Hair for toy

Abstract

To provide hair for toys having a function of being deformable in any shape by applying external stress thereto in a specific temperature range, fixing the deformed state in the specific temperature range and restoring to an original state if necessary, having excellent playability due to the repetitive deformability, and suppressing fusion of filaments, and toy using the hair for the toys.SOLUTION: Hair for toys is composed of filaments comprising a 4-methyl-1-pentene-α-olefin copolymer including a 4-methyl-1-pentene-derived constitutional unit and a C2-20 α-olefin-derived constitutional unit other than the 4-methyl-1-pentene, and a low-density polyethylene, and the filaments having the mean outer diameter of 0.2 to 3 mm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to hair for toys, and more particularly to hair for toys that can be easily deformed into any shape by application of an external stress in a specific temperature range, and further that can fix the state deformed into any shape by application of an external stress in a specific temperature range, and can restore to its original shape as necessary. [Background technology]

[0002] Conventionally, fibers made of polyamide, polyolefin, vinylidene chloride resin, vinyl chloride resin, etc. have been used as hair for toys. Toy hair made of these fibers cannot be deformed unless a special tool is used at a high temperature above the softening point of the fiber, and it has been difficult to deform the hair and give it curls, etc.

[0003] In order to solve such problems, hair made of shape-memory alloys or shape-memory resins has been disclosed (see, for example, Patent Documents 1 and 2). Shape memory alloys and shape memory resins can be deformed from an initial shape to any shape, and then fixed in the deformed shape, and have the property of returning to the initial shape when heated to a specific temperature or higher, but the hair disclosed in Reference 1 uses metal, and therefore has poor hair texture. Also, the hair disclosed in Reference 2 uses resin, but depending on the resin used, the spinnability of the fibers that make up the hair is poor, and the fibers may fuse together at a specific temperature or higher, which does not satisfy marketability. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Utility Model Application Publication No. 62-137086 [Patent Document 2] Japanese Utility Model Application Publication No. 2-14198 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above-mentioned problems, and aims to provide toy hair which can be easily deformed into any shape by application of external stress in a specific temperature range, and further which can fix the deformed state in a specific temperature range and has the function of restoring to the original shape as necessary, and which has a good texture and suppresses fusion between filaments, and a toy such as a doll using this toy hair. [Means for solving the problem]

[0006] The present invention relates to a structural unit derived from 4-methyl-1-pentene and a C unit other than 4-methyl-1-pentene. 2-20 The present invention provides toy hair that is made up of filaments having an average outer diameter of 0.2 to 3 mm and that contains a 4-methyl-1-pentene / α-olefin copolymer containing an α-olefin-derived structural unit and low-density polyethylene. The present invention also requires that the 4-methyl-1-pentene / α-olefin copolymer and low-density polyethylene are melt-blended, that the mass ratio of the 4-methyl-1-pentene / α-olefin copolymer to the low-density polyethylene is 20:80 to 99:1, and that the composition contains a thermochromic material. A further feature is a toy equipped with the toy hair. Effect of the Invention

[0007] The present invention can provide toy hair which can be deformed into any shape by application of external stress in a specific temperature range, and further has the function of being able to fix the deformed state in a specific temperature range and to restore it to its original state as necessary, which can be repeatedly deformed, has excellent playability, has a good texture, and is suppressed from fusing together filaments, and a toy such as a doll which uses this toy hair. [Brief description of the drawings]

[0008] [Figure 1] 1 is a graph illustrating hysteresis characteristics in a color density-temperature curve of a heat-discolorable, reversible thermochromic composition. [Diagram 2] 1 is a graph illustrating the hysteresis characteristic in a color density-temperature curve of a heat-discolorable, reversible thermochromic composition having color memory properties. [Diagram 3] 1 is a graph illustrating the hysteresis characteristic in a color density-temperature curve of a reversible thermochromic composition that develops color upon heating. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The toy hair according to the present invention (hereinafter sometimes referred to as "hair") is composed of filaments containing 4-methyl-1-pentene-α-olefin copolymer and low density polyethylene. It can be easily deformed into any shape in a specific temperature range, and has the function of being able to fix the deformed state in a specific temperature range (shape retention), and can restore the deformed shape to its original shape as needed (shape recovery). Here, shape retention and shape recovery are collectively referred to as "shape memory", and the filaments constituting the toy hair according to the present invention have shape memory. Each component constituting the toy hair according to the present invention will be described below.

[0010] The filaments constituting the toy hair according to the present invention contain a 4-methyl-1-pentene / α-olefin copolymer (hereinafter, sometimes referred to as "polymer (I)"). The 4-methyl-1-pentene / α-olefin copolymer contains at least a structural unit (Ia) derived from 4-methyl-1-pentene and a C structural unit other than 4-methyl-1-pentene. 2-20 The structural unit (Ib) derived from an α-olefin is represented by the formula: 2-20 "α-olefin" means not including 4-methyl-1-pentene, unless otherwise specified.

[0011] In the 4-methyl-1-pentene-α-olefin copolymer, the blending ratio of the structural unit (Ia) and the structural unit (Ib) is not particularly limited. In order to obtain excellent copolymerizability and physical properties of the copolymer, when the total of the structural unit (Ia) and the structural unit (Ib) is taken as 100 mol%, it is preferable that the structural unit (Ia) is 50-95 mol% and the structural unit (Ib) is 5-50 mol%, and more preferably the structural unit (Ia) is 70-90 mol% and the structural unit (Ib) is 10-30 mol%.

[0012] Used in 4-methyl-1-pentene / α-olefin copolymers, C 2-20 Examples of the α-olefin include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and functionalized vinyl compounds.

[0013] The linear α-olefin preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 2 or 3 carbon atoms. Examples of linear α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred, and ethylene or propylene is more preferred.

[0014] The branched α-olefin preferably has 5-20 carbon atoms, and more preferably 5-15 carbon atoms. Examples of branched α-olefins include 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1-pentene.

[0015] The cyclic olefin has 3 to 20 carbon atoms, and preferably 5 to 15 carbon atoms. Examples of the cyclic olefin include cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.

[0016] Examples of aromatic vinyl compounds include mono- or polyalkylstyrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene.

[0017] The conjugated diene has 4-20 carbon atoms, and preferably 4-10 carbon atoms. Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene.

[0018] Examples of functionalized vinyl compounds include C 2-20 olefins containing hydroxyl groups, such as linear or branched α-olefins having terminal hydroxyl groups; 2-20 Examples of the unsaturated carboxylic acids include linear or branched halogenated α-olefins; (meth)acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, and 10-undecenoic acid; unsaturated amines such as allylamine, 5-hexenamine, and 6-heptenamine; succinic anhydrides such as (2,7-octadienyl)succinic anhydride and pentapropenylsuccinic anhydride; unsaturated carboxylic acid anhydrides such as anhydrides obtained from the above-mentioned unsaturated carboxylic acids; unsaturated carboxylic acid halides such as halides obtained from the above-mentioned unsaturated carboxylic acids; unsaturated epoxy compounds; and ethylenically unsaturated silane compounds.

[0019] The α-olefins can be used alone or in combination of two or more kinds.

[0020] As α-olefins, 2-4 Preferred are linear α-olefins such as ethylene, propylene, 1-butene, etc. Ethylene or propylene is more preferred, and propylene is even more preferred, since it is easy to improve the flexibility of the filament.

[0021] The blending ratio of 4-methyl-1-pentene and α-olefin in the 4-methyl-1-pentene-α-olefin copolymer is, for example, 13 It can be measured by C NMR.

[0022] The 4-methyl-1-pentene·α-olefin copolymer preferably satisfies the requirements (i) to (v) described below.

[0023] The 4-methyl-1-pentene·α-olefin copolymer (i) has an intrinsic viscosity [η] in decalin at 135° C. of preferably 0.5 to 5.0 dL / g, more preferably 0.6 to 4.0 dL / g, and further preferably 1.0 to 2.5 dL / g. The intrinsic viscosity [η] can be adjusted by the amount of hydrogen added in the polymerization step when preparing the copolymer. The intrinsic viscosity [η] is a value measured at 135° C. using decalin, and can be measured by the following method.

[0024] (Method of measuring intrinsic viscosity) Approximately 20 mg of 1,4-methyl-1-pentene·α-olefin copolymer was dissolved in 15 ml of decalin to prepare a decalin solution, and the specific viscosity (η sp ) is measured. 2. Add 5 ml of decalin to the decalin solution to dilute it, and measure the specific viscosity (η sp ) is measured in the same manner. 3. The increase in viscosity per unit concentration (C) of 4-methyl-1-pentene·α-olefin copolymer, i.e., the reduced viscosity (η red = η sp / C). 4. Plot the relationship between concentration and reduced viscosity, and calculate the intrinsic viscosity [η] from the intercept when the concentration (C) is extrapolated to 0. Alternatively, calculate the intrinsic viscosity [η] using the following formula (I).

number

[0025] The 4-methyl-1-pentene / α-olefin copolymer (ii) preferably has a melting point (Tm) measured by differential scanning calorimetry (DSC) of 200°C or less or substantially no melting point, more preferably has a melting point of 110 to 180°C or substantially no melting point, and further preferably has a melting point of less than 160°C or substantially no melting point. The melting point (Tm) is determined by the C 2-20 The amount of the α-olefin can be adjusted by changing the blending ratio of the α-olefin. The melting point (Tm) can be measured by differential scanning calorimetry as described below.

[0026] (Differential Scanning Calorimetry) Approximately 5 mg of 1,4-methyl-1-pentene·α-olefin copolymer is placed in an aluminum container, sealed with a lid, and used as the measurement sample. 2. Place the measurement sample in the measuring device, heat it up to 290°C at a heating rate of 10°C / min, hold it at 290°C for 5 minutes, and cool it down to -50°C at a cooling rate of 10°C / min. 3. The melting point (Tm) is calculated from the temperature at the apex of the endothermic peak due to melting in the obtained DSC curve.

[0027] In a DSC curve, the area of ​​the endothermic peak is the enthalpy of fusion (ΔH f ) If there is no melting point, no endothermic peak is observed, so the area of ​​the endothermic peak, i.e., the enthalpy of fusion (ΔH f ) is not required. In the present invention, "substantially no melting point" means that there is substantially no melting enthalpy in the DSC curve. f) may be 0 to 10 J / g, and preferably 0 to 5 J / g.

[0028] The 4-methyl-1-pentene / α-olefin copolymer preferably has a density of (iii) 820 to 850 kg / m 3 , more preferably 825 to 850 kg / m 3 , more preferably 825 to 845 kg / m 3 , particularly preferably 825 to 840 kg / m 3 The density is the C 2-20 The type of α-olefin, or 4-methyl-1-pentene and C 2-20 The amount of the α-olefin can be adjusted by changing the blending ratio of the α-olefin. The density can be measured by a method in accordance with JIS K7112.

[0029] The 4-methyl-1-pentene·α-olefin copolymer (iv) has a molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) of preferably 1.0 to 3.5, more preferably 1.3 to 3.0, and even more preferably 1.5 to 2.5. The molecular weight distribution (Mw / Mn) can be adjusted by the type of polymerization catalyst used in preparing the copolymer. The molecular weight distribution (Mw / Mn) can be determined by measuring the mass average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography as described below.

[0030] (Gel Permeation Chromatography) 1. The column temperature was set to 140°C, and the mobile phase was made of o-dichlorobenzene and 0.025% by mass of an antioxidant (dibutylhydroxytoluene), and the flow rate was 1.0 mL / min. The concentration of 2.4-methyl-1-pentene·α-olefin copolymer is adjusted to 15 mg / 10 mL, 500 μL is injected, and detection is performed using a differential refractometer.

[0031] The 4-methyl-1-pentene / α-olefin copolymer (v) has a melt flow rate (MFR) in accordance with JIS K7210 of preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably 0.5 to 30 g / 10 min. From the viewpoint of fluidity when forming filaments, it is suitable that the melt flow rate is within the above range. The melt flow rate is a value measured in accordance with JIS K7210 at 230° C. under a load of 2.16 kg.

[0032] The method for producing the 4-methyl-1-pentene-α-olefin copolymer is not particularly limited, and it can be produced by various methods. For example, 4-methyl-1-pentene and C 2-20 It can be produced by polymerizing an α-olefin.

[0033] The filaments constituting the toy hair according to the present invention comprise low-density polyethylene (hereinafter sometimes referred to as "polyethylene" or "polymer (II)"). The low density polyethylene is not particularly limited, and includes, for example, linear low density polyethylene.

[0034] The low-density polyethylene has a melt flow rate (MFR) of preferably 0.1 to 60 g / 10 min, more preferably 1 to 40 g / 10 min. From the viewpoint of fluidity when forming filaments, it is suitable that the melt flow rate is within the above range. The melt flow rate is a value measured at 190° C. under a load of 2.16 kg in accordance with JIS K6922-2.

[0035] The low density polyethylene may be used alone or in combination of two or more kinds.

[0036] As mentioned above, the filaments of the present invention have shape memory properties. This is believed to be due to the side chain moieties (-CH2-CH(CH3)2) in the structural units (polymethylpentene) derived from 4-methyl-1-pentene in the 4-methyl-1-pentene-α-olefin copolymer, and it is believed that the good shape memory properties are expressed by the side chain moieties being intricately entangled with each other to form pseudo-crosslinking points.

[0037] In 4-methyl-1-pentene-α-olefin copolymer (polymer I), a network structure is formed starting from the pseudo-crosslinking points. In the temperature range below the glass transition temperature of polymer I, the thermal motion (micro-Brownian motion) of the molecular chains is restricted, and the elastic modulus is high due to energy elasticity, and the filament exhibits rigid properties. When the temperature rises and reaches a temperature range above the glass transition temperature of polymer I, the elastic modulus decreases due to entropy elasticity based on micro-Brownian motion, and the filament exhibits viscous properties, making it possible to deform the filament by applying external stress. If the filament is cooled to a temperature range below the glass transition temperature of polymer I while maintaining the state in which it has been deformed by applying external stress, the micro-Brownian motion of the molecular chains is restricted again, the elastic modulus increases, and the filament can be fixed in the deformed state. This state is maintained even if the external stress is removed. When the temperature reaches a temperature range above the glass transition temperature of polymer I again, the elastic modulus decreases due to micro-Brownian motion, and the crosslinking points move to their initial positions to return to a stable state, making it possible to restore the filament to its original shape. In other words, the shape memory properties of the filaments according to the present invention are related to the glass transition temperature of the 4-methyl-1-pentene / α-olefin copolymer, and the glass transition temperature of the 4-methyl-1-pentene / α-olefin copolymer can be regarded as the temperature at which the filaments can be deformed.

[0038] Low-density polyethylene improves the spinnability of filaments without impairing shape memory, and also has the effect of suppressing filament fusion when 4-methyl-1-pentene-α-olefin copolymer transitions to a viscous state at temperatures above its glass transition temperature. This makes it easier to avoid problems such as sticking when filaments come into close contact with each other. This is presumably because the branched structure of low-density polyethylene is prone to entanglement with the aforementioned side chains, and the properties of low-density polyethylene are unlikely to change even at temperatures above the glass transition temperature of 4-methyl-1-pentene-α-olefin copolymer. Therefore, by using a resin composition that combines 4-methyl-1-pentene / α-olefin copolymer and low-density polyethylene, it is possible to obtain filaments that have shape memory and excellent spinnability in which fusion between filaments is suppressed, and this can be used as toy hair that has excellent marketability.

[0039] The filaments constituting the toy hair are produced in the form of monofilaments or multifilaments by melt spinning using a melt spinning device or the like. The form of the filament is not particularly limited, but a form having a region in which 4-methyl-1-pentene / α-olefin copolymer (polymer I) and low-density polyethylene (polymer II) are melt-integrated is preferred because it is easy to exert the effect of suppressing the tackiness of the filament by the low-density polyethylene. For example, there can be mentioned (1) a form in which polymer (I) and polymer (II) are melt-blended and integrated, (2) a core-sheath type form in which a part or all of the outer periphery of a core made of polymer (I) is covered by a sheath made of polymer (II), and (3) a side-by-side type form in which polymer (I) and polymer (II) are joined in parallel. In the case of a core-sheath type, it is preferable that the entire outer periphery of the core is covered with the sheath. Among these, the filament form in which the filaments are integrated by melt blending is preferred, since this easily achieves both shape memory and suppression of fusing of the filaments.

[0040] 4-Methyl-1-pentene·α-olefin copolymer and low-density polyethylene form a mixture in which the polymers are compatible with each other by melt blending. Therefore, it is possible to adjust the glass transition temperature of the mixture by adjusting the blending ratio of each polymer. Here, "compatible with each other" includes not only the state in which the polymers are completely compatible with each other, but also the state in which they are partially compatible with each other (a state in which one polymer is dispersed in the other polymer and a state in which the polymers are compatible with each other are mixed). That is, in the case of a form in which 4-methyl-1-pentene·α-olefin copolymer and low-density polyethylene are melt-blended, the shape memory properties of the filament are affected by the glass transition temperature of the mixture of polymer (I) and polymer (II), and the glass transition temperature of the mixture can be regarded as the deformable temperature of the filament.

[0041] The glass transition temperature (hereinafter sometimes referred to as "Tg") of 4-methyl-1-pentene·α-olefin copolymer (Polymer I) or a mixture of 4-methyl-1-pentene·α-olefin copolymer and low-density polyethylene can be measured by differential scanning calorimetry (DSC) as described below in accordance with the method for measuring transition temperatures of plastics specified in JIS K 7121.

[0042] (Differential Scanning Calorimetry) 1. Approximately 5 mg of polymer I or the mixture is placed in an aluminum container, sealed with a lid, and used as a measurement sample. 2. Place the measurement sample in the measurement device and hold it at -20°C until the device stabilizes. Then, heat it up to 70°C at a rate of 20°C / min (1st heating) and hold it at 70°C for 5 minutes. 3. The temperature is decreased to -20°C at a rate of 20°C / min, and the sample is kept at -20°C for 5 minutes. 4. Heat again to 70°C at a rate of 20°C / min. (2nd heating) 5. The glass transition temperature is determined from the change in the baseline in the DSC curve obtained from the 2nd heating.

[0043] The glass transition temperature of the 4-methyl-1-pentene / α-olefin copolymer (polymer I) or the glass transition temperature of a mixture of the 4-methyl-1-pentene / α-olefin copolymer and the low-density polyethylene is preferably in the temperature range of 0 to 70°C, more preferably 10 to 60°C, even more preferably 20 to 50°C, and particularly preferably 20 to 40°C. Filaments having a glass transition temperature of polymer I or the mixture within the above temperature range can be repeatedly deformed into any shape, fixed and maintained in the deformed shape, and restored to the original shape by applying commonly used conventional heating means, cooling means, or deformation means.

[0044] Heating means include heat from the hands, medium such as hot water, steam or laser light, hot air devices using an electric resistance heating element (Nichrome wire, positive characteristic resistance heating element, etc.) as a heat source, box-type heating devices, hair dryers, etc. The cooling means may be a device that uses a refrigerant such as cold water, a cold air device that uses a Peltier element as a cold heat source, a box-type cooling device, a freezer, a refrigerator, or a cooling agent. The deformation means can be by hand, trowel, or various shaped jigs. Examples of each can be given. In particular, when 4-methyl-1-pentene / α-olefin copolymer or a mixture of 4-methyl-1-pentene / α-olefin copolymer and low-density polyethylene has a glass transition temperature in the temperature range of 20 to 40°C, it becomes possible to easily deform it into any shape, fix and maintain the deformed shape, and restore it to its original shape by applying everyday heat or cold (e.g., heat from fingers, hot water, iced water, etc.) at or near the temperature range of the living environment.

[0045] In the filament according to the present invention, the mass ratio of the 4-methyl-1-pentene / α-olefin copolymer to the low-density polyethylene is preferably 20:80 to 99:1, more preferably 25:75 to 85:15, and even more preferably 30:70 to 80:20. By having the mass ratio within the above range, it becomes easy to achieve both suppression of fusibility of the filament and high degree of shape memory property.

[0046] The filaments according to the present invention can be deformed into shapes such as circles, ellipses, squares, rectangles, hearts, stars, spirals, and spirals by applying an external stress and bending the filaments in a temperature range equal to or higher than the glass transition temperature of the 4-methyl-1-pentene / α-olefin copolymer (polymer I) or a mixture of the 4-methyl-1-pentene / α-olefin copolymer and low-density polyethylene. In addition, the filament length can be changed by applying an external stress to elongate the polymer in a temperature range above the glass transition temperature of the 4-methyl-1-pentene·α-olefin copolymer (polymer I) or a mixture of the 4-methyl-1-pentene·α-olefin copolymer and low-density polyethylene.

[0047] Specifically, a filament of a certain length (initial length) can be elongated by applying an external stress in a temperature range equal to or higher than the glass transition temperature of the polymer I or the mixture, and when it is elongated to less than twice its original length (preferably less than 1.5 times its original length), it can be fixed in the elongated state by cooling it to a temperature range below the glass transition temperature of the polymer I or the mixture. This state is maintained even after the external stress is removed. When the temperature again reaches a temperature range equal to or higher than the glass transition temperature of the polymer I or the mixture, the filament shrinks and can be restored to its initial length. On the other hand, when the filament is stretched to twice its original length or more, it can be fixed in the stretched state by cooling to a temperature range below the glass transition temperature of polymer I or the mixture. This state is maintained even after the external stress is removed. When the temperature reaches a range above the glass transition temperature of polymer I or the mixture again, the filament shrinks, but remains longer than its initial length and does not return to its initial length. That is, when the filament is stretched to a length less than twice its initial length, it will return to its initial length when it is contracted from the stretched state, and this can be repeated. When the filament is stretched to a length more than twice its initial length, it will remain longer than its initial length even when it is contracted from the stretched state, and will not return to its initial length. In this case, it can be restored to its original state (initial length) by cutting it with scissors or the like. Therefore, in the toy using the filament according to the present invention as hair, when the hair is stretched to a length less than a certain ratio of the initial length, the hair can be repeatedly stretched and contracted to freely change the length of the hair. Also, when the hair is stretched to a length equal to or greater than a certain ratio of the initial length, the hair can be irreversibly lengthened or cut with scissors or the like to change the length of the hair to any desired length.

[0048] The filament according to the present invention has an average outer diameter in the range of 0.2 to 3 mm, preferably 0.5 to 2 mm. The average outer diameter corresponds to the average of the outer diameters at a plurality of points on a single filament. The outer diameter can be calculated, for example, by image analysis software or a planimeter based on a cross-sectional photograph of the filament taken by an optical microscope or an electron microscope. If the cross-sectional shape of the filament is not circular, the outer diameter is the diameter of the circle when the cross-sectional area is taken as the area of ​​a circle. Filaments having a desired outer diameter or average outer diameter can be obtained by appropriately adjusting conditions such as temperature and speed in the process of extruding the resin composition forming the filaments from a spinneret and drawing it when producing the filaments using a melt spinning device. If the average outer diameter is less than 0.2 mm, the filaments tend to tangle when the shape of the filaments is changed, which can make maintenance difficult. On the other hand, if the average outer diameter exceeds 3 mm, the filaments become too thick and it becomes difficult to exhibit the properties of hair.

[0049] When the average outer diameter is 0.2 to 0.5 mm, the filament can be applied to toys such as dolls as toy hair by using a hair implantation sewing machine, or by fixing the end of the filament using a fixing piece capable of bundling multiple filaments and then fixing the fixing piece to the part of the toy where the hair will be implanted, for example. When the average outer diameter is 0.5 to 1.5 mm, the filament can be applied to toys such as dolls as toy hair by, for example, using a fixing piece capable of bundling multiple filaments to fix a part of the filament and then fixing the fixing piece to the part of the toy where the hair is to be implanted, or by interposing the filament between metal wires, twisting the metal wires to fix the filament to the metal wires, and then fixing the metal wire to the part of the toy where the hair is to be implanted. When the average outer diameter is 1 to 3 mm (preferably 1.5 to 3 mm), in addition to the method of fixing the filament to the part of the toy to be implanted as toy hair using the above-mentioned fixing piece or metal wire, the filament can be applied to toys such as dolls as toy hair by molding it integrally with the toy (for example, the head or scalp of a doll).

[0050] The cross-sectional shape of the filament can be exemplified by circular shapes such as a perfect circle or an ellipse; polygonal shapes such as a trilobal shape, a triangle, a square, a pentagon, a star, and a Y-shape; however, from the viewpoint of spinnability and processability, the cross-sectional shape is preferably a circle. When the filament has a core-sheath type configuration, when the cross section of the hair is observed, the core and sheath do not need to be arranged concentrically (a concentric core-sheath type), and the core and sheath may be heterocentric in that the centers of the core and sheath are different.

[0051] The filaments according to the invention can be colored with a coloring agent. Examples of colorants include general dyes, fluorescent dyes, general pigments, glittering pigments, fluorescent pigments, phosphorescent pigments, thermochromic materials, photochromic materials, etc. In addition, resin particles containing these colorants and microencapsulated pigments encapsulating these colorants can also be used as colorants.

[0052] Examples of thermochromic materials include a thermochromic composition consisting of at least (i) an electron-donating color-forming organic compound and (ii) an electron-accepting compound, and a thermochromic composition (reversible thermochromic composition) consisting of at least component (i), component (ii), and (iii) a reaction medium that determines the temperature at which the color reaction of components (i) and (ii) occurs. Examples of photochromic materials include photochromic compounds such as spirooxazine derivatives, spiropyran derivatives, naphthopyran derivatives, and diarylethene derivatives, and photochromic compositions (reversible photochromic compositions) composed of at least these photochromic compounds and oligomers.

[0053] As the reversible thermochromic composition, a reversible thermochromic composition of the heat-discoloring type having a relatively small hysteresis width (ΔH) (ΔH=1 to 7°C) described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, etc. can be used. The heat-discoloring type means that the composition is decolored by heating and colored by cooling. This reversible thermochromic composition discolors around a certain temperature (discoloration point), and exhibits a discolored state in a temperature range above the high-temperature discoloration point and a colored state in a temperature range below the low-temperature discoloration point. Of the two states, only one specific state exists in the room temperature range, and the other state is maintained while the heat or cold required to manifest that state is applied, but returns to the state that it exhibits in the room temperature range when the application of heat or cold is removed (see FIG. 1).

[0054] As the reversible thermochromic composition, a heat-discolorable reversible thermochromic composition having a large hysteresis width (ΔH=8 to 80° C.) described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, etc. can be used. The heat-discolorable type means that the color disappears when heated and the color appears when cooled. This reversible thermochromic composition changes color along a path that is significantly different when the temperature is increased from a lower temperature side than the color-changing temperature range than when the temperature is decreased from a higher temperature side than the color-changing temperature range, and has color memory in a specific temperature range [the temperature range between the color-changing onset temperature t2 and the color-fading onset temperature t3 (the temperature range in which two phases are essentially maintained)] in which the color is developed in a temperature range below the complete color-developing temperature t1, or the color is decolorized in a high temperature range above the complete color-fading temperature t4 (see Figure 2).

[0055] As the reversible thermochromic composition, a heat-coloring type reversible thermochromic composition using a gallic acid ester, as described in JP-B-51-44706, JP-A-2003-253149, etc., can also be used. The heat-coloring type means that the color develops when heated and the color disappears when cooled (see FIG. 3).

[0056] When a colorant is used as the colorant, a reversible thermochromic material such as a reversible thermochromic composition, a microencapsulated pigment encapsulating a reversible thermochromic composition (hereinafter sometimes referred to as a "reversible thermochromic microencapsulated pigment"), or a resin particle containing a reversible thermochromic composition (hereinafter sometimes referred to as a "reversible thermochromic resin particle"); a reversible photochromic material such as a reversible photochromic composition, a microencapsulated pigment encapsulating a reversible photochromic composition (hereinafter sometimes referred to as a "reversible photochromic microencapsulated pigment"), or a resin particle containing a reversible photochromic composition (hereinafter sometimes referred to as a "reversible photochromic resin particle"), is used, a reversible color change can be brought about in the filament by a temperature change or irradiation with light. In addition, by using these color-changing colorants in combination with non-color-changing colorants such as general dyes or general pigments, it is possible to cause the filament to undergo an alternating color change from color (1) to color (2).

[0057] It is preferable to use the reversible thermochromic composition or the reversible photochromic composition as a microencapsulated pigment by encapsulating it in a microcapsule, because by encapsulating it in a microcapsule, a chemically and physically stable pigment can be formed, and the reversible thermochromic composition or the reversible photochromic composition can be kept in the same composition under various conditions of use, and can exert the same action and effect.

[0058] Microencapsulation can be achieved by known methods such as an isocyanate-based interfacial polymerization method, an in situ polymerization method such as a melamine-formaldehyde-based method, a liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melting dispersion cooling method, an air suspension coating method, and a spray drying method, and can be appropriately selected depending on the application.

[0059] Depending on the purpose, a secondary resin film may be further provided on the surface of the microcapsules to impart durability or to modify the surface properties for practical use.

[0060] The reversible thermochromic microcapsule pigment or the reversible photochromic microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1, and by having the mass ratio of inclusions to wall film within the above range, it is possible to prevent a decrease in color density and clarity during color development. More preferably, the mass ratio of inclusions to wall film is 6:1 to 1:1.

[0061] A colored filament can be obtained by incorporating a colorant into a resin composition from which the filament is formed. Alternatively, a colored filament can be obtained by printing or applying a liquid composition such as a printing ink or paint, which is prepared by dispersing a colorant in a vehicle containing a binder resin and, if necessary, various additives, onto the surface of the filament by various printing or application means to provide a colored layer.

[0062] The blending ratio of the colorant to the total mass of the resin composition forming the filament is not particularly limited, but is preferably 0.01 to 30 mass%, more preferably 0.1 to 20 mass%, and even more preferably 1 to 15 mass%. When the colorant is the above-mentioned discolorable colorant, the blending ratio of the colorant to the total mass of the resin composition forming the filament is not particularly limited, but is preferably 0.1 to 30 mass%, more preferably 1 to 20 mass%, and even more preferably 5 to 15 mass%. By having the blending ratio of the colorant within the above range, the dispersion stability of the colorant in the resin composition is excellent, and filaments having the desired color density can be easily obtained.

[0063] The blending ratio of the colorant to the total mass of the liquid composition is not particularly limited, but is preferably 0.01 to 50 mass %, more preferably 0.1 to 30 mass %, and even more preferably 1 to 15 mass %. When the colorant is the above-mentioned discolorable colorant, the blending ratio of the colorant to the total mass of the liquid composition is not particularly limited, but is preferably 0.5 to 40 mass %, more preferably 1 to 30 mass %, and even more preferably 5 to 15 mass %. When the blending ratio of the colorant is within the above range, the dispersion stability of the colorant in the vehicle is excellent, and a colored layer having a desired color density can be easily obtained.

[0064] When a reversible thermochromic microencapsulated pigment or a reversible photochromic microencapsulated pigment is used as a colorant, the average particle size of the microencapsulated pigment is preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm, and even more preferably 0.5 to 10 μm. If the average particle size exceeds 30 μm, the pigment is likely to lack dispersion stability and processability when blended into a resin composition or a liquid composition. On the other hand, if the average particle size is less than 0.1 μm, it is difficult to exhibit high-concentration color development.

[0065] The average particle size was determined by determining the particle region using image analysis particle size distribution measurement software (manufactured by Mountec Co., Ltd., product name: MacView), calculating the projected area equivalent circle diameter (Heywood diameter) from the area of ​​the particle region, and measuring the average particle size of particles equivalent to a sphere of equal volume using this value. In addition, if the particle size of all or the majority of the particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to an equal volume sphere by the Coulter method using a particle size distribution analyzer (product name: Multisizer 4e, manufactured by Beckman Coulter, Inc.). Furthermore, the volumetric particle size and average particle size may be measured using a calibrated laser diffraction / scattering particle size distribution analyzer (manufactured by HORIBA, Ltd., product name: LA-300) based on values ​​measured using the above software or a measuring device using the Coulter method.

[0066] The filament according to the present invention may also contain various additives as required. Examples of additives include flame retardants, dispersants such as waxes, light stabilizers such as ultraviolet absorbers, antioxidants, antiaging agents, singlet oxygen quenchers, ozone quenchers, superoxide anion quenchers, ozone quenchers, visible light absorbers, and infrared absorbers, fluorescent whitening agents, surfactants, antistatic agents, water repellents, antifungal agents, insect repellents, phthalic acid-based, aliphatic dibasic acid ester-based, phosphate ester-based, and epoxy-based plasticizers such as phenol-based and trimellitic acid-based plasticizers, and lubricants. Furthermore, in order to improve processability and physical properties, calcium carbonate, magnesium carbonate, titanium oxide, talc, etc. may be added.

[0067] Since the filament according to the present invention can be deformed into any shape by the application of heat or cold, fixed and maintained in the deformed shape, and restored to its original shape, it is preferable to use a thermochromic material that changes color with temperature change as the colorant. Since the color can be changed repeatedly, the thermochromic material is preferably the reversible thermochromic material described above, and a reversible thermochromic microencapsulated pigment is more preferable.

[0068] The glass transition temperature (Tg) of the 4-methyl-1-pentene·α-olefin copolymer (polymer I) or the mixture of the 4-methyl-1-pentene·α-olefin copolymer and low-density polyethylene is preferably approximately the same as the complete coloring temperature t1 or complete decolorization temperature t4 of the reversible thermochromic material (reversible thermochromic composition). This allows the temperature at which the filament changes from a rigid state to a viscous state to the temperature at which the color-changing colorant changes color to be synchronized, and it is possible to determine whether the filament has reached a temperature at which it can be deformed by the color change of the color-changing colorant.

[0069] Here, "substantially the same" includes temperatures T and t1, or temperatures T and t4 being exactly the same, where T is the glass transition temperature. In the present invention, the difference between temperatures T and t1 (Δt1=T-t1) is 0 or more and 2 or less, or the difference between temperatures T and t4 (Δt4=t4-T) is 0 or more and 2 or less. In other words, "substantially the same" in the present invention means that 0≦Δt1≦2 or 0≦Δt4≦2 is satisfied. With respect to Δt1 or Δt4, preferably, 0≦Δt1≦1 or 0≦Δt4≦1, more preferably, 0≦Δt1<1 or 0≦Δt4<1, and further preferably, Δt1=0 (T=t1) or Δt4=0 (T=t4).

[0070] An example is shown below in which the glass transition temperature of polymer I or the mixture is the same as the complete color development temperature t1 of the reversible thermochromic material, that is, Δt1=0 (T=t1). When the filament is heated to a temperature t4 or higher, the reversible thermochromic material loses its color and the filament changes color. At this time, the filament is flexible and can be deformed into any shape by application of an external force. After the filament is deformed into any shape by application of an external force, if it is cooled below temperature T (temperature t1) while the external force is still applied, the reversible thermochromic material develops color and the filament changes color, and the filament can be fixed in the deformed shape even if the external force is removed. Therefore, it can be determined that the properties of the filament have changed and the temperature at which the filament can be maintained in the deformed shape without application of an external force has been reached by the change from the decolorized state of the reversible thermochromic material to the colored state, i.e., the color change of the filament.

[0071] An example will be given below in which the glass transition temperature of polymer I or the mixture is the same as the complete decolorization temperature t4 of the reversible thermochromic material, that is, Δt4=0 (T=t4). When the colored filament is heated to temperature T (temperature t4) or higher, the reversible thermochromic material loses its color and the filament changes color, and the filament can be deformed into any shape by application of an external force. Therefore, it can be determined that the properties of the filament have changed and the temperature at which the filament can be deformed into any shape by application of an external force has been reached by the change of the reversible thermochromic material from the colored state to the decolored state, i.e., the color change of the filament.

[0072] The glass transition temperature of polymer I or the mixture is between the complete color development temperature t1 and the complete decolorization temperature t4 of the reversible thermochromic material, and preferably satisfies at least one of Δt1 ≧ 5 or Δt4 ≧ 5, and more preferably satisfies Δt1 ≧ 5 and Δt4 ≧ 5. This makes it possible to determine from the color change of the filament that the temperature has reached a temperature sufficiently higher than the temperature at which the properties of the filament change, and that the filament can be easily deformed into any shape by application of an external force, or that after the filament has been deformed into any shape by application of an external force, the temperature has reached a temperature sufficiently lower than the temperature at which the properties of the filament change, and that the deformed shape is well maintained without application of an external force. With respect to Δt1 or Δt4, it is preferable that Δt1≧10 or Δt4≧10.

[0073] An example in which the glass transition temperature of polymer I or the mixture is between the complete coloring temperature t1 and the complete decoloring temperature t4 of the reversible thermochromic material and satisfies Δt1≧5 and Δt4≧5 is shown below. The filament is in a colored state at temperature T, and when heated to temperature t4 or higher, the reversible thermochromic material loses its color, causing the filament to change color, and the filament can be easily deformed into any shape by application of an external force. Therefore, it can be determined from the change from the colored state to the decolored state of the reversible thermochromic material, i.e., the color change of the filament, that the temperature has reached a level sufficiently higher than the temperature at which the properties of the filament change, and the filament can be easily deformed into any shape by application of an external force. When the filament is deformed into an arbitrary shape by application of an external force and then cooled to a temperature below t1 while the external force is still applied, the reversible thermochromic material develops color and the color of the filament changes, and the deformed shape of the filament is well maintained even after the external force is removed. Therefore, it can be determined by the change from the decolorized state of the reversible thermochromic material to the colored state, i.e., the color change of the filament, that the temperature has reached a temperature sufficiently lower than the temperature at which the properties of the filament change, and the deformed shape of the filament is well maintained without the application of an external force. Here, when the filament that has been heated to a temperature t4 or higher and deformed into an arbitrary shape is cooled to a temperature range exceeding temperature t1 and lower than temperature T while applying an external force, the filament can be maintained in the deformed shape without applying an external force while the reversible thermochromic material is in the decolorized state. As long as it is not cooled to a temperature t1 or lower, the filament can be repeatedly deformed into an arbitrary shape and maintained in the deformed shape while the reversible thermochromic material is in the decolorized state. Also, when cooled to a temperature t1 or lower, the reversible thermochromic material becomes in a colored state. When heated to a temperature range exceeding temperature T and lower than temperature t4, the filament can be deformed into an arbitrary shape by applying an external force while the reversible thermochromic material is in the colored state. As long as it is not heated to a temperature t4 or higher, the filament can be repeatedly deformed into an arbitrary shape and maintained in the deformed shape while the reversible thermochromic material is in the colored state. In other words, the reversible thermochromic material can be selectively maintained in either a colored state or a decolored state, while the filament can be repeatedly deformed into any shape and the deformed shape can be maintained.

[0074] The toy hair according to the present invention has filaments that have shape memory, have a good texture, and are prevented from fusing together, so that toys equipped with toy hair made of these filaments have excellent marketability. The toy is not particularly limited, but examples thereof include doll toys, animal-shaped toys, and their accessories, and an example of the accessories is hair extensions for dolls. The toy hair can be used by implanting it in the head, face, body, limbs, etc. of the doll toy or animal-shaped toy.

[0075] Further examples of products using the filament according to the present invention include the following. (1) Clothing Coverings such as T-shirts, sweatshirts, blouses, dresses, swimsuits, raincoats, skiwear, etc.; footwear such as shoes and shoelaces; cloth personal items such as towels, handkerchiefs, furoshiki, etc.; gloves; ties; hats; ribbons; scarves; mufflers, etc. (2) Indoor decorations Curtains, curtain strings, table hangings, rugs, cushions, carpets, rugs, upholstery, seats, mats, etc. (3) Decorations False eyelashes, beards, eyebrows, wigs, hair extensions, etc. (4)Other Calendars, cards, picture books, bags, embroidery thread, fishing tackle, coasters, wallets, teaching materials, etc. EXAMPLES

[0076] The following examples are given, but the present invention is not limited thereto. In the examples, "parts" refers to "parts by mass" unless otherwise specified.

[0077] In the following Examples and Comparative Examples, the average outer diameter of the filaments was determined by the following method.

[0078] [Measuring the average outer diameter] The average outer diameter of the filament was determined by cutting a 10 cm filament into 5 equal parts, observing the cut cross sections of each of the 5 cut filaments with an optical electron microscope, and determining the maximum outer diameter. The average outer diameter of these filament outer diameters (maximum outer diameters) was calculated and determined as the average outer diameter. A straight line was drawn connecting any two points on the outer circumference of the cut cross section image of the filament observed with an optical microscope, and the point where the length of the straight line was maximum was identified, and the length of the straight line at that point was measured and determined as the maximum outer diameter of the filament.

[0079] Example 1 A resin composition for the filaments was prepared by melt-blending 20 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absotomer EP-1001) and 80 parts of low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., product name: Novatec LD LJ803) at 200°C. This resin composition was fed to a general-purpose melt spinning apparatus, spun at 200° C. and stretched to obtain monofilaments having an average outer diameter of 0.8 mm.

[0080] The filaments of Examples 2 to 6 were obtained in the same manner as Example 1, except that the materials and blending amounts were changed to those shown in Table 1. The average outer diameter of each of the filaments of Examples 2 to 6 was 0.8 mm.

[0081] Example 7 A resin composition for forming the filaments was prepared by melt-blending at 200°C 75 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absortomer EP-1001), 5 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absortomer EP-1013), and 20 parts of low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., product name: Novatec LD LJ803). This resin composition was fed to a general-purpose melt spinning device, spun at 200° C. and stretched to obtain monofilaments having an average outer diameter of 0.9 mm.

[0082] Example 8 A resin composition for forming the filaments was prepared by melt-blending at 200°C 76 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absotomer EP-1001), 19 parts of low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., product name: Novatec LD LJ803), 0.2 parts of a general pink pigment, and 4.8 parts of a reversible thermochromic microencapsulated pigment. This resin composition was fed to a general-purpose melt spinning apparatus, spun at 200° C. and stretched to obtain monofilaments having an average outer diameter of 1.4 mm. When this filament was heated to above 38°C, the microencapsulated pigment completely disappeared, revealing the pink color of the regular pigment; when it was cooled to below 14°C, the microencapsulated pigment completely developed, revealing a purple color that was a mixture of the blue color of the microencapsulated pigment and the pink color of the regular pigment; the color changed reversibly with temperature change.

[0083] The above-mentioned reversible thermochromic microencapsulated pigment was prepared as follows. A reversible thermochromic composition consisting of 1 part of 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of cyclohexylmethyl stearate as component (C) was added to a mixed solution consisting of 35 parts of aromatic isocyanate prepolymer as a wall film material and 40 parts of cosolvent, and then emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution. After continuing to stir while heating, 2.5 parts of water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. A reversible thermochromic microcapsule pigment with an average particle size of 8 μm was obtained from the above microcapsule dispersion by centrifugation. The reversible thermochromic microencapsulated pigment had a complete color-developing temperature t1 of 14°C and a complete decolorization temperature t4 of 38°C, and reversibly changed from blue to colorless due to temperature change.

[0084] Comparative Example 1 100 parts of low-density polyethylene (product name: Novatec LD LJ803, manufactured by Japan Polyethylene Co., Ltd.) was fed to a general-purpose melt spinning device, spun at 200°C, and stretched to obtain monofilaments with an average outer diameter of 0.8 mm.

[0085] Comparative Example 2 100 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absotomer EP-1001) was fed into a general-purpose melt spinning device, spun at 200°C, and stretched to obtain monofilaments with an average outer diameter of 0.8 mm.

[0086] Comparative Example 3 A resin composition for the filaments was prepared by melt-blending 80 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absotomer EP-1001) and 20 parts of high-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., product name: Novatec HD H590N) at 200°C. This resin composition was fed to a general-purpose melt spinning device, spun at 200° C. and stretched to obtain monofilaments having an average outer diameter of 0.8 mm.

[0087] Comparative Example 4 A resin composition for the filaments was prepared by melt-blending 80 parts of 4-methyl-1-pentene·α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absotomer EP-1001) and 20 parts of polypropylene (manufactured by SunAllomer Co., Ltd., product name: SunAllomer PM600A) at 200°C. This resin composition was fed to a general-purpose melt spinning device, spun at 200° C. and stretched to obtain monofilaments having an average outer diameter of 0.8 mm.

[0088] [Table 1]

[0089] The materials in Table 1 are explained according to the note numbers. (1) Mitsui Chemicals, Inc., Product name: Absotomer EP-1001 The blending ratio of structural units derived from 4-methyl-1-pentene: 72 mol%, the blending ratio of structural units derived from propylene: 28 mol% ·Intrinsic viscosity [η]: 1.4dL / g Melting point (Tm): None ·Density: 840kg / cm 3 ·Molecular weight distribution (Mw / Mn): 2.1 Melt flow rate (MFR): 10g / 10min Glass transition temperature (Tg): 30℃ (2) Mitsui Chemicals, Inc., product name: Absortomer EP-1013 The blending ratio of structural units derived from 4-methyl-1-pentene: 85 mol%, the blending ratio of structural units derived from propylene: 15 mol% ·Intrinsic viscosity [η]: 1.5dL / g Melting point (Tm): 130℃ ·Density: 838kg / cm 3 ·Molecular weight distribution (Mw / Mn): 2.0 Glass transition temperature (Tg): 40℃ Melt flow rate (MFR): 10g / 10min (3) Product name: Novatec LD LJ803, manufactured by Japan Polyethylene Co., Ltd. Melt flow rate (MFR): 22g / 10min (4) Product name: Novatec LD LF441A, manufactured by Japan Polyethylene Co., Ltd. Melt flow rate (MFR): 2g / 10min (5) Manufactured by Japan Polyethylene Co., Ltd., Product name: Novatec HD HJ590N Melt flow rate (MFR): 40g / 10min (6) Sanallomer Co., Ltd., Product name: Sanallomer PM600A Melt flow rate (MFR): 7.5g / 10min (7) Pink general pigment (8) Reversible thermochromic microencapsulated pigment

[0090] [Spinnability test] The appearance of the filaments produced under the spinning conditions described in the Examples and Comparative Examples was visually confirmed, and the spinnability of the filaments was evaluated according to the following criteria. The test results are shown in Table 2 below. A: The filament had a uniform outer diameter and looked good. B: The filament had many thick and thin areas and had an uneven outer diameter.

[0091] [Glass transition temperature measurement] According to the method for measuring the glass transition temperature of plastics specified in JIS K7121, the filaments of Examples 1 to 8 and Comparative Examples 1 to 4 were each cut to a length of 0.5 mm or less to prepare test pieces, and approximately 10 mg of the test pieces were placed in an aluminum container and sealed with a lid to prepare samples for measuring the glass transition temperature. Each measurement sample was set in a differential scanning calorimeter (DSC) (METTLER TOLEDO Co., Ltd., product name: FP900 Thermosystem (FP-85)) and held at -20°C until the device stabilized, then heated from -20°C to 70°C at a heating rate of 20°C / min (1st heating) and held at 70°C for 5 minutes. Next, quenched from 70°C to -20°C at a cooling rate of 20°C / min and held at -20°C for 5 minutes. Again, heated from -20°C to 70°C at a heating rate of 20°C / min (2nd heating) to obtain a DSC curve. The glass transition temperature of each filament was obtained from the DSC curve obtained by the 2nd heating. The glass transition temperatures of each filament are listed in Table 2 below.

[0092] [Weldability test] For each of the filaments of Examples 1 to 8 and Comparative Examples 1 to 4, one end of 20 filaments having a length of 10 cm was fastened with tape to prepare a sample for a fusibility test. The test sample was placed in a thermostatic chamber set at (Tg+10)°C, and a weight of 500g was placed on top. After one minute had passed, the test sample was removed from the thermostatic chamber, and the filament fusion property was evaluated based on the degree of adhesion between the filaments and the ease of peeling, according to the following criteria. The evaluation results are shown in Table 2 below. A: The filaments were not attached to each other, or they were attached but could be easily peeled off. B: The filaments were stuck to each other, but could be peeled off. C: The filaments were tightly attached to each other and difficult to separate. Here, "Tg" in the fusibility test refers to the glass transition temperature of each filament obtained by the above-mentioned glass transition temperature measurement.

[0093] [Shape memory test] Each of the filaments of Examples 1 to 8 and Comparative Examples 1 to 4 was cut to a length of 15 cm to prepare a linear shape memory test sample. The test sample was placed in a thermostatic chamber set at a deformation temperature of (Tg+10)°C, heated for 5 minutes, removed from the thermostatic chamber, and wound around a cylinder with a diameter of 1 cm to deform the test sample into a coil shape. The test sample was immediately placed in a thermostatic chamber set at a fixed temperature of (Tg-10)°C, cooled for 5 minutes to fix the shape. The test sample was then removed from the thermostatic chamber, removed from the cylinder, and immediately placed back in the thermostatic chamber set at (Tg-10)°C. After 5 minutes, the test sample was removed from the thermostatic chamber, and the test sample was evaluated for its ability to maintain its deformed shape (coil shape) (shape retention) based on the inner diameter of the coil produced by the test sample, using the following criteria. The evaluation results are shown in Table 2 below. A: The inner diameter of the coil was 1 cm (equal to the inner diameter of the cylinder), and the test specimen retained the same shape as the deformed shape. B: The inner diameter of the coil was greater than 1 cm and less than 1.5 cm. The test sample changed slightly from its deformed shape, but this was at a level that did not pose a problem in practical use. C: The inner diameter of the coil was greater than 1.5 cm, and the test specimen did not retain the same shape as the deformed shape.

[0094] Next, the coil-shaped test sample after evaluating the shape retention was placed back into the thermostatic chamber set at (Tg+10)° C. After 5 minutes had passed, the test sample was removed from the thermostatic chamber and visually confirmed to see whether the test sample had restored to its original shape (linear shape with a length of 15 cm) (shape restorability), and the shape of the test sample was evaluated according to the following criteria. The evaluation results are shown in Table 2 below. A: The test specimen returned to a straight shape from the deformed shape. B: The test specimen did not return to a straight shape from the deformed shape. Here, "Tg" in the shape memory test refers to the glass transition temperature of each filament obtained by the above-mentioned glass transition temperature measurement. In addition, products that were rated "C" for shape retention were not tested for shape recovery.

[0095] [Table 2] *Since the glass transition temperature of the filament of Comparative Example 1 could not be determined, the fusibility test and the shape memory test were not performed.

[0096] Application example 1 Making doll toys Using 100 filaments of Example 4 cut to a length of 300 mm, five filaments of each type were bent from the center and fixed pieces were attached to the bent parts. The fixed pieces were then embedded in the head of a doll as hair and combined with the torso to create a doll toy. The hair of the above doll toy was initially straight. When the straight hair was wrapped around cylindrical hair curlers with a diameter of 9 mm while immersed in warm water at 39°C, and then immersed in cold water at 15°C and the curlers were removed, the hair became curled to the same diameter as the curlers, and maintained that shape unless an external force was applied. Furthermore, when the hair was stretched out in a straight line and immersed again in hot water at 39°C and then in cold water at 15°C, the hair returned to its original straight line and could easily be restored to its original state. The bending deformation described above could be repeated. In addition, when hair in its initial straight shape was immersed in warm water at 39°C and stretched by hand to a length of 420 mm, and then immersed in cold water at 15°C and the external force from the fingers was removed, the hair stretched to 1.4 times its initial length and maintained that shape unless an external force was applied. Furthermore, when the hair was again immersed in warm water at 39°C, it restored to its original length (300 mm). When the hair was then straightened with the fingers and immersed in cold water at 15°C, the hair returned to its original straight shape and could easily be restored to its original state. The above-mentioned elongation deformation could be repeated.

[0097] Application example 2 Creation of animal-shaped toys Ten filaments of Example 8 were cut to a length of 150 mm and cooled to below 14°C. Then, hair was attached to the tail of a polyvinyl chloride horse-shaped toy by a conventional method (e.g., a hair-embedding machine) to produce an animal-shaped toy. The hair of the animal-shaped toy described above was initially straight, and at room temperature (e.g., 25°C), it was purple, a mixture of the blue from the microcapsule pigment and the pink from the general pigment. When the straight hair was immersed in warm water at 39°C, the microcapsule pigment completely disappeared and the hair changed from purple to pink. Then, when the hair was wrapped around the outer circumference of a heart-shaped molded body while immersed in warm water, and then removed from the molded body at room temperature (25°C), the hair took on a heart shape and maintained that shape for several minutes. When the hair was immersed in cold water at 10°C, the microcapsule pigment completely developed color and the hair changed from pink to purple. When the hair was again immersed in 39°C water, the microcapsule pigment completely disappeared and the hair changed from purple to pink. When the hair was then left at room temperature (25°C) in a straightened state, it returned to its original straight shape and could be easily restored to its original state. When the hair was then immersed in 10°C water, the microcapsule pigment completely developed color and the hair changed from pink to purple. The bending deformation described above could be repeated. When the hair in its initial straight shape was immersed in warm water at 39°C, the microcapsule pigment completely disappeared and the hair changed from purple to pink. When the hair was stretched to a length of 300 mm by hand while immersed in warm water and then immersed in cold water at 10°C, the microcapsule pigment completely developed color and the hair changed from pink to purple. When the external force of the fingers was removed while the hair was immersed in cold water, the hair was stretched to twice its initial length and maintained that shape unless an external force was applied. When the hair was again immersed in warm water at 39°C, the microcapsule pigment completely disappeared and the hair changed from purple to pink. When the hair was then straightened with the fingers and immersed in cold water at 10°C, the hair returned to a straight shape, but did not return to its original length (150 mm). Although the above-mentioned stretching deformation can be repeated, the hair is stretched beyond a certain ratio, so it does not return to its original length, and the length of the hair becomes irreversible. Therefore, by cutting the lengthened hair with scissors, it is possible to change it to any length or return it to its original state (initial length). [Explanation of symbols]

[0098] t1 full color temperature t2 color development start temperature t3 decolorization start temperature t4 complete color erasure temperature T1 complete decolorization temperature T2 decolorization start temperature T3 color development start temperature T4 full color temperature ΔH Hysteresis width

Claims

1. The constituent units are derived from 4-methyl-1-pentene and C other than 4-methyl-1-pentene. ２－２０ A 4-methyl-1-pentene / α-olefin copolymer comprising a constituent unit derived from an α-olefin, Low-density polyethylene and, It consists of filaments containing and having an average outer diameter of 0.2 to 3 mm. Hair for toys.

2. The toy hair according to claim 1, comprising the 4-methyl-1-pentene-α-olefin copolymer and low-density polyethylene, which are melt-blended together.

3. The toy hair according to claim 1, wherein the mass ratio of the 4-methyl-1-pentene / α-olefin copolymer to low-density polyethylene is 20:80 to 99:

1.

4. The toy hair according to claim 1, comprising a heat-color-changing material.

5. A toy comprising the toy hair described in any one of claims 1 to 4.

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