example 6)
A melt-spinning device for linear low-density polyethylene 3 (manufactured by SIGMA-ALDRICH, trade name: 428878, MFR = 1.0 g / 10 minutes (190 ° C., load 2.16 kg), density = 0.920 g / cm 3 ). It was put into the extruder of No. 1 and melt-kneaded at 220 ° C. Next, the resin at 220 ° C. was discharged from a spinning nozzle having a discharge hole diameter of 1.0 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 ml / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 2.0 m / min.
The obtained undrawn yarn was drawn on a hot plate under the conditions of a yarn temperature of 90 ° C. and a draw ratio of 9.4 times as the first drawing. As the second-stage stretching, hot plate stretching was performed under the conditions of yarn temperature: 100 ° C. and drawing ratio: 1.1 times. Further, in the third stage, a thermal annealing treatment was performed under the conditions of a yarn temperature of 110 ° C. and a draw ratio of 1.0 times.
The degree of crystallinity and the degree of crystal orientation of the obtained fibers were measured. The results are shown in Table 2.
直鎖状低密度ポリエチレン３（ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製、商品名：４２８０７８、ＭＦＲ＝１．０ｇ／１０分（１９０℃、荷重２．１６ｋｇ）、密度＝０．９２０ｇ／ｃｍ３）を溶融紡糸装置の押出機に投入し、２２０℃で溶融混練した。次いで、２２０℃の樹脂を吐出孔径：１．０ｍｍφ、吐出孔数：１ホールの紡糸ノズルから、０．６３ｍｌ／分の吐出量で吐出した。２．０ｍ／分の引取り速度でボビンに巻き取って未延伸糸を得た。
得られた未延伸糸について、１段目の延伸として、糸温度：９０℃、延伸倍率：９．４倍の条件で熱板延伸を行った。連続して２段目の延伸として、糸温度：１００℃、延伸倍率：１．１倍の条件で熱板延伸を行った。さらに、３段目は、糸温度：１１０℃、延伸倍率：１．０倍の条件で熱アニール処理を行った。
得られた繊維について、結晶化度及び結晶配向度を測定した。結果を表２に示す。 (Comparative Example 6)
A melt-spinning device for linear low-density polyethylene 3 (manufactured by SIGMA-ALDRICH, trade name: 428878, MFR = 1.0 g / 10 minutes (190 ° C., load 2.16 kg), density = 0.920 g / cm 3 ). It was put into the extruder of No. 1 and melt-kneaded at 220 ° C. Next, the resin at 220 ° C. was discharged from a spinning nozzle having a discharge hole diameter of 1.0 mmφ and a number of discharge holes of 1 hole at a discharge rate of 0.63 ml / min. An undrawn yarn was obtained by winding on a bobbin at a take-up speed of 2.0 m / min.
The obtained undrawn yarn was drawn on a hot plate under the conditions of a yarn temperature of 90 ° C. and a draw ratio of 9.4 times as the first drawing. As the second-stage stretching, hot plate stretching was performed under the conditions of yarn temperature: 100 ° C. and drawing ratio: 1.1 times. Further, in the third stage, a thermal annealing treatment was performed under the conditions of a yarn temperature of 110 ° C. and a draw ratio of 1.0 times.
The degree of crystallinity and the degree of crystal orientation of the obtained fibers were measured. The results are shown in Table 2.
得られた繊維を２０ｃｍの長さに切断して、上端を回転軸に固定して、下端に４９ｇのおもりを取り付けることで、２０ＭＰａの張力をかけた。続いて、繊維がコイル形状に折りたたまれるまで加撚操作を行い、コイル形状の繊維を作製した。同様の方法で、コイル形状の繊維をもう一本作製し、２本のコイル形状の繊維を合撚した。
得られたコイル形状の繊維について、単繊維直径ｄ及びコイル外径Ｄ’をデジタルマイクロスコープにて観測し、コイル平均直径Ｄ及びバネ指数Ｄ／ｄを算出した。また、得られた繊維の密度、ゲル分率を測定し、熱伸縮評価を行った。なお、得られた繊維は、架橋構造を有さないため、熱収縮率は低いものであった。これらの結果を表２に示す。 The obtained fiber was cut to a length of 20 cm, the upper end was fixed to a rotating shaft, and a weight of 49 g was attached to the lower end to apply a tension of 20 MPa. Subsequently, a twisting operation was performed until the fibers were folded into a coil shape to produce coil-shaped fibers. In the same manner, another coil-shaped fiber was produced, and two coil-shaped fibers were twisted together.
For the obtained coil-shaped fibers, the single fiber diameter d and the coil outer diameter D'were observed with a digital microscope, and the coil average diameter D and the spring index D / d were calculated. In addition, the density and gel fraction of the obtained fibers were measured, and thermal expansion and contraction evaluation was performed. Since the obtained fiber does not have a crosslinked structure, the heat shrinkage rate was low. These results are shown in Table 2.
得られたコイル形状の繊維について、単繊維直径ｄ及びコイル外径Ｄ’をデジタルマイクロスコープにて観測し、コイル平均直径Ｄ及びバネ指数Ｄ／ｄを算出した。また、得られた繊維の密度、ゲル分率を測定し、熱伸縮評価を行った。なお、得られた繊維は、架橋構造を有さないため、熱収縮率は低いものであった。これらの結果を表２に示す。 The obtained fiber was cut to a length of 20 cm, the upper end was fixed to a rotating shaft, and a weight of 49 g was attached to the lower end to apply a tension of 20 MPa. Subsequently, a twisting operation was performed until the fibers were folded into a coil shape to produce coil-shaped fibers. In the same manner, another coil-shaped fiber was produced, and two coil-shaped fibers were twisted together.
For the obtained coil-shaped fibers, the single fiber diameter d and the coil outer diameter D'were observed with a digital microscope, and the coil average diameter D and the spring index D / d were calculated. In addition, the density and gel fraction of the obtained fibers were measured, and thermal expansion and contraction evaluation was performed. Since the obtained fiber does not have a crosslinked structure, the heat shrinkage rate was low. These results are shown in Table 2.
（実施例７）
可逆的熱伸縮性を有する繊維Ａとして、直径０．２１ｍｍのナイロン繊維（商品名：銀鱗（登録商標）１．５号、東レ社製）を使用し、該繊維６０ｃｍに７０ｇの荷重をかけ、３５０回撚りをかけることで長さ１４０ｍｍのオーバーツイスト型のコイル形状の繊維を作製した。作製時には、撚りによって荷重が回転しないよう制御した。また、撚りの速度は１秒間６回転とした。
得られたコイル形状の繊維を、２０％伸長をかけた状態で、１８０℃で６０分間保持することで熱セットを行った。作製されたコイル形状の繊維のコイル形状の直径は４８０μｍであった。 (Example 7)
As the fiber A having reversible thermal elasticity, a nylon fiber having a diameter of 0.21 mm (trade name: Ginscale (registered trademark) No. 1.5, manufactured by Toray Industries, Inc.) was used, and a load of 70 g was applied to the fiber 60 cm. By twisting 350 times, an overtwist type coil-shaped fiber having a length of 140 mm was produced. At the time of production, the load was controlled not to rotate due to twisting. The twisting speed was 6 rotations per second.
The obtained coil-shaped fiber was held at 180 ° C. for 60 minutes in a state of being stretched by 20% to perform heat setting. The diameter of the coil shape of the produced coil-shaped fiber was 480 μm.
可逆的熱伸縮性を有する繊維Ａとして、直径０．２１ｍｍのナイロン繊維（商品名：銀鱗（登録商標）１．５号、東レ社製）を使用し、該繊維６０ｃｍに７０ｇの荷重をかけ、３５０回撚りをかけることで長さ１４０ｍｍのオーバーツイスト型のコイル形状の繊維を作製した。作製時には、撚りによって荷重が回転しないよう制御した。また、撚りの速度は１秒間６回転とした。
得られたコイル形状の繊維を、２０％伸長をかけた状態で、１８０℃で６０分間保持することで熱セットを行った。作製されたコイル形状の繊維のコイル形状の直径は４８０μｍであった。 (Example 7)
As the fiber A having reversible thermal elasticity, a nylon fiber having a diameter of 0.21 mm (trade name: Ginscale (registered trademark) No. 1.5, manufactured by Toray Industries, Inc.) was used, and a load of 70 g was applied to the fiber 60 cm. By twisting 350 times, an overtwist type coil-shaped fiber having a length of 140 mm was produced. At the time of production, the load was controlled not to rotate due to twisting. The twisting speed was 6 rotations per second.
The obtained coil-shaped fiber was held at 180 ° C. for 60 minutes in a state of being stretched by 20% to perform heat setting. The diameter of the coil shape of the produced coil-shaped fiber was 480 μm.
得られたコイル形状の繊維を経糸とし、電熱線（東京特殊電線社製、巻芯：ポリアリレート、発熱素線：ニッケルクロム合金、絶縁被膜：エチレン－テトラフルオロエチレン共重合体、直径：９３０μｍ、抵抗値：３００Ω／ｍ（２０℃時））を緯糸として、図７に示すような平織の織物を作製した。なお、図６は、この織物に用いたコイル形状の繊維の一部を示す写真である。また、図１０は、作製した織物の一部を示す写真である。織物の末端において、電熱線はどの箇所もループで折り返す形で配置し、１枚の織物の中で電熱線は１本のみ使用した。また、１枚の織物の中でコイル形状の繊維は８本使用した。作製した織物の長辺の長さは１００ｍｍ、短辺の長さは５ｍｍであった。この織物を２枚重ねて、アクチュエータモジュールとした。コイル形状の繊維には、１本あたり１０ｇの荷重をかけた。
このアクチュエータモジュールの電熱線に直流電源装置を用いて通電し、織物の表面温度が約９０℃になるまで通電加熱を行い、熱収縮を行った。表面温度は、熱画像カメラＡ６７００ＳＣ（商品名、チノー社製）を使用して確認した。該織物は５％収縮し（熱収縮率：５％）、その後空冷することにより元の長さに戻った。同じ条件で加熱と空冷をさらに５回繰り返し行った（合計６回）が、該織物の長さは通電加熱前と変わらなかった（復元率：１００％）。すなわち、作製した織物は、可逆的熱伸縮性を有することが確認できた。また、通電によって到達する電熱線の温度も変化はなく、得られたアクチュエータモジュールは、高い耐久性を維持できることが確認された。 Using the obtained coil-shaped fiber as warp, heating wire (manufactured by Tokyo Special Electric Wire Co., Ltd., core: polyarylate, heating element wire: nichrome alloy, insulating coating: ethylene-tetrafluoroethylene copolymer, diameter: 930 μm, A plain weave woven fabric as shown in FIG. 7 was produced using a resistance value of 300 Ω / m (at 20 ° C.) as a warp and weft. Note that FIG. 6 is a photograph showing a part of the coil-shaped fibers used in this woven fabric. Further, FIG. 10 is a photograph showing a part of the produced woven fabric. At the end of the woven fabric, the heating wires were arranged so as to be folded back in a loop at every place, and only one heating wire was used in one woven fabric. In addition, eight coil-shaped fibers were used in one woven fabric. The length of the long side of the produced woven fabric was 100 mm, and the length of the short side was 5 mm. Two pieces of this woven fabric were stacked to form an actuator module. A load of 10 g was applied to each coil-shaped fiber.
The heating wire of this actuator module was energized using a DC power supply device, and energized and heated until the surface temperature of the woven fabric reached about 90 ° C. to perform heat shrinkage. The surface temperature was confirmed using a thermal image camera A6700SC (trade name, manufactured by Chino Co., Ltd.). The woven fabric shrank by 5% (heat shrinkage rate: 5%) and then returned to its original length by air cooling. Heating and air cooling were repeated 5 times (6 times in total) under the same conditions, but the length of the woven fabric was the same as that before the energization heating (restoration rate: 100%). That is, it was confirmed that the produced woven fabric had reversible thermal elasticity. In addition, the temperature of the heating wire reached by energization did not change, and it was confirmed that the obtained actuator module can maintain high durability.
このアクチュエータモジュールの電熱線に直流電源装置を用いて通電し、織物の表面温度が約９０℃になるまで通電加熱を行い、熱収縮を行った。表面温度は、熱画像カメラＡ６７００ＳＣ（商品名、チノー社製）を使用して確認した。該織物は５％収縮し（熱収縮率：５％）、その後空冷することにより元の長さに戻った。同じ条件で加熱と空冷をさらに５回繰り返し行った（合計６回）が、該織物の長さは通電加熱前と変わらなかった（復元率：１００％）。すなわち、作製した織物は、可逆的熱伸縮性を有することが確認できた。また、通電によって到達する電熱線の温度も変化はなく、得られたアクチュエータモジュールは、高い耐久性を維持できることが確認された。 Using the obtained coil-shaped fiber as warp, heating wire (manufactured by Tokyo Special Electric Wire Co., Ltd., core: polyarylate, heating element wire: nichrome alloy, insulating coating: ethylene-tetrafluoroethylene copolymer, diameter: 930 μm, A plain weave woven fabric as shown in FIG. 7 was produced using a resistance value of 300 Ω / m (at 20 ° C.) as a warp and weft. Note that FIG. 6 is a photograph showing a part of the coil-shaped fibers used in this woven fabric. Further, FIG. 10 is a photograph showing a part of the produced woven fabric. At the end of the woven fabric, the heating wires were arranged so as to be folded back in a loop at every place, and only one heating wire was used in one woven fabric. In addition, eight coil-shaped fibers were used in one woven fabric. The length of the long side of the produced woven fabric was 100 mm, and the length of the short side was 5 mm. Two pieces of this woven fabric were stacked to form an actuator module. A load of 10 g was applied to each coil-shaped fiber.
The heating wire of this actuator module was energized using a DC power supply device, and energized and heated until the surface temperature of the woven fabric reached about 90 ° C. to perform heat shrinkage. The surface temperature was confirmed using a thermal image camera A6700SC (trade name, manufactured by Chino Co., Ltd.). The woven fabric shrank by 5% (heat shrinkage rate: 5%) and then returned to its original length by air cooling. Heating and air cooling were repeated 5 times (6 times in total) under the same conditions, but the length of the woven fabric was the same as that before the energization heating (restoration rate: 100%). That is, it was confirmed that the produced woven fabric had reversible thermal elasticity. In addition, the temperature of the heating wire reached by energization did not change, and it was confirmed that the obtained actuator module can maintain high durability.
（比較例７）
実施例１と同様にしてコイル形状の繊維を作製し、その表面に銀含有ペースト（商品名：ＰＥ８７４、デュポン社製）を膜厚が２００μｍとなるように塗布した。
該コイル形状の繊維を１０本並べて、両端をそれぞれ１０本まとめて固定し、１本あたり１０ｇの荷重をかけた。
コイル形状の繊維に塗布された銀含有ペーストを利用して直流電源装置を用いて通電し、実施例１と同様に、繊維の表面温度が約９０℃になるまで通電加熱を行い、熱収縮を行った。表面温度は、熱画像カメラＡ６７００ＳＣ（商品名、チノー社製）を使用して確認した。コイル形状の繊維が５％収縮し、その後空冷することにより元の長さに戻った。同じ条件で加熱と空冷をさらに５回繰り返し行った（合計６回）ところ、通電によって到達するコイル形状の繊維の表面温度が最初の通電加熱時の表面温度より下がり、耐久性に問題が発生した。 (Comparative Example 7)
A coil-shaped fiber was produced in the same manner as in Example 1, and a silver-containing paste (trade name: PE874, manufactured by DuPont) was applied to the surface thereof so that the film thickness was 200 μm.
Ten fibers of the coil shape were arranged side by side, and ten fibers at both ends were fixed together, and a load of 10 g was applied to each fiber.
The silver-containing paste applied to the coil-shaped fiber is used to energize using a DC power supply device, and as in Example 1, energization heating is performed until the surface temperature of the fiber reaches about 90 ° C. to heat shrinkage. gone. The surface temperature was confirmed using a thermal image camera A6700SC (trade name, manufactured by Chino Co., Ltd.). The coil-shaped fibers shrank by 5% and then returned to their original length by air cooling. When heating and air cooling were repeated 5 more times under the same conditions (6 times in total), the surface temperature of the coil-shaped fibers reached by energization became lower than the surface temperature at the time of the first energization heating, and a problem occurred in durability. ..
実施例１と同様にしてコイル形状の繊維を作製し、その表面に銀含有ペースト（商品名：ＰＥ８７４、デュポン社製）を膜厚が２００μｍとなるように塗布した。
該コイル形状の繊維を１０本並べて、両端をそれぞれ１０本まとめて固定し、１本あたり１０ｇの荷重をかけた。
コイル形状の繊維に塗布された銀含有ペーストを利用して直流電源装置を用いて通電し、実施例１と同様に、繊維の表面温度が約９０℃になるまで通電加熱を行い、熱収縮を行った。表面温度は、熱画像カメラＡ６７００ＳＣ（商品名、チノー社製）を使用して確認した。コイル形状の繊維が５％収縮し、その後空冷することにより元の長さに戻った。同じ条件で加熱と空冷をさらに５回繰り返し行った（合計６回）ところ、通電によって到達するコイル形状の繊維の表面温度が最初の通電加熱時の表面温度より下がり、耐久性に問題が発生した。 (Comparative Example 7)
A coil-shaped fiber was produced in the same manner as in Example 1, and a silver-containing paste (trade name: PE874, manufactured by DuPont) was applied to the surface thereof so that the film thickness was 200 μm.
Ten fibers of the coil shape were arranged side by side, and ten fibers at both ends were fixed together, and a load of 10 g was applied to each fiber.
The silver-containing paste applied to the coil-shaped fiber is used to energize using a DC power supply device, and as in Example 1, energization heating is performed until the surface temperature of the fiber reaches about 90 ° C. to heat shrinkage. gone. The surface temperature was confirmed using a thermal image camera A6700SC (trade name, manufactured by Chino Co., Ltd.). The coil-shaped fibers shrank by 5% and then returned to their original length by air cooling. When heating and air cooling were repeated 5 more times under the same conditions (6 times in total), the surface temperature of the coil-shaped fibers reached by energization became lower than the surface temperature at the time of the first energization heating, and a problem occurred in durability. ..
Ｄ：コイル平均直径
ｄ：単繊維直径
Ｄ’：コイル外径
Ｌａ：加熱により収縮する部分ａの長さ
Ｌｂ：加熱により収縮しない又は熱収縮性が低い部分ｂの長さ
１、１’ 可逆的熱伸縮性を有するコイル形状の繊維Ａ
２、２’ 電熱線
３ アクチュエータモジュールの外枠
D: Coil average diameter d: Single fiber diameter D': Coil outer diameter La: Length of part a that shrinks due to heating Lb: Length of part b that does not shrink due to heating or haslow heat shrinkage 1, 1'Reversible Coil-shaped fiber A with thermal elasticity
2, 2'heating wire 3 outer frame of actuator module
ｄ：単繊維直径
Ｄ’：コイル外径
Ｌａ：加熱により収縮する部分ａの長さ
Ｌｂ：加熱により収縮しない又は熱収縮性が低い部分ｂの長さ
１、１’ 可逆的熱伸縮性を有するコイル形状の繊維Ａ
２、２’ 電熱線
３ アクチュエータモジュールの外枠
D: Coil average diameter d: Single fiber diameter D': Coil outer diameter La: Length of part a that shrinks due to heating Lb: Length of part b that does not shrink due to heating or has
2, 2'heating wire 3 outer frame of actuator module
Claims (33)
- ゲル分率が１０％以上であり、結晶配向度が８０％以上であり、結晶化度が６０％以下である成形体。 A molded product having a gel fraction of 10% or more, a crystal orientation degree of 80% or more, and a crystallinity degree of 60% or less.
- ゲル分率が１０％以上であり、結晶配向度が６０％以上であり、コイル形状である成形体。 A molded product having a gel fraction of 10% or more, a crystal orientation degree of 60% or more, and a coil shape.
- 加熱による単位温度当たりの収縮率が０．０７％／℃以上である請求項１または２に記載の成形体。 The molded product according to claim 1 or 2, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher.
- 加熱により５０℃の温度変化を与えた時の収縮率が３．５％以上である請求項１～３のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 3, wherein the shrinkage rate when a temperature change of 50 ° C. is applied by heating is 3.5% or more.
- 成形体内部に架橋構造を有する請求項１～４のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 4, which has a crosslinked structure inside the molded product.
- 前記架橋構造がシラン架橋を含む請求項５に記載の成形体。 The molded product according to claim 5, wherein the crosslinked structure includes a silane crosslink.
- 可逆的熱伸縮性を有し、加熱による単位温度当たりの収縮率が０．０７％／℃以上である請求項１～６のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 6, which has reversible thermal elasticity and has a shrinkage rate of 0.07% / ° C. or more per unit temperature due to heating.
- －３０℃から２００℃の温度領域において、単位温度当たりの収縮率が０．０７％／℃以上である請求項１～７のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 7, wherein the shrinkage rate per unit temperature is 0.07% / ° C. or higher in the temperature range of -30 ° C to 200 ° C.
- １～２０ＭＰａの引張荷重状態で、加熱による単位温度当たりの収縮率が０．０７％／℃以上である請求項１～８のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 8, wherein the shrinkage rate per unit temperature due to heating is 0.07% / ° C. or higher under a tensile load of 1 to 20 MPa.
- ５０℃の温度変化の加熱による収縮後に５０℃降温したときの復元率が、９０％以上である請求項１～９のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 9, wherein the restoration rate when the temperature is lowered by 50 ° C after shrinking due to a temperature change of 50 ° C is 90% or more.
- オレフィン系重合体からなる請求項１～１０のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 10, which is made of an olefin polymer.
- ポリエチレンからなる請求項１～１１のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 11 made of polyethylene.
- 前記成形体が、繊維状、板状、シート状もしくはフィルム状であり、又はこれらの１種以上の多層構造を有する請求項１～１２のいずれか一項に記載の成形体。 The molded product according to any one of claims 1 to 12, wherein the molded product is in the form of a fiber, a plate, a sheet, or a film, or has a multilayer structure of one or more of these.
- 前記成形体が繊維状であり、該繊維状成形体の単繊維の繊度が５０～１００００ｄｔｅｘである請求項１３に記載の成形体。 The molded product according to claim 13, wherein the molded product is fibrous and the fineness of the single fiber of the fibrous molded product is 50 to 10000 dtex.
- 前記成形体が繊維状であり、該繊維状成形体の単繊維の直径が８０～１２００μｍである請求項１３または１４に記載の成形体。 The molded product according to claim 13 or 14, wherein the molded product is fibrous and the diameter of a single fiber of the fibrous molded product is 80 to 1200 μm.
- コイル形状に形成された請求項１～１５のいずれか一項に記載の成形体。 The molded body according to any one of claims 1 to 15, which is formed in a coil shape.
- 以下（１）～（３）をすべて満たす請求項１６に記載の成形体。
（１）繊維軸に対して垂直方向から測定したX線回折パターンについて、２θ＝１０°から３０°の区間に１つ以上のピークがある。
（２）最も強度の高いピーク以外にピークがないか、または次に強度の高いピークの強度に対する最も強度の高いピークの強度が２倍以上である。
（３）最も強度の高いピークにおける繊維軸方向配向度が、コイル状材料について７５％以上９０％以下である。 The molded product according to claim 16, which satisfies all of the following (1) to (3).
(1) Regarding the X-ray diffraction pattern measured from the direction perpendicular to the fiber axis, there is one or more peaks in the section from 2θ = 10 ° to 30 °.
(2) There is no peak other than the peak with the highest intensity, or the intensity of the peak with the highest intensity is more than double the intensity of the peak with the next highest intensity.
(3) The degree of fiber axial orientation at the peak with the highest strength is 75% or more and 90% or less for the coiled material. - バネ指数Ｄ／ｄが０．５以上であり、前記コイル形状の平均直径Ｄが１００～２０００μｍである請求項１６または１７に記載の成形体。
Ｄはコイル平均直径（μｍ）を示し、ｄは単繊維直径（μｍ）を示す。 The molded product according to claim 16 or 17, wherein the spring index D / d is 0.5 or more, and the average diameter D of the coil shape is 100 to 2000 μm.
D indicates the coil average diameter (μm), and d indicates the single fiber diameter (μm). - 密度が０．８８１～０．９４１ｇ／ｃｍ３である直鎖状低密度ポリエチレン、及び密度が０．９４２～０．９７０ｇ／ｃｍ３の高密度ポリエチレンから選択される１つ以上のポリエチレン２０～８０質量％と、密度が０．８６０～０．８８０ｇ／ｃｍ３である直鎖状低密度ポリエチレン２０～８０質量％と、を含有する混合物を含む請求項１６～１８のいずれか一項に記載の成形体。 One or more polyethylenes 20-80 selected from linear low density polyethylene with a density of 0.881 to 0.941 g / cm 3 and high density polyethylene with a density of 0.942 to 0.970 g / cm 3 . The invention according to any one of claims 16 to 18, which comprises a mixture containing 20 to 80% by mass of linear low density polyethylene having a density of 0.860 to 0.880 g / cm 3 and a density of 0.860 to 0.880 g / cm 3. Molded body.
- 前記混合物の密度が０．８６０～０．９４０ｇ／ｃｍ３である請求項１９に記載の成形体。 The molded product according to claim 19, wherein the density of the mixture is 0.860 to 0.940 g / cm 3 .
- 撚数が１～３０回／ｍｍである請求項１６～２０のいずれか一項に記載の成形体。 The molded product according to any one of claims 16 to 20, wherein the number of twists is 1 to 30 times / mm.
- 可逆的熱伸縮性を有する成形体であって、可逆的熱伸縮性を有さない部分を部分的に有する請求項１～２１のいずれか一項に記載の成形体。 The molded body according to any one of claims 1 to 21, which is a molded body having reversible thermal elasticity and partially has a portion not having reversible thermal elasticity.
- 請求項１～２２のいずれか一項に記載の成形体を含む繊維製品。 A textile product containing the molded product according to any one of claims 1 to 22.
- 織物、編物、不織布、又は紐である請求項２３に記載の繊維製品。 The textile product according to claim 23, which is a woven fabric, a knitted fabric, a non-woven fabric, or a string.
- 前記繊維製品が織物であって、経糸または緯糸の一方が前記成形体を含み、他方が前記成形体を含まず且つ絶縁被膜で覆われた電熱線を含む請求項２３に記載の繊維製品。 The textile product according to claim 23, wherein the textile product is a woven fabric, one of which is a warp or a weft containing the molded body, and the other is a heating wire which does not contain the molded body and is covered with an insulating coating.
- 前記電熱線が、連続した１本の電熱線である請求項２５に記載の繊維製品。 The textile product according to claim 25, wherein the heating wire is one continuous heating wire.
- 前記電熱線が、複数本の電熱線からなる請求項２５に記載の繊維製品。 The textile product according to claim 25, wherein the heating wire is composed of a plurality of heating wires.
- 前記電熱線の直径が２０～２０００μｍである請求項２５～２７のいずれか一項に記載の繊維製品。 The textile product according to any one of claims 25 to 27, wherein the heating wire has a diameter of 20 to 2000 μm.
- 前記織物の組織が、平織、綾織、カラミ織および朱子織のいずれか、またはこれらの組織の組み合わせである請求項２３～２８のいずれか一項に記載の繊維製品。 The textile product according to any one of claims 23 to 28, wherein the texture of the woven fabric is any of plain weave, twill weave, karamii weave and satin weave, or a combination of these textures.
- 一辺の長さが５０～１０００ｍｍ、他方の辺の長さが５～２００ｍｍである請求項２３～２９のいずれか一項に記載の繊維製品。 The textile product according to any one of claims 23 to 29, wherein the length of one side is 50 to 1000 mm and the length of the other side is 5 to 200 mm.
- 請求項１～２２のいずれか一項に記載の成形体が並行配列および／または直列配列されているアクチュエータ。 An actuator in which the compacts according to any one of claims 1 to 22 are arranged in parallel and / or in series.
- 請求項２３～２９のいずれか一項に記載の繊維製品が積層した積層物を含むアクチュエータモジュール。 An actuator module including a laminate in which the textile products according to any one of claims 23 to 29 are laminated.
- 請求項３２に記載のアクチュエータモジュールを駆動部として備えるアシストスーツ。 An assist suit including the actuator module according to claim 32 as a drive unit.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020183059A JP2022073216A (en) | 2020-10-30 | 2020-10-30 | Compact having reversible thermal elasticity, and actuator |
| JP2020-183087 | 2020-10-30 | ||
| JP2020183078A JP2022073227A (en) | 2020-10-30 | 2020-10-30 | Shaped article of coil shape having reversible heat stretch properties and actuator |
| JP2020-183078 | 2020-10-30 | ||
| JP2020183087 | 2020-10-30 | ||
| JP2020-183059 | 2020-10-30 | ||
| JP2021060552A JP2022156721A (en) | 2021-03-31 | 2021-03-31 | Woven fabric having reversible thermal elasticity, actuator module, and assist suit |
| JP2021-060552 | 2021-03-31 | ||
| JP2021-070931 | 2021-04-20 | ||
| JP2021070931A JP2022073903A (en) | 2020-10-30 | 2021-04-20 | Compact having bridge structure, and actuator |
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| WO2022092303A1 true WO2022092303A1 (en) | 2022-05-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2021/040167 WO2022092303A1 (en) | 2020-10-30 | 2021-10-29 | Molded article having reversible thermal stretchability, fiber product, actuator, and assist suit |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62257415A (en) * | 1985-11-30 | 1987-11-10 | Mitsui Petrochem Ind Ltd | Molded article of molecule orientated and silane crosslinked ultra-high-molecular-weight polyethylene and production thereof |
| JPH0835124A (en) * | 1985-04-01 | 1996-02-06 | Raychem Corp | High-strength polymer fiber |
| WO2019230103A1 (en) * | 2018-05-31 | 2019-12-05 | パナソニックＩｐマネジメント株式会社 | Actuator device, actuator band, and actuator band manufacturing method |
| WO2020054633A1 (en) * | 2018-09-10 | 2020-03-19 | 東レ株式会社 | Fiber for actuators, and actuator and fiber product using same |
-
2021
- 2021-10-29 WO PCT/JP2021/040167 patent/WO2022092303A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0835124A (en) * | 1985-04-01 | 1996-02-06 | Raychem Corp | High-strength polymer fiber |
| JPS62257415A (en) * | 1985-11-30 | 1987-11-10 | Mitsui Petrochem Ind Ltd | Molded article of molecule orientated and silane crosslinked ultra-high-molecular-weight polyethylene and production thereof |
| WO2019230103A1 (en) * | 2018-05-31 | 2019-12-05 | パナソニックＩｐマネジメント株式会社 | Actuator device, actuator band, and actuator band manufacturing method |
| WO2020054633A1 (en) * | 2018-09-10 | 2020-03-19 | 東レ株式会社 | Fiber for actuators, and actuator and fiber product using same |
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