JPH101545A - Thermoplastic resin composition and its molded product capable of temperature-dependent deformation and shaping - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give a molded product provided with the ability to be easily and freely deformed and to be set in the shape after deformation by the application of an ordinary heating or cooling means and desirably used in the fields of toys or decoration by melt-blending a thermoplastic resin and a thermoplastic polymer having a specified glass transition temperature. SOLUTION: This composition is prepared by melt-blending a thermoplastic resin (A) and at least one thermoplastic polymer (B) having a glass transition temperature in the range of -20 to 70 deg.C in an A:B weight ratio of 95:5 to 20:80 and has the ability to be freely deformed into a shaping according to the stress resulting when an external stress is applied in the region from the glass transition temperature of component B to below its melting point and to be set in the shape after the deformation in the region of temperature below the glass transition temperature. For example, a thermoplastic elastomer each as a polyamide, polyurethane of the like is used as resin A, and a saturated polyester resin, a vinyl acetate or the like is used as polymer B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition and a temperature-dependent deformable and shapeable molded article using the same. In detail, a thermoplastic resin and a thermoplastic polymer having a glass transition temperature in a specific temperature range are melt-blended, and can be freely deformed into an arbitrary shape by applying an external stress in an appropriate temperature range equal to or higher than the glass transition temperature, The deformed shape is provided with a function of being fixed in a temperature range lower than the glass transition temperature, and appropriate shape deformation-shaping can be easily performed as necessary. TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having applicability in various fields and a temperature-dependent deformation-shape molding using the same.

[0002]

2. Description of the Related Art Hitherto, as a thermosensitive deformable material whose form is changed by a temperature change, a bimetal, a shape memory alloy or a resin in which materials having different coefficients of thermal expansion are joined together is known. The bimetal is used as a temperature-sensitive actuator such as a temperature-sensitive switch, and the shape memory alloy or resin is applied to industrial parts and daily necessities. Even if any of the above-mentioned materials changes its form in response to a temperature change, it lacks the degree of freedom of material selection, and it is difficult to obtain various molded products. In addition, the cost is relatively high, and the applicability to toys or decorative elements is limited.

[0003]

SUMMARY OF THE INVENTION According to the present invention, the shape can be easily and freely deformed and the deformed shape can be fixed by applying the temperature range of the living temperature range or daily heating or cooling means. With the addition of a thermochromic function, a relatively low-cost toy or decoration field with simple deformation-shaping and versatility that cannot be achieved with the conventional thermosensitive deformable material. It is an object of the present invention to provide a suitable thermoplastic resin composition and a temperature-dependent deformation-shape molding using the same.

[0004]

According to the present invention, a thermoplastic resin (A) and one or more thermoplastic polymers (B) having a glass transition temperature in the range of -20 ° C to 70 ° C are used. , (A) / (B) = 95/5 to 20/80 (weight ratio)
The requirement is a thermoplastic resin composition melt-blended at a ratio of: Furthermore, one or more of the thermoplastic resin (A) and the thermoplastic polymer (B) having a glass transition temperature in the range of −20 ° C. to 70 ° C. are (A) / (B) =
It is melt-blended at a ratio of 95/5 to 20/80 (weight ratio), and an external stress is applied in a temperature range from the glass transition temperature of the thermoplastic polymer (B) to the melting point and lower than the melting point. A requirement is a thermoplastic resin composition that is freely deformable into an adapted shape and has a function of being fixed to the deformed shape in a temperature range lower than the glass transition temperature. Further, the thermoplastic resin (A) has a glass transition temperature of -20.
One or more of the thermoplastic polymers (B) in the range of not lower than 70 ° C. and not higher than (A) / (B) = 95/5 to 2
0/80 (weight ratio)
By applying an external stress in a temperature range not lower than the glass transition temperature of the thermoplastic polymer (B) and lower than the melting point, the thermoplastic polymer (B) can be deformed into a shape adapted to the stress, and is deformed in a temperature range lower than the glass transition temperature. A temperature-dependent deformation-shape molding having a function of being fixed in a deformed shape is a requirement. Further, the thermoplastic resin (A) is selected from thermoplastic elastomers, and the thermoplastic elastomer is a polyamide, polyurethane, styrene, polyolefin, polybutadiene, polyester, or ethylene-vinyl acetate. The thermoplastic polymer (B) is selected from polymers having a different chemical structure from the thermoplastic resin (A), and the thermoplastic polymer (B) is selected from polymers having different chemical structures from the thermoplastic resin (A). B) exists in a dispersed state or a mixture of a dispersion and a compatible state. The thermoplastic polymer (B) comprises a saturated polyester resin, an acrylate resin, a methacrylate resin, or vinyl acetate. One or more polymers selected from resins, and further, a reversible thermochromic microcapsule pigment is contained in a dispersed state. It is a requirement Rukoto like.

[0005] As described above, the present invention provides a thermoplastic resin (A) and a thermoplastic polymer (B) having a specific glass transition temperature by melt-blending to form a composite thermoplastic resin. The resin (A) or the thermoplastic polymer (B) has a function of being deformable in a specific temperature range and a function of fixing a shape deformed in the temperature range in a specific temperature range, which cannot be exhibited by each single substance. -The shaping property can be easily achieved by a temperature in the living temperature range or daily heating and cooling means, and further, the shaped shape is released in a temperature range equal to or higher than the glass transition temperature to another arbitrary shape. It is characterized by a temperature-dependent deformable and shapeable material having durability that can withstand repeated use, such as being deformable and shapeable.

[0006] In the above-mentioned composite thermoplastic resin body in which the thermoplastic polymer (B) is melt-blended, the thermoplastic polymer (B) is in a temperature range below the glass transition temperature.
Although it has a rigid property, it changes to a viscoelastic property at a temperature higher than the glass transition temperature, and the flexural modulus decreases, so that the rigidity and flexural modulus of the originally rigid thermoplastic polymer (B) are relatively high. As a result, the deformable shape returns to a rigid property in a temperature range equal to or lower than the glass transition temperature and is fixed.
Here, in order to maintain the properties of the composite thermoplastic resin body invariably for a long period of time and to maintain the above-mentioned functions, it is preferable to use a thermoplastic elastomer as the thermoplastic resin (A). The combination (B) is effectively a combination selected from amorphous thermoplastic polymers.

[0007] In the above-mentioned combination of the thermoplastic resin (A) and the thermoplastic polymer (B), a combination of resins having different chemical structures from each other is preferable because the above-mentioned functions can be effectively exhibited. Resins with the same chemical structure,
That is, in the case of a combination of resins of the same quality, a homogeneous compatible solution is formed, and the viscoelastic properties of the thermoplastic resin (B) above the glass transition temperature are appropriately controlled by the thermoplastic resin (A). When the molded bodies are left in a stacked state, they tend to stick to each other, while the fixing function in a temperature range lower than the glass transition temperature is relatively reduced. Will be.

The thermoplastic resin (A) includes polyamide resins (6-nylon, 6,6 nylon, 12-nylon, 6,9 nylon, 612 nylon, 6-6,6 copolymer nylon, 6-12 nylon). Polymerized nylon, 6-6,6-
Polyester resin such as 12-copolymer nylon, 6,9-12-copolymer nylon), polyethylene terephthalate, polybutylene terephthalate, etc., acrylonitrile-
Styrene copolymer resin, acrylonitrile-butadiene-
Styrene resin, polycarbonate resin, vinyl chloride-vinyl chloride copolymer, copolymerized acrylonitrile resin,
Polyamide-based thermoplastic elastomer such as polyamide-polyether block copolymer resin, styrene-based thermoplastic elastomer such as styrene-butadiene block copolymer resin, polyolefin-based thermoplastic elastomer such as polypropylene-ethylene propylene rubber block copolymer resin, polybutadiene Examples thereof include polymers selected from any of thermoplastic elastomers such as a thermoplastic elastomer, a polyester thermoplastic elastomer, and a thermoplastic elastomer such as an ethylene-vinyl acetate copolymer. Deformation processing in the present invention is performed at a temperature in the range of the glass transition temperature or higher and the softening point to the melting point of the thermoplastic resin (A) or the thermoplastic polymer (B) or lower, preferably 100 ° C or lower, more preferably 35 ° C or lower. Processed in a temperature range of 80 ° C.

The thermoplastic polymer (B) has a glass transition temperature of -20 ° C to 70 ° C, preferably -5 ° C to 65 ° C.
° C, more preferably from 20 ° C to 65 ° C, still more preferably from 30 ° C to 60 ° C, under an ambient temperature of 35 ° C to 80 ° C, deformed using an appropriate jig or finger, and below the deformation temperature. It is fixed to the shape after deformation in the temperature range of. Generally, it is generally desirable that the fixing be performed in a temperature range of 30 ° C. or lower to about −5 ° C.

As the thermoplastic polymer (B), saturated polyester resin, acrylate resin, methacrylate resin, vinyl acetate resin, polyamide resin,
Epoxy resin (uncured), hydrocarbon resin, soft vinyl chloride resin, ethylene vinyl acetate-copolymer resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acryl copolymer resin, styrene resin, acrylic-styrene copolymer Resins and the like can be mentioned. Among the above-mentioned resins, a saturated polyester resin, an acrylic resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, a styrene resin and the like are suitably used.

By selecting the thermoplastic polymer (B) having the above glass transition temperature range, the temperature at or near the living temperature range, or various kinds of conventionally known heating,
By applying a cooling / heating means or an appropriate stress deformation means, deformation and shaping into an arbitrary shape can be easily and repeatedly performed, which is particularly effective for toy use.

As the above-mentioned heat or cold means, use of a freezer or a refrigerator, a heat medium such as hot water, or a hot air device using an energizing resistance heating element (such as a nichrome wire or a positive characteristic resistance heating element) as a heat source. A box-type heating device, a trowel or an appropriate shaping jig, a cold air device using ice chips and various regenerators, a Peltier element or the like as a cold heat source, a box-type cooling device, various shapes of shaping jigs, and the like. It can be used as appropriate according to the purpose. A / B = 95/5 to 20/80 (weight ratio) is effective for the blending ratio of the thermoplastic resin (A) and the thermoplastic polymer (B), and is preferably 95/10 to 50/5.
0, the viscosity increases as the weight of the thermoplastic polymer (B) increases, and if it exceeds 90% by weight, the viscosity is too high and stickiness occurs. On the other hand, in a system of less than 5% by weight, the effect of lowering the flexural modulus during the deformation treatment is insufficient, and the viscoelasticity is not sufficiently exhibited, and the desired deformability is hardly generated. Here, each of (A) and (B) is not limited to a single one, and may be used in combination.

The thermoplastic resin composition of the present invention can be formed into a molded product by dissolving it in a solvent or dispersing it in a vehicle and applying it to a support to form a coating film. Even in the case of a coating film, since the above-described deformation-shaping effect is exhibited, when combined with a stress-deformable support, the support itself also exhibits synchronized behavior.

In the deformation-shaping behavior of the thermoplastic resin composition of the present invention and a molded article using the same, the thermoplastic resin (A) has a viscoelasticity at a temperature higher than the glass transition temperature of the thermoplastic polymer (B). When the state transitions to the state, the properties do not change, and the tackiness is appropriately suppressed, which contributes to the avoidance of troubles due to sticking when the molded bodies adhere to each other. Furthermore, sheets, filaments, and shaped bodies of various shapes can be provided by supplementing flexibility, durability, and the like.
Here, in the deformation processing, the inflection to an arbitrary shape can be easily formed without substantially changing the original dimensions, and further, the original dimensions are changed by stretching or pressing to deform. -Shaping can also be performed.

As a special case, in a system where the glass transition temperature of the thermoplastic resin (A) is in the range of -20 ° C. to 70 ° C., only the thermoplastic polymer (B) has a glass transition temperature. Deformability can be imparted by blending both even in a temperature range of 10 to 20 ° C. lower than the glass transition temperature of (B).

The resin composition of the present invention and a molded article using the same have a shape memory property, and can be heated or cooled by applying heat or cold.
Shape memory that returns to an appropriate original shape can also be developed. In addition, the shape memory is heated to around the melting temperature, fixed to an arbitrary shape and cooled to form an initial shape, and then heated to a deformable temperature lower than the melting temperature to give another shape and cooled. Of course, the shape is fixed, and of course, when heated again, it naturally exhibits a shape-memory property that substantially recovers to the substantially initial shape.

A thermochromic material can be blended with the resin composition constituting the present invention and a molded article using the same, if desired. As the thermochromic material, a thermochromic material containing three components of an organic compound medium that reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound is preferably used. Specifically, Japanese Patent Publication No. 51-35
No. 414, JP-B-51-44706, JP-B-1-17154, etc., namely, (1) (A) an electron-donating color-forming organic compound and (B) A thermochromic material comprising, as essential components, three components of a compound having a phenolic hydroxyl group and (c) a linear aliphatic monohydric alcohol. Or (2) a compound selected from (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) an ester obtained from an aliphatic monohydric alcohol and an aliphatic monocarboxylic acid. Thermochromic material with three components as essential components. Or (3) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol, an aliphatic monocarboxylic acid, and a chain aliphatic monohydric alcohol. Thermochromic material containing three components of the compound selected from the ester obtained from the above as essential components. Or (4) (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) a higher aliphatic monohydric alcohol, an aliphatic monocarboxylic acid, and a chain aliphatic monohydric alcohol. Thermochromic material containing three components of the compound selected from the ester obtained from the above as essential components. Alternatively, JP-A-7-18
No. 6546, which exhibits high color density and high brightness such as yellow, yellow-orange, orange, red-orange, red, etc. having fluorescence at the time of color development, and colorless with no color residue at the time of decoloration. (A) an electron-donating color-forming organic compound selected from pyridine, quinazoline, and bisquinazoline-based compounds; (ii) a compound having an electron-accepting property with respect to the electron-donating color-forming organic compound; C) The above (a), (b)
A thermochromic material composed of a compatibilizer containing, as an essential component, three components of a compound which is a reaction medium for causing a reversible reaction of electrons in a specific temperature range by the component is exemplified.

Also, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, etc., thermochromic materials exhibiting large hysteresis characteristics and discoloring, ie, a thermochromic material, that is, the shape of a curve plotting a change in coloring density due to a temperature change indicates a change in temperature. A type of discoloring material that changes color following a significantly different path between when the temperature is increased from a temperature lower than the temperature range and when the temperature is decreased from a temperature higher than the discoloration temperature. It is also effective to use a thermochromic material that has a feature of being able to store and retain a state changed at a temperature equal to or lower than the low-temperature side color change point or higher than the high-temperature side color change point in a normal temperature range between the side color change points.

Also, Japanese Patent Publication No. 1-293 proposed by the present applicant.
As described in JP-A-98-98, a thermosensitive material having a high sensitivity and a hysteresis width of 3 ° C. or less with respect to a color density-temperature curve due to a temperature change is effective.

Although the thermochromic material described above is effective even when applied as it is, it is most preferable to use it in a microcapsule. This is because the thermochromic materials can be maintained at the same composition under the various use conditions and can exhibit the same effects. By being encapsulated in the microcapsule, a chemically and physically stable pigment can be constituted, and the particle diameter is 0.1 to 100 μm, preferably 2 to 30 μm.
The range of m satisfies the practicality.

The microencapsulation can be performed by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from an aqueous solution, phase separation method from an organic solvent, melt dispersion cooling method, There are a medium suspension coating method, a spray drying method and the like, which are appropriately selected according to the application. Further, a secondary resin film may be further provided on the surface of the microcapsules according to the purpose to impart durability or to modify the surface characteristics for practical use.

The thermochromic material is dispersed in a medium containing a fixing agent for forming a coating resin layer, applied as a coloring material such as ink or paint, and reversibly applied to a substrate by coating or spraying. A thermochromic layer can be formed. The thermochromic material is 0.5 to 40% by weight, preferably 1 to 30% by weight in the coating resin layer.
It can be contained. When the amount is less than 0.5% by weight, a clear thermochromic effect is hard to be visually recognized, and when the amount exceeds 40% by weight, the amount is excessive and may be in a decolored state and a residual color may be generated.

The reversible thermochromic layer is formed by a conventionally known method, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition. It can be formed by means such as coating, flow coating, roller coating, and dip coating.

The color change of the thermochromic layer can be varied by mixing an appropriate amount of the non-thermochromic coloring dye in the reversible thermochromic layer. Further, an image such as a character or a pattern may be arranged below the reversible thermochromic layer by the non-thermochromic colored dye / pigment so that these images are hidden.

By setting the discoloration temperature of the thermochromic material and the temperature at which the form changes by heating or cooling to be substantially the same, the form change and the color change can be synchronized, and as a toy or decorative element, It is even more effective.

The resin composition of the present invention and a molded article using the same may contain a conventional light stabilizer such as an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, or a superoxide anion. A light stabilizer selected from a quencher, an ozone decolorant, a visible light absorber, and an infrared absorber may be appropriately blended, or the light stabilizer may be included in a fixing agent to form a light stabilizer layer on the surface. In addition, conventionally used various plasticizers, for example, phthalic acid type, aliphatic dibasic acid ester type,
By applying a phosphate ester type, epoxy type, phenol type, trimellitic acid type or the like in the range of 1 to 30% by weight, the deformable temperature can be lowered or flexibility can be imparted. Further, calcium carbonate, magnesium carbonate, titanium oxide, talc, and other coloring pigments can be added to improve processability, physical properties, and the like.

The resin composition of the present invention is formed into pellets, and various conventional molding methods such as injection molding, extrusion molding, blow molding, melt spinning, and compression molding can be applied.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition of the present invention and the temperature-dependent deformable and shapeable molded article using the same will be described more specifically with reference to examples. However, the present invention is not limited to these examples. It is not something to be done. In addition, the composition in an Example is shown by a weight part.

Example 1 400 parts of an ethylene-vinyl acetate copolymer resin (trade name: Evaflex P1407, manufactured by Mitsui DuPont Polychemical Co., Ltd.) as the thermoplastic resin (A), and a polyester resin as the thermoplastic polymer (B) [Product name: Chemit R-
251; Toray Co., Ltd., glass transition point 25 ° C] 200
And 1 part of a red pigment were mixed and melt-mixed with an extruder at 170 ° C. to obtain a thermoplastic resin composition.

The above composition was molded into a 15 cm long octopus foot using an injection molding machine under the condition of a cylinder temperature of 180 ° C. to obtain a temperature-dependent deformation-shape molding.

The octopus toy was obtained by assembling the molded article as a foot of an octopus-shaped molded article.

The octopus toy was immersed in a hot water bath at 35 ° C. or higher, and the feet were deformed into a desired shape, and then cooled in water at 10 ° C. in that shape to fix the deformed shape. .

The shape change can be roughly repeated at a glass transition point of 25 ° C. or higher of the polyester resin, and the deformation can be repeated at the glass transition point or higher, and the shape can be repeatedly fixed at the glass transition point or lower. At a temperature of 15 ° C. or lower, the temperature is maintained unless an external force is applied.

Example 2 A copolymerized polyamide resin (trade name: Daiamide N1901, Daicel Huls Co., Ltd.) as the thermoplastic resin (A)
400 parts, polyester resin as a thermoplastic polymer (B) [trade name: Polyester TP-2]
17, Nippon Gosei Co., Ltd., glass transition point 40 ° C) 200
Parts were mixed and melt-mixed with an extruder at 180 ° C. to obtain a thermoplastic resin composition.

The composition was molded into a rod having a diameter of 2 mm by an extruder at a cylinder temperature of 180 ° C. to obtain a temperature-dependent deformation-shape molding.

The molded body was softened when immersed in a 42 ° C. hot water bath, and could be easily wound around a 2 cm diameter cylinder in the hot water bath. Then, as it is, 20
After cooling with water at ℃, even if the tube was pulled out, the wound spring shape was fixed, and the shape was maintained as long as no external force was applied.

When immersed again in a hot water bath of 42 ° C. or higher, it became deformable. After being stretched to a linear state, it was cooled with water at 20 ° C. and maintained a linear state at room temperature.

The above-mentioned shape change, that is, deformation at about 42 ° C. or more and fixing at about 30 ° C. or less can be repeated, and a desired shape could be obtained. Incidentally, the deformation and fixing temperatures generally changed around the glass transition temperature of the used polyester resin.

Example 3 250 parts of polyhexamethylene terephthalate (melting point 150 ° C.) as the thermoplastic resin (A) and vinyl acetate resin as the thermoplastic polymer (B) [trade name: Denka Sakunol SN-10, manufactured by Denki Kagaku Kogyo Co., Ltd.] Glass transition point 2
9 ° C.], and melt-mixed at 170 ° C. with an extruder to obtain a thermoplastic resin composition.

The composition was extruded at 180 ° C. using an extruder to obtain a sheet-shaped, temperature-dependent, deformable and shapeable molded article having a thickness of 0.5 mm.

The obtained molded body is cut into a ribbon shape having a width of 3 cm, folded in a water bath at 35 ° C. in a corrugated shape every 3 cm in a longitudinal direction, and cooled as it is with water at 20 ° C. The body was fixed in a bellows shape, and this shape was maintained at room temperature of 25 ° C. or lower unless an external force was applied.

The deformation and fixing of the shape could be repeated at about 35 ° C. or higher and repeated at about 25 ° C. or lower.

Example 4 As the thermoplastic resin (A), a copolymerized polyamide resin [trade name: DAIAMID N1901, Daicel Huls Co., Ltd.]
(Melting point: 155 ° C.) 300 parts, polyester resin as the thermoplastic polymer (B) [trade name: Elitel UE-32]
50, manufactured by Unitika Ltd., glass transition point 40 ° C] 150
Parts were mixed and melt-mixed at 190 ° C. with an extruder to obtain a thermoplastic resin composition.

The composition is spun at 190 ° C. from a die having 24 discharge holes using a general-purpose melt-spinning apparatus and stretched to obtain a temperature-dependent deformable-shapeable molded article. A drawn yarn having a diameter of about 80 μm (single yarn) was obtained. The drawn yarn is wound around a cylinder, heated in an oven at 45 ° C. for 3 minutes, and then left at room temperature of 25 ° C.
When the cylinder was removed, a drawn yarn deformed to the same diameter as the cylinder could be obtained.

The deformed drawn yarn was stretched straight and fixed, heated in an oven at 45 ° C. for 3 minutes, taken out and allowed to stand at room temperature, whereupon it was fixed straight.

The deformation and the fixing of the shape could be repeated at about 45 ° C. or higher and repeated at about 25 ° C. or lower.

Example 5 As a thermoplastic resin (A), 300 parts of a 35 mol% modified polybutylene terephthalate (melting point: 168 ° C.) was used.
As a thermoplastic polymer (B), 150 parts of an acrylic resin (trade name: Dianal BR-117, manufactured by Mitsubishi Rayon Co., Ltd., glass transition temperature: 35 ° C.) are mixed, and melt-mixed with an extruder at 180 ° C. A thermoplastic resin composition was obtained.

The composition was extruded into a rod having a diameter of 2 cm at a cylinder temperature of 190 ° C. using an extruder to obtain a temperature-dependent deformation-shape molding.

The molded body was softened when immersed in a hot water bath at 38 ° C., and could be easily wound around a cylinder having a diameter of 2 mm in the hot water bath. Then, as it is, 20
After cooling with water at ℃, even if the tube was removed, the wound spring shape was fixed, and the spring shape was maintained as long as no external force was applied.

When immersed again in a hot water bath of 38 ° C. or higher, it became deformable. After being stretched to a linear state, it was cooled with water at 20 ° C. to maintain a linear shape at room temperature.

Further, deformation at about 35 ° C. or more and fixing of the shape at about 20 ° C. or less can be repeated, and a desired shape can be obtained.

The deformation and fixation could be expressed roughly at the glass transition temperature of the acrylic resin used.

Example 6 Preparation of reversible thermochromic microcapsule pigment 2 parts of 1,2-benz-6-diethylaminofluoran
A reversible thermochromic material comprising 6 parts of 1,1-bis (4-hydroxyphenyl) -n-octane and 50 parts of stearyl caprate is microencapsulated by an epoxy resin / amine interfacial polymerization method to obtain an average particle size of 10 to 10. A 20 μm reversible thermochromic microcapsule pigment was obtained. The obtained pigment was reversibly changed to colorless at about 34 ° C. or higher and pink at about 28 ° C. or lower.

10 parts of the dried and dehydrated microcapsule pigment and 300 parts of the thermoplastic resin composition obtained in Example 4 were mixed and melt-mixed at 190 ° C. in an extruder to obtain thermochromic properties. A thermoplastic resin composition was obtained. The composition changed colorlessly above about 34 ° C. and reversibly pink below 28 ° C.

Subsequently, the composition was molded into a rod having a diameter of 2 mm at a cylinder temperature of 190 ° C. using an extruder to obtain a pink temperature-dependent deformation-shape molding.

When the pink molded body was immersed in a hot water bath at 45 ° C., it became soft and colorless, and could be easily wound around a 2 cm diameter cylinder in the hot water bath. Then, by cooling with water at 20 ° C. as it is, pink color is formed, and the wound molded body is removed even if the cylinder is pulled out.
The shape of the wound spring was fixed, and the shape was maintained as long as no external force was applied.

Again, when immersed in a hot water bath of 45 ° C. or higher, it becomes deformable and turns colorless, and after being stretched to a linear state,
Upon cooling with water at 20 ° C., the color developed pink, while maintaining a linear state at room temperature. Further, deformation at about 45 ° C. or more and fixing of the shape at about 30 ° C. or less were repeatable, and a desired shape could be obtained.

The above deformation and fixation could be expressed roughly at the glass transition temperature of the polyester resin used.

In addition, by kneading the reversible thermochromic microcapsule pigment, not only the shape change but also the color change can be observed in the molded article, and it also functions as an indicator of the deformation temperature and the shape fixing temperature. It was possible. Also in the following examples, by blending the thermochromic microcapsule pigment, the color change can be visually recognized together with the form change.

Example 7 As a thermoplastic resin (A), a polyamide-based thermoplastic elastomer [trade name: Daiamide E62, Daicel. Hyrus Co., Ltd.], 400 parts, and 300 parts of a polyester resin (trade name: Eril UE-3215, manufactured by Unitika Ltd., glass transition point: 45 ° C.) as a thermoplastic polymer (B) were mixed at 190 ° C. The mixture was melted and mixed with a ruder to obtain a thermoplastic resin composition.

The composition is spun at 190 ° C. from a die having 24 discharge holes using a general-purpose melt spinning apparatus and stretched to obtain a temperature-dependent deformable-shapeable molded article. A drawn yarn having a diameter of about 80 μm (single yarn) was obtained. The drawn yarn is wound around a cylinder, heated in an oven at 45 ° C. for 3 minutes, and then left at room temperature of 25 ° C.
When the cylinder was removed, a drawn yarn deformed to the same diameter as the cylinder could be obtained.

The deformed drawn yarn was straightened and fixed, heated in an oven at 45 ° C. for 3 minutes, taken out and left at room temperature, whereupon it was fixed straight.

The deformation and the fixing of the shape could be repeated at about 50 ° C. or higher and repeated at about 30 ° C. or lower.

Example 8 As a thermoplastic resin (A), a polyester elastomer [trade name: Perprene P-40H, manufactured by Toyobo Co., Ltd.] 4
00 parts, a polyester resin as the thermoplastic polymer (B) [trade name: Polyester TP-249, Nippon Gosei Co., Ltd.]
200 parts, glass transition point 36 ° C)
Was melt-mixed with an extruder to obtain a thermoplastic resin composition, and then molded into the shape of a doll's foot.

A doll toy was obtained by incorporating the molded body as a doll's foot. Immerse the doll toy in a 40 ° C hot water bath,
After deforming the foot part to the desired shape,
By cooling with water at 0 ° C., the deformed shape was fixed. In addition, deformation and fixing of the shape are deformed at about 40 ° C. or higher.
In general, fixation at 25 ° C. or less could be repeated.

Example 9 Polyurethane elastomer (trade name: Desmopan 385, manufactured by Bayer Ltd.) as the thermoplastic resin (A) 40
0 parts, a polyester resin as the thermoplastic polymer (B) [trade name: Elitel UE-3500, Unitika Ltd.]
Manufactured, glass transition point 35 ° C] 200 parts
Was melt-mixed with an extruder to obtain a thermoplastic resin composition.

The composition was molded into a rod having a diameter of 2 mm by using an extruder at a cylinder temperature of 200 ° C. to obtain a temperature-dependent deformation-shape molding.

The molded body was softened when immersed in a water bath at 38 ° C., and could be easily wound around a cylinder having a diameter of 2 cm in the water bath. Then, as it is, 20
After cooling with water at ℃, even if the tube was removed, the wound spring shape was fixed, and the spring shape was maintained as long as no external force was applied.

When immersed again in a hot water bath of 38 ° C. or higher, it became deformable. After being stretched in a linear state, it was cooled with water at 20 ° C. to maintain a linear shape at room temperature.

The deformation at about 35 ° C. or more and the fixing of the shape at about 20 ° C. or less can be repeated, and a desired shape can be obtained.

The above deformation and fixation could be expressed roughly on the basis of the glass transition temperature of the polyester resin used.

[0072]

The thermoplastic resin composition of the present invention and a molded article using the same can be used at a temperature within the living temperature range, or in a temperature range near the living temperature range, or under the ambient temperature of ordinary heat or cooling means. By applying an external stress with a jig or a finger or the like, it can be deformed into an arbitrary shape, and is fixed to the deformed shape by water cooling, natural leaving, or other cooling means. The fixed shape is released by heating above the glass transition temperature and freely deformed into another shape.
It can be shaped. In addition, the molded article is rich in flexibility and durability, and can provide sheets, filaments, and shaped articles of any shape by conventional general-purpose molding means, and satisfies the repeated deformation-shaping effect. As described above, the deformation is performed in a relatively low temperature range, the deformation is fixed by the temperature drop, and the deformation-shaping of an arbitrary shape can be repeated, so that toys, stationery, teaching materials, decorations, and other deformability are possible. The present invention can provide a thermoplastic resin composition having applicability in a variety of fields in which a temperature-dependent deformation-shape-forming article using the same is used.

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Claims (16)

[Claims] 1. A thermoplastic resin (A) and one or two or more thermoplastic polymers (B) having a glass transition temperature in the range of −20 ° C. to 70 ° C. are (A) / (B) = 95 /
A thermoplastic resin composition melt-blended at a ratio of 5 to 20/80 (weight ratio). 2. A thermoplastic resin (A) and one or two or more thermoplastic polymers (B) having a glass transition temperature in the range of −20 ° C. to 70 ° C. are (A) / (B) = 95 /
By being melt-blended at a ratio of 5 to 20/80 (weight ratio), by applying an external stress in a temperature range not lower than the glass transition temperature and lower than the melting point of the thermoplastic polymer (B),
A thermoplastic resin composition capable of being deformed into a shape adapted to the stress and having a function of being fixed to the deformed shape in a temperature range lower than a glass transition temperature. 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is selected from thermoplastic elastomers. 4. The thermoplastic elastomer includes polyamide, polyurethane, styrene, polyolefin, and the like.
The thermoplastic resin composition according to claim 3, which is a polymer selected from any of a polybutadiene-based, polyester-based, and ethylene-vinyl acetate-based copolymer. 5. The thermoplastic resin composition according to claim 1, wherein the thermoplastic polymer (B) is selected from polymers having a different chemical structure from the thermoplastic resin (A). 6. The thermoplastic resin composition according to claim 1, wherein the thermoplastic polymer (B) exists in a dispersed state or a mixed state of dispersion and compatibility. 7. The thermoplastic polymer (B) is one or two selected from a saturated polyester resin, an acrylate resin, a methacrylate resin, and a vinyl acetate resin.
7. The thermoplastic resin composition according to claim 1, which is at least one kind of polymer. 8. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is selected from resins having a melting point or a softening point of 100 ° C. or higher. 9. The thermoplastic resin composition according to claim 1, which has a form of a coating film. 10. The thermoplastic resin composition according to claim 1, wherein the reversible thermochromic microcapsule pigment is contained in a dispersed state. 11. A thermoplastic polymer (B) molded from the thermoplastic resin composition according to any one of claims 1 to 810.
By applying an external stress in a temperature range equal to or higher than the glass transition temperature and lower than the melting point, it is freely deformable into a shape adapted to the stress, and has a function of being fixed to the deformed shape in a temperature range lower than the glass transition temperature. Temperature-dependent deformation-shaping molding provided. 12. The thermoplastic polymer (B) has a glass transition temperature in a temperature range of 20 ° C. to 70 ° C., and is approximately 100 ° C.
12. The temperature-dependent deformation-impartment according to claim 11, which can be deformed into an arbitrary shape by applying an external stress at an ambient temperature of not more than ℃ and has a function of fixing the deformed state in a temperature range not more than a glass transition temperature. Shaped molded body. 13. The temperature-dependent deformable and shapeable molded article according to claim 11, which is a sheet, a filament, or a shaped article having an arbitrary shape. 14. The thermoplastic resin (A) is selected from a polyamide resin, a polyester resin, and a thermoplastic elastomer, and the thermoplastic polymer (B) is a saturated polyester resin, an acrylate resin, a methacrylate ester. 12. A resin selected from the group consisting of a resin and a vinyl acetate resin.
To 13 temperature-dependent deformation-shape moldings. 15. The temperature-dependent deformation-shape molding according to claim 11, wherein the reversible thermochromic layer is formed at an appropriate position on the outer surface, and the color change is visually recognized together with the morphological change. . 16. The thermoplastic resin composition according to claim 1, which is a toy or a decorative element.
Any of the temperature-dependent deformation-shape moldings according to any one of Items 1 to 15.