KR20090004936A - Heat-storing composition, and heat-storing fiber, sheet and film each made of the same - Google Patents

Abstract

Disclosed is a heat-storing composition containing a temperature regulating agent and a thermoplastic resin. This heat-storing composition is characterized in that the temperature regulating agent is composed of a polymer, an oligomer or a crosslinked product of an oligomer, while having a melting point of from-10 to 100°C, a latent heat of not less than 30 J/g, and a weight average molecular weight of 5,000-65,000.

Description

Heat storage composition, and heat storage fiber, sheet | seat, and film which consist of it {HEAT-STORING COMPOSITION, AND HEAT-STORING FIBER, SHEET AND FILM EACH MADE OF THE SAME}

The present invention relates to a heat storage composition and heat storage fibers, sheets and films obtained by processing the same.

BACKGROUND ART Various temperature regenerative members have been used for garments used in an environment where temperature changes are significant.

As a heat-regulating heat storage member, a microcapsule containing a substance having a melting point near room temperature is fixed to a cloth, or a heat storage fiber obtained by spinning a synthetic resin containing a microcapsule is known as a fabric.

As heat storage fiber, the composite fiber which made the composition which consists of a paraffin wax which is a heat storage material, and a polyethylene resin as a core material is proposed (patent document 1).

Moreover, the heat storage fiber characterized by extending the composition which has the temperature control function which disperse | distributed a heat storage material to the longitudinal direction of a thread is proposed (patent documents 2-4).

However, these fibers had a problem in that stable production could not be performed because the yarn breaks frequently during spinning.

The present applicant proposes the heat storage composite fiber using the heat storage composition which mix | blends the heat storage material which consists of a polymer or an oligomer, or the heat storage material which consists of these crosslinked bodies to a synthetic resin (patent document 5).

However, depending on the conditions of the spinning, such as the yarn diameter, stable production may not be possible and further study was required.

Patent Document 1: Japanese Patent Application Laid-Open No. 8-311716

Patent Document 2: Japanese Patent Application Publication No. 2004-510068

Patent Document 3: Japanese Patent Publication No. 2005-515317

Patent Document 4: Japanese Patent Publication No. 2005-503497

Patent Document 5: Japanese Unexamined Patent Publication No. 2004-003087

This invention is made | formed in view of the above-mentioned problem, and an object of this invention is to provide the heat storage composition which can be processed, without breaking a thread at the time of spinning.

Disclosure of the Invention

According to this invention, the following heat storage compositions etc. are provided.

1. A heat storage composition comprising a temperature control agent and a thermoplastic resin, wherein the temperature control agent is a crosslinked product of a polymer, oligomer or oligomer, the melting point of the temperature control agent is -10 to 100 ° C, the latent heat is 30 J / g or more, and the weight average A heat storage composition having a molecular weight of 5,000 to 65,000.

2. The heat storage composition according to 1, wherein the temperature regulator is dispersed in the thermoplastic resin and the average particle diameter of the temperature regulator is less than 13 µm.

3. The heat storage composition according to 1 or 2, wherein the ratio of the temperature controller in the heat storage composition is 5 to 70 mass%, and the ratio of the thermoplastic resin is 30 to 95 mass%.

4. The heat storage composition according to any one of 1 to 3, wherein the weight average molecular weight of the temperature controller is 5,000 to 30,000.

5. In any one of 1 to 4, wherein the thermoplastic resin is at least one selected from polypropylene resin, polyethylene resin, polyester resin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin, and ethylene-vinyl alcohol copolymer resin. The regenerative composition described.

6. The heat storage fiber formed by melt spinning the heat storage composition as described in any one of said 1-5.

7. Sheet or film which consists of heat storage composition in any one of said 1-5.

ADVANTAGE OF THE INVENTION According to this invention, the heat storage composition which can reduce the thread break at the time of spinning can be provided. Moreover, when a sheet | seat or a film is shape | molded using this heat storage composition, opacity and thickness change can be reduced.

Best Mode for Carrying Out the Invention

The heat storage composition of the present invention includes a temperature control agent and a thermoplastic resin.

The temperature regulator used in the present invention is a crosslinked product of a polymer, oligomer or oligomer having a melting point of −10 to 100 ° C. and a latent heat of 30 J / g or more. The weight average molecular weight (Mw) of this temperature regulator is 5,000-65,000. In this invention, the temperature regulator is highly disperse | distributed to a thermoplastic resin by using the temperature regulator whose Mw is the said range. This can effectively prevent thread break during spinning. In addition, when Mw is less than 5,000, a temperature regulator may bleed on the yarn surface, and may liquefy at the time of use, and may become sticky. On the other hand, when it exceeds 65,000, since the dispersibility as a temperature regulator deteriorates, spinning and molding workability may fall. Mw becomes like this. Preferably it is 5,000-30,000, More preferably, it is 5,000-20,000.

As a thermostat which is a crosslinked body of a polymer, an oligomer, and an oligomer, the following (A)-(C) is mentioned, for example.

(A) A crystalline unit composed of the main chain (X), the coupling (Y) and the side chain (Z) shown in formula (1), wherein the side chain (Z) can be crystallized with each other as a main component Polymer or oligomer

(B) The main component is a crystalline unit composed of the main chain portion (X), the coupling portion (Y) and the side chain (Z) shown in the above formula (1), wherein the side chain (Z) can be crystallized with each other. Polymer or oligomer crosslinked product (crosslinking temperature regulator).

(C) A polymer or oligomer (polyether temperature regulator) having a main chain which is a polyether main chain and a unit having side chains which can be crystallized with each other.

These temperature regulators are phase-changed (melted and solidified) by the crystallization or crystallization of the side chain (Z) in the temperature regulators (A) and (B) in the desired temperature range, and in the temperature regulator (C) Phase change (melting, coagulation) is caused by the coagulation dissociation of the side chains, at which time a large latent heat is released or absorbed. Therefore, these temperature regulators absorb and melt heat when the outside air temperature rises, and release and coagulate when the outside air temperature decreases, so that the fluctuation of the outside air temperature is reduced and a constant temperature is easy to be maintained, thus functioning as a temperature regulator. Exert. Moreover, in the temperature regulators (A) and (B), since the main chain part (X) of Formula (1) does not melt in said temperature range, and in the temperature regulator (B), it becomes a three-dimensional network structure by crosslinking. The whole material does not spill and the shape is maintained. Moreover, these temperature regulators (A), (B) and (C) can adjust melting | fusing point easily by adjusting the length of a side chain.

First, the temperature regulators (A) and (B) are demonstrated.

In the temperature regulators (A) and (B), the main chain portion (X) of the formula (1) is not particularly limited as long as it is not a structure that inhibits crystallization of the side chain (Z), but preferably

It is at least one kind selected from.

The coupling | bonding part Y is a part which couple | bonds the principal chain part X and the side chain Z, and means a 1 atomic unit. The side chain (Z) is not particularly limited as long as it can be crystallized, but preferably contains a hydrocarbon group of 9 or more carbon atoms, more preferably a linear alkyl group of 9 or more carbon atoms.

The bonding portion and the side chain (YZ) are preferably at least one kind selected from -CO-OR, -O-CO-R, -OR, and -CH ₂ -R, R is a hydrocarbon group having 9 or more carbon atoms, and Preferably it is a C9 or more linear alkyl group.

The crystalline unit which consists of especially preferable principal chain part (X), coupling | bonding part (Y), and side chain (Z) is a polymethacrylate type | system | group, polyacrylate type, polyvinyl ester system, polyvinyl ether system, or Hydrocarbon type.

As an example of a preferable temperature control agent (A), polydocosyl methacrylate, polyheneicosyl methacrylate, polyeicosyl acrylate, polynonadecyl acrylate, polyhepta decyl acrylate, polypalmityl acrylate, poly Pentadecyl acrylate, polystearyl acrylate, polylauryl acrylate, polymyristyl acrylate, polymyristyl methacrylate, polypentadidecyl methacrylate, polypalmityl methacrylate, polyheptadecyl methacrylate Latex, polynonadecyl methacrylate, polyeicosyl methacrylate, polystearyl methacrylate, poly (palmyl / stearyl) methacrylate, polyvinyl laurate, polyvinyl myristate, polyvinyl palmitate, Polyvinyl stearate, polylauryl vinyl ether, polymyristyl vinyl ether, poly palmityl vinyl ether, poly And the like aryl vinyl ether, poly-α-olefin advanced. Especially preferably, they are poly higher alpha olefin. Higher alpha olefin is a C10 or more alpha olefin here, More preferably, it is an alpha olefin which has 16-18 carbon atoms. The polyhigh alpha olefin may contain a structural unit derived from a high alpha olefin, may be a homopolymer of a high alpha olefin, may be a copolymer, or may be a copolymer with olefins such as ethylene and propylene.

It is preferable that content of the higher alpha olefin unit in a poly higher alpha olefin is 50 mol% or more, Especially preferably, it is 100 mol%. If the content of the higher α-olefin unit is 50 mol% or more, the crystallinity is increased, so that the capacity as an efficient heat storage material can be obtained.

Moreover, the crosslinked body which is an example of the said temperature regulator (A) is mentioned as an example of a preferable temperature regulator (B).

Preferably, the weight of the main chain (X), the coupling portion (Y) and the side chain (Z) satisfies the following formula.

Z / (X + Y + Z) ≥ 0.75

That is, the ratio which occupies for the crystalline unit of side chain (Z) is 75 weight% or more. If it is less than 75 weight%, the side chain (Z) cannot be crystallized and there exists a possibility that it may not exhibit temperature composition.

The temperature regulators (A) and (B) can also exhibit a desired function by containing another unit in the range which does not impair the characteristic.

For example, the temperature regulators (A) and (B) may contain hydrophilic units. Since these temperature regulators have a long chain hydrocarbon group as a side chain, hydrophobicity is high, but hydrophilicity can be improved by containing a hydrophilic unit. Moreover, when these temperature regulators are used in combination with another hydrophilic substance, adhesiveness with respect to another substance improves.

Although the monomer which forms such a hydrophilic unit is not specifically limited, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc. are mentioned. The hydrophilic unit formed of 2-hydroxyethyl methacrylate is represented by the following formula (4). In addition, the hydrophilic unit formed from 2-hydroxyethyl acrylate is represented by following formula (5).

Content of a hydrophilic unit becomes like this. Preferably it is 50 weight% or less, More preferably, it is 30 weight% or less. When it exceeds 50 weight%, there exists a possibility that the crystallinity of side chain (Z) may fall.

The manufacturing method of a thermostat (A) and (B) is not specifically limited.

For example, the temperature regulator (A) can be produced by polymerizing a monomer capable of forming a crystalline unit or a monomer capable of forming a crystalline unit and a hydrophilic unit.

Moreover, it is preferable to synthesize | combine with the homogeneous-type catalyst called what is called a metallocene catalyst about the polyhigh alpha olefin mentioned above. Metallocene-based catalysts are described, for example, in WO 03/070790. Especially, it is preferable to use the transition metal compound of C2 symmetry and C1 symmetry which can synthesize an isotactic polymer. Specifically, the catalyst containing the following (a) and (b) is preferable.

(a) 2 cross-linked transition metal compound

(b): at least one component selected from (b-1) a compound capable of forming an ionic complex by reacting with a transition metal compound or derivative thereof of component (a), and (b-2) aluminoxane

In the presence of a polymerization catalyst, a higher alpha olefin having 10 or more carbon atoms is polymerized.

As said two-crosslinked transition metal compound, it is preferable that a transition metal compound having a double-crosslinked biscyclopentadienyl derivative as a ligand contains silicon in a crosslinking group between ligands, for example, (1,2'-dimethyl Silylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride and the like.

Dimethylanilinium tetrakispentafluorophenylborate etc. are mentioned as a component (b-1).

Examples of the component (b-2) include chained aluminoxanes such as methylaluminoxane and cyclic aluminoxanes.

In addition to the components (a) and (b), organic aluminum compounds such as trimethylaluminum and triisobutylaluminum may be used as the component (c).

The temperature regulator (B) can be produced by polymerizing a monomer capable of forming a crystalline unit or a monomer capable of forming a crystalline unit and a hydrophilic unit with a crosslinking agent.

Examples of the crosslinking agent (monomer) forming the crosslink include polyethylene glycol (1000) diacrylate, polyethylene glycol (1000) dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, and the like, and preferably polyethylene glycol ( 1000) dimethacrylate, ethylene glycol dimethacrylate.

The amount of the crosslinking agent is usually preferably 0.1 to 20% by weight, more preferably 0.2 to 3% by weight, based on the monomer capable of forming the crystalline unit and the hydrophilic unit. If it is less than 0.1 weight%, a crosslinking effect hardly appears. On the other hand, even if it exceeds 20 weight%, there is almost no difference in an effect.

Next, a temperature regulator (C) is demonstrated.

The temperature regulator (C) is a polymer or oligomer whose main component is a unit having a main chain which is polyether and a side chain which can be crystallized with each other as described above.

In the temperature regulator (C), the side chain is not particularly limited as long as it can be crystallized.

As a specific temperature regulator (C), the polyglycerol system which has a unit represented by Formula (2), or the polyalkylene glycol system which has a unit represented by Formula (3) is mentioned.

(In formula, R <^1> is at least 1 sort (s) chosen from a C11 or more hydrocarbon group, R <^2> is at least 1 sort (s) chosen from a C14 or more hydrocarbon group.)

R ¹ or R ² is preferably a linear alkyl group having the above carbon number. Specific examples thereof include undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, hencosyl group, docosyl group, tricosyl group and the like. Can be mentioned.

Particularly preferred are tridecyl group (C13), pentadecyl group (C15), heptadecyl group (C17), and heteroethyl group (C21).

For example, when R <^1> is a tridecyl group of 13 carbon atoms, and R <^2> is a tetradecyl group of 14 carbon atoms, the temperature regulator of this invention has a unit represented by Formula (6) or Formula (7), respectively.

In the above configuration, the main chain is not crystallized at a predetermined temperature, but the long side chains may be crystallized with each other.

Examples of polyglycerin-based temperature regulators include decaglycerin-lauric acid (C12) reactants, decaglycerin-myritic acid (C14) reactants, decaglycerin-palmitic acid (C16) reactants, decaglycerin-stearic acid (C18) reactants , Decaglycerin-behenic acid (C22) reactant, and the like. Of these, preferred are the decaglycerin-myritic reactant, the decaglycerin-palmitic acid reactant, the decaglycerin-stearic acid reactant and the decaglycerin-behenic acid reactant.

Moreover, the polymer etc. of alkylene oxides, such as a dodecylene oxide, tetradecylene oxide, hexadecylene oxide, an octadecylene oxide, etc. are mentioned as an example of a polyalkylene glycol system temperature regulator. Among these, preferred are polymers such as hexadecylene oxide and octadecylene oxide.

The temperature regulator (C) can also exhibit the desired function by changing the functional group of a side chain in the range which does not impair the characteristic.

For example, since a thermostat (C) has a long chain hydrocarbon group as a side chain, hydrophobicity is high, but hydrophilicity can be improved by containing hydrophilic functional groups, such as alcohol. As a result, when apply | coating a temperature regulator etc. to a base material, adhesiveness with respect to a base material etc. improves.

As for the temperature regulator (C), 5% weight reduction temperature in air measured with the TG-DTA measuring apparatus becomes like this. Preferably it is 200 degreeC or more, More preferably, it is 240 degreeC or more.

If it is less than 200 degreeC, it may evaporate at the time of heat processing process. In addition, a 5% weight loss temperature is the temperature at the time of heating the temperature regulator (C) and reducing 5 weight% of the whole.

The manufacturing method of a temperature regulator (C) is not specifically limited. For example, a polyglycerol-type temperature control agent is made by reacting the hydroxyl group which exists in a polyglycerol (polyether main chain), and the carboxyl group of the carboxylic acid (side chain) which has a linear alkyl group using a well-known esterification reaction. It can manufacture.

On the other hand, a polyalkylene glycol-type temperature regulator can be manufactured by ring-opening-polymerizing an alkylene oxide.

The above-mentioned temperature regulators (A) to (C) reversibly undergo a phase transition of crystallization and non-crystallization with a latent heat having a large side chain in a predetermined temperature range, but the main chain does not have such phase transition. For this reason, it is not necessary to use a microcapsule since it is hard to cause a bleed out compared with wax etc.

Melting | fusing point of the temperature regulator used by this invention is -10-100 degreeC. The lower limit of this range is preferably 0 ° C, more preferably 10 ° C. Preferably the upper limit of this range is 80 degreeC, More preferably, it is 50 degreeC, Especially preferably, it is 40 degreeC.

When melting | fusing point exceeds 100 degreeC, since these temperature regulators always exist in a solid state under daily use atmosphere, the property which absorbs the heat of crystallization at the time of temperature rising cannot be utilized, and it becomes difficult to fully exhibit a function as a temperature regulator.

Moreover, when melting | fusing point is less than -10 degreeC, since these temperature regulators always exist in a liquid state in daily use atmosphere, the property which discharge | releases heat at the time of solidification cannot be utilized, and it becomes difficult to fully exhibit a function as a temperature regulator.

The difference between the melting point and the solidification point of the temperature controller is usually within 15 ° C. If it is larger than 15 ° C, the interval between endothermic and heat dissipation is large, so that it becomes difficult to exhibit a function in a narrow temperature range desired as a temperature regulator.

The latent heat of the temperature control agent is 30 J / g or more, preferably 50 J / g or more, and more preferably 70 J / g or more in the range of the melting point. If the latent heat is less than 30 J / g, the effect as a temperature regulator may be insufficient.

In addition, in this application, melting | fusing point, freezing point, and latent heat are respectively measured by differential scanning calorimetry (DSC), and melting | fusing point means the temperature of the peak of a melting peak, and freezing point means the temperature of the peak of a crystallization peak (JIS K7121). Here, melting | fusing point is the temperature of the peak of the melting peak obtained when heating to a temperature higher than the time of the end of a melting peak once, cooling to predetermined temperature, and then heating again.

It is preferable that melting | fusing point of the thermoplastic resin which comprises the heat storage composition of this invention is 100 degreeC or more. Specifically, polyurethane resins, acrylic resins, polyamide resins, polyvinyl chloride resins (PVC resins), polypropylene resins, polyethylene resins, polystyrene resins, polyester resins (e.g. PET), polycarbonate resins, ethylene-vinyl Alcohol copolymer resin, thermoplastic elastomer resin, polyphenylene sulfide resin, ABS resin, etc. are mentioned. Among them, polypropylene resin, polyethylene resin, polyester resin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin and ethylene-vinyl alcohol copolymer resin are preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

In addition, the thermoplastic resin may be a wet spinning unique resin (for example, rayon).

In the heat storage composition of the present invention, the temperature regulator is highly dispersed in the thermoplastic resin. Specifically, it is preferable that the average particle diameter of the temperature regulator is dispersed to less than 13 µm. In this invention, a temperature regulator can be highly disperse | distributed in a thermoplastic resin by using what has a comparatively small weight average molecular weight of a temperature regulator. Thereby, the thread break at the time of spinning can be reduced significantly. When the average particle diameter of a thermoregulator is 13 micrometers or more, there exists a possibility that a thread may break at the time of spinning.

Herein, the average particle diameter of the temperature regulator refers to the composition cross section of the composition (e.g. pellets) before spinning with a transmission electron microscope, and randomly selects and measures the long diameters of a plurality of dispersed temperature regulators, and then averages the average. It means to make something. In addition, when the temperature regulator is more highly dispersed and commercialized, the average particle diameter may not be measured.

The average particle diameter of the temperature regulator dispersed in the heat storage composition of this invention becomes like this. More preferably, it is 10 micrometers or less, More preferably, it is 5 micrometers or less, Especially preferably, it is 0.5 micrometer or less.

The average particle diameter of a thermostat can be adjusted by controlling the molecular weight of a thermoregulator, the molecular weight of a thermoplastic resin, etc.

The ratio of the temperature regulator and the thermoplastic resin in the heat storage composition of the present invention is preferably a temperature regulator / thermoplastic resin (mass%): 5/95 to 70/30. If the temperature regulator is less than 5 mass%, the temperature control function may not be sufficiently exhibited, and if it exceeds 70 mass%, there is a fear that sufficient dispersion may not be obtained. More preferably, it is 5-50 mass%.

An epoxy group containing acrylic polymer, an aryl ether copolymer, etc. can be mix | blended with the heat storage composition of this invention as a compatibility improving material. This improves the compatibility of the thermoplastic resin and the temperature control agent, thereby increasing the amount of the temperature control agent blended.

The heat storage composition of the present invention also contains various additives such as antioxidants, light agents, inorganic fillers (calcium carbonate, talc, etc.), foaming agents (chemical foams, etc.), and aging within a range that does not impair the properties thereof. An inhibitor, an antibacterial agent, an antifungal agent, a coloring agent, a pigment, an antistatic agent, a flame retardant, a processing aid, a stabilizer, a plasticizer, a crosslinking agent, a reaction promoter, etc. can be mix | blended.

The latent heat of the heat storage composition of the present invention is usually -10 to 100 ° C, in terms of heat storage function, preferably 1 J / g or more, and more preferably 5 J / g or more. If the latent heat is less than 1 J / g, the effect of heat storage may not be sufficient. Moreover, Preferably it is -10-80 degreeC, More preferably, it is 1 J / g or more, More preferably, it is 5 J / g or more in 0-50 degreeC. By this characteristic, the temperature control function can be sufficiently exhibited with respect to the outside air temperature.

The heat storage composition of the present invention can be produced by kneading a temperature controller and a thermoplastic resin with a known method, for example, a kneading extruder or the like.

Moreover, heat storage fiber can be manufactured by carrying out melt spinning of the heat storage composition of this invention with a well-known extruder type | mold complex spinning machine. The heat storage fiber of the present invention is preferably a core-sheath structure.

In the case of the sheath structure, as the resin constituting the sheath portion, polyamide resin, polyester resin, polyurethane resin, ethylene vinyl acetate copolymer, polyvinylidene chloride resin, polyvinyl chloride resin, acrylic resin, polyethylene resin, poly Propylene resin and the like can be used.

At the time of spinning, it is preferable that the particle diameter of a temperature control agent is 1/3 or less with respect to the diameter of a yarn (in core structure, the diameter of a core part), and if it is 1/5 or less, it is more preferable.

Although spinning temperature changes with fiber raw materials to be used, it is about 180-350 degreeC normally.

Moreover, when manufacturing said heat storage fiber, a moisture absorbent, a wetting agent, a coloring agent, a stabilizer, a flame retardant, an electrostatic agent, antioxidant, antioxidant, an antibacterial agent, an antifungal agent, a pigment, an antistatic agent, suitably in the range which does not impair the characteristic, A flame retardant, a processing aid, a plasticizer, a crosslinking agent, a reaction promoter, a blowing agent, and the like can be added.

In addition, the cross-sectional shape of the heat storage fiber is not limited to a circular shape, but may be a release cross section such as a triangle or a square.

In the present invention, there is no problem of evaporation or leakage since the temperature regulator used for producing the heat storage fiber is relatively high in molecular weight compared with wax or monomer. Moreover, since it is an oligomer or a polymer, kneading | mixing and fiberization are possible and processing of continuous spinning, weaving, etc. is easy. That is, the heat storage fiber of the present invention is excellent in spinning property and easy to manufacture.

Since the core portion of the heat storage fiber contains the above temperature control agent, the heat storage fiber generates latent heat at the melting point of the temperature control agent. That is, latent heat is preferably generated at -10 to 100 ° C, preferably at least 1 J / g, more preferably at least 5 J / g. If the latent heat is less than 1 J / g, the effect of heat storage may be insufficient. Moreover, Preferably it produces latent heat of 1 J / g or more, More preferably, 5 J / g or more at -10-80 degreeC, More preferably, it is 0-50 degreeC.

By this characteristic, the temperature control function can be sufficiently exhibited with respect to the outside air temperature.

Moreover, by making a core part into said temperature control agent or a thermoplastic resin, a temperature control agent can be disperse | distributed uniformly in a fiber and the nonuniformity of a spinning diameter, a tensile strength, etc. can be suppressed. In addition, by making the initial portion into the above-mentioned thermoplastic resin, the surface of the fiber can be made the same as that of the conventional synthetic fiber, and the processing and dyeing of the woven and knitted fabric can also be carried out by the same method as in the prior art, and the handling becomes easy.

The sheet or film can be produced by molding the heat storage composition of the present invention by a known method, for example, an extruder equipped with a sheet or a mold for film. In the heat storage composition of the present invention, since the temperature regulator is highly dispersed as described above, opacity (cloudiness) due to poor dispersion of the temperature regulator is unlikely to occur.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

(1) Preparation of heat storage composition

30 mass% of 1-hexadecene 1-octadecene copolymer [(C ₁₆ H ₃₂ ) _m. (C ₁₈ H ₃₆ ) _n ] (Mw = 8500) as a temperature regulator, and polypropylene (a prime polymer company) as a thermoplastic resin 70 mass% of manufacture, Y2005GP) was put into the extrusion granulator (manufactured by Ikegai Co., Ltd.), and melt kneaded to obtain a pellet-shaped composition. The granulation temperature at this time was 280 degreeC.

In this composition, when the dispersion state of the temperature regulator was observed with a transmission electron microscope (TEM), the average particle diameter of the temperature regulator was 0.3 µm.

(2) radioactive evaluation

The composition produced in the above (1) was melted by a kneading extruder (KCK-80, manufactured by KCK Engineering Co., Ltd.) and extruded into a strand shape from a mold. Extrusion was carried out at 240 degreeC, and the strand was hanged from the height of 2 m to the bottom surface. It was observed whether or not thread break occurred in this strand. Evaluation was performed based on the following criteria. The results are shown in Table 1. In addition, the thread diameter means the diameter of the hardened strand, and it evaluated by changing to 7 micrometers-1000 micrometers, as shown in Table 1. The thread diameter was performed by adjusting the discharge amount of an extruder (screw rotation speed etc.).

○: 1 minute without a single yarn

(Triangle | delta): When there is less than 10 times of single yarn for 1 minute

X: When there is a single yarn 10 times or more for 1 minute

(3) Evaluation of the sheet

The sheet | seat of 500 micrometers in thickness was shape | molded by the multilayer extruder (2 type 3-layer molding machine) (made by Tanabe Plastics Machine Co., Ltd.). The composition produced in the above (1) was used as the core resin, and polypropylene (Prime Polymer Co., E-203 GV) was used as the surface layer resin. Molding temperature was 200 degreeC, the thickness of the core part was 300 micrometers, and the thickness of the surface layer part was 150 micrometers, respectively.

About this sheet, the surface was visually observed and the following references | standards evaluated. The results are shown in Table 1.

○: 10 cm square sheet without opacity and transparent

(Triangle | delta): When the opacity is within 5 places in a 10 cm square sheet.

X: When there are six or more opacity in the 10-cm square sheet

Example 2-6 Comparative Example 1

Except having changed the molecular weight (Mw) of the temperature regulator as shown in Table 1, it carried out similarly to Example 1, and produced and evaluated the heat storage composition. The results are shown in Table 1. In addition, the physical property of the temperature control agent used by each example and the average particle diameter in a pellet-form composition are shown in Table 2.

In addition, evaluation of the temperature regulator was performed by the following method.

(1) melting point, latent heat

A differential scanning calorimeter (DSC-7: manufactured by Perkin Elmer Japan) was used to measure the sample amount: 3 mg, the temperature increase and the rate of elevation: 10 minutes / minute.

(2) molecular weight (Mw)

It measured by GPC measuring apparatus (made by Nippon spectroscopy).

Column: TOSO GMHHR-H (S) HT

Detector: RI detector WATERS 150C for liquid chromatogram

Measuring temperature: 145 ℃

Solvent: 1,2,4-trichlorobenzene

Sample concentration: 2.2 mg / ml

The weight average molecular weight (Mw) used the polystyrene conversion value calculated | required from the calibration curve of standard polystyrene.

(3) Average particle diameter of the temperature control agent

The cross section of the pellet of the composition was evaluated by observing with a transmission electron microscope (TEM).

[Production example]

Hereinafter, the manufacturing method of the poly advanced alpha olefin temperature regulator (1-hexadecene 1-octadecene copolymer) used by the said Example and the comparative example is shown.

Synthesis Example 1 Preparation of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium chloride (hereinafter catalyst A) ''

Under a nitrogen stream, 2.5 g (7.2 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indene) and 100 ml of ether were added to a 200 ml Schlenk bottle. It cooled to -78 degreeC, and after adding 9.0 ml (14.8 mmol) of hexane solutions (1.60 mol / L) of n-butyllithium (n-BuLi), it stirred at room temperature for 12 hours.

The solvent was distilled off, the solid obtained was washed with 20 ml of hexane, and dried under reduced pressure to obtain a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indene) as a white solid. Obtained quantitatively.

The obtained lithium salt 6.97 mmol was melt | dissolved in 50 ml of THF (tetrahydrofuran) in a Schlenk bottle, 2.1 ml (14.2 mmol) of iodine methyl trimethylsilane was slowly dripped at room temperature, and it stirred for 12 hours.

The solvent was distilled off, and 50 ml of ether was added, and it wash | cleaned with saturated aqueous ammonium chloride solution. After separating, the organic phase was dried and the solvent was distilled off to remove 3.01 g of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindene) (5.9 mmol). ) Was obtained (yield 84%).

Next, 3.04 g (5.9 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above under nitrogen stream and 50 ml of ether Was added to the Schrank bottle. It cooled to -78 degreeC, 7.4 mL (11.8 mmol) of the hexane solution (1.60 mol / L) of n-butyllithium (n-BuLi) was added, and it stirred at room temperature for 12 hours.

The solvent was distilled off and the obtained solid was wash | cleaned with 40 ml of hexane, 3.06g of lithium salts were obtained as an ether adduct. The following results were obtained as a result of obtaining this ¹ H-NMR.

3.06 g of the lithium salt obtained above was suspended in 50 ml of toluene under nitrogen stream. This was cooled to -78 degreeC, and 1.2 g (5.1 mmol) of zirconium tetrachlorides which were suspended in 20 ml of toluene in another Schrank bottle, and previously cooled to -78 degreeC were dripped. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours.

After distilling off the solvent of the reaction solution, the residue was recrystallized with dichloromethane to thereby (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl). 0.9 g (1.33 mmol) of yellow microcrystals of zirconium chloride (catalyst A) were obtained (yield 26%). As a result of this ¹ H-NMR, the following results were obtained.

Preparation Example 1

180 ml of 1-hexadecene (C16), 20 ml of 1-octadecene (C18), and 200 ml of toluene were added to a 1 liter autoclave heated and the polymerization temperature was adjusted to 120 ° C. 4 micromol of aninium tetrakispentafluoroborate was added, and 0.8 MPa of hydrogen was introduce | transduced and it superposed | polymerized for 2 hours. After completion of the polymerization reaction, the reaction product was precipitated with acetone, and then heated and dried under reduced pressure, thereby obtaining 260 g of a higher α-olefin polymer. Mw of the obtained polymer was 8500.

Preparation Example 2

360 ml of 1-hexadecene (C16) and 40 ml of 1-octadecene (C18) were added to a heat-dried 1 liter autoclave, and the polymerization temperature was 120 ° C, followed by 2.0 mmol of triisobutylaluminum and catalyst A. 4 mol of mol and dimethylanilinium tetrakispentafluoroborate were added, 0.8 Mpa of hydrogen was introduce | transduced, and it superposed | polymerized for 2 hours. After the completion of the polymerization reaction, the reactant was precipitated with acetone, and then heated and dried under reduced pressure to obtain 250 g of a higher α-olefin polymer. Mw of the obtained polymer was 10000.

Preparation Example 3

360 ml of 1-hexadecene (C16) and 40 ml of 1-octadecene (C-18) were added to a heat-dried 1 liter autoclave, and the polymerization temperature was 110 ° C, and then 2 µmol of catalyst A and dimethylanilinium tetra 4 micromol of kispentafluoroborate was added, 0.1 Mpa of hydrogen was further introduced, and it superposed | polymerized for 2 hours. After the completion of the polymerization reaction, the reactant was precipitated with acetone, and then heated and dried under reduced pressure to obtain 290 g of a higher α-olefin polymer. Mw of the obtained polymer was 15000.

Preparation Example 4

360 ml of 1-hexadecene (C16) and 40 ml of 1-octadecene (C18) were added to a 1 liter autoclave heated and dried to a polymerization temperature of 100 ° C., and then 2 µmol of catalyst A and dimethylanilinium tetrakispenta were added. 4 µmol of fluoroborate was added, and hydrogen was further introduced in 0.3 MPa to polymerize for 2 hours. After completion of the polymerization reaction, the reaction product was precipitated with acetone, and then heated and dried under reduced pressure, thereby obtaining 255 g of a higher α-olefin polymer. Mw of the obtained polymer was 20000.

Preparation Example 5

360 ml of 1-hexadecene (C16) and 40 ml of 1-octadecene (C18) were added to a heat-dried 1 liter autoclave, and the polymerization temperature was 90 ° C., 2.0 mmol of triisobutylaluminum and 2 A of catalyst A were used. 4 mol of mol and dimethylanilinium tetrakispentafluoroborate were added, 0.15 Mpa of hydrogen was introduce | transduced, and it superposed | polymerized for 2 hours. After the completion of the polymerization reaction, the reactant was precipitated with acetone, and then heated and dried under reduced pressure to obtain 280 g of a higher α-olefin polymer. Mw of the obtained polymer was 40000.

Preparation Example 6

360 ml of 1-hexadecene (C16) and 40 ml of 1-octadecene (C18) were added to a heat-dried 1 liter autoclave, and the polymerization temperature was 80 ° C., and then 2 µmol of catalyst A and dimethylanilinium tetrakispenta were added. 4 mol of fluoroborate was added, 0.2 Mpa of hydrogen was further introduced, and the polymerization was carried out for 2 hours. After the completion of the polymerization reaction, the reactant was precipitated in acetone, and then heated and dried under reduced pressure to obtain 210 g of a higher α-olefin polymer. Mw of the obtained polymer was 65,000.

Preparation Example 7

360 ml of 1-hexadecene (C16) and 40 ml of 1-octadecene (C18) were added to a 1 liter autoclave heated and dried to a polymerization temperature of 75 ° C., 2.0 mmol of triisobutylaluminum and 2 µm of catalyst A were used. 4 mol of mol and dimethylanilinium tetrakispentafluoroborate were added, 0.05 Mpa of hydrogen was introduce | transduced, and it superposed | polymerized for 2 hours. After completion of the polymerization reaction, the reactant was precipitated with acetone, and then heated and dried under reduced pressure to obtain 220 g of a higher α-olefin polymer. Mw of the obtained polymer was 100,000.

Since the heat storage composite fiber obtained from the heat storage composition of the present invention has a temperature adjusting function, the heat storage composite fiber is suitable for use in contact or non-contact around the body and for temperature control over body temperature.

Specifically, sports medical care such as ski wear, rainwear, winter medical care, socks, pantyhose, general medical care such as shirts and menswear, bedding such as cotton, gloves, shoes, furniture, artificial leather for cars, thermal insulation, cold storage It can be used for food packaging materials, building materials and the like which are required, and in particular, it can be preferably used for textile products, furniture and leather products for automobiles.

Claims (7)

A heat storage composition comprising a temperature control agent and a thermoplastic resin, The temperature regulator is a polymer, oligomer or crosslinked oligomer, The heat storage composition whose melting point of the said temperature regulator is -10-100 degreeC, latent heat is 30 J / g or more, and a weight average molecular weight is 5,000-65,000. The method of claim 1, The temperature regulating agent is dispersed and present in the thermoplastic resin, and the heat storage composition has an average particle diameter of less than 13 μm. The method according to claim 1 or 2, The heat storage composition whose ratio of the said temperature regulator which occupies for a heat storage composition is 5-70 mass%, and the ratio of the said thermoplastic resin is 30-95 mass%. The method according to any one of claims 1 to 3, The heat storage composition whose weight average molecular weights of the said temperature regulator are 5,000-30,000. The method according to any one of claims 1 to 4, The thermoplastic resin is selected from polypropylene resin, polyethylene resin, polyester resin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin and ethylene-vinyl alcohol copolymer resin. The heat storage fiber formed by melt spinning the heat storage composition as described in any one of Claims 1-5. The sheet or film which consists of a heat storage composition as described in any one of Claims 1-5.