WO2007119652A1

WO2007119652A1 - Heat-storing composition, and heat-storing fiber, sheet and film each made of the same

Info

Publication number: WO2007119652A1
Application number: PCT/JP2007/057435
Authority: WO
Inventors: Atsuhiko Ubara; Masanori Sera; Osamu Isogai; Takenori Fujimura
Original assignee: Idemitsu Technofine Co., Ltd.
Priority date: 2006-04-11
Filing date: 2007-04-03
Publication date: 2007-10-25
Also published as: KR20090004936A; CN101421358A; JPWO2007119652A1

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

Specification

Thermal storage composition, and thermal storage fiber, sheet and film comprising the same

[0001] The present invention relates to a heat storage composition, and a heat storage fiber, sheet, and Finolem obtained by processing the composition.

Background art

[0002] Various heat storage members for temperature adjustment are used for clothes and the like used in an environment where temperature changes are remarkable.

As the heat storage member for temperature control, a microphone mouth capsule in which a substance having a melting point near room temperature is sealed, or a synthetic resin containing microcapsules is spun, and the resulting heat storage fiber is used as a fabric. Is known.

[0003] As a heat storage fiber, a composite fiber having a core material composed of a paraffin wax which is a heat storage material and a polyethylene resin is proposed (Patent Document 1).

Further, a heat storage fiber has been proposed, characterized in that a composition having a temperature control function in which a heat storage material is dispersed is extended in the length direction of the yarn (Patent Documents 2 to 4). .

However, these fibers have a problem that they cannot be stably produced because yarn breakage frequently occurs during spinning.

[0004] The present applicant has proposed a heat storage composite fiber using a heat storage composition obtained by blending a heat storage material having a polymer or oligomer power, or a heat storage material composed of a crosslinked product thereof with a synthetic resin. Speak (Patent Document 5).

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

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

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

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

Patent Document 4: Japanese Translation of Special Publication 2005-503497

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-003087 [0005] The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a heat storage composition that can be processed without spinning during spinning.

Disclosure of the invention

[0006] According to the present invention, the following heat storage composition and the like are provided.

1. A heat storage composition containing a temperature adjusting agent and a thermoplastic resin, wherein the temperature adjusting agent is a polymer, an oligomer or a crosslinked oligomer, and the melting point of the temperature adjusting agent is 10 to: LOO ° C, latent heat Is a heat storage composition having a weight average molecular weight of 5,000-65,000.

2. The heat storage composition according to 1, wherein the temperature adjusting agent is dispersed in a thermoplastic resin, and the average particle size of the temperature adjusting agent is less than 13 m.

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

4. The heat storage composition according to any one of 1 to 3, wherein the temperature adjusting agent has a weight average molecular weight of 5,000 to 30,000.

5. The thermoplastic resin is a polypropylene resin, a polyethylene resin, a polyester resin, a polystyrene resin, a polyamide resin, an ABS resin, a polycarbonate resin, and an ethylene butyl alcohol copolymer resin. The heat storage composition according to any one of 1 to 4, which is a seed.

6. A heat storage fiber obtained by melt spinning the heat storage composition according to any one of 1 to 5 above.

7. A sheet or film comprising the heat storage composition according to any one of 1 to 5 above.

[0007] According to the present invention, a heat storage composition that can reduce yarn breakage during spinning can be provided. Moreover, when a sheet or film is formed using this heat storage composition, fogging and thickness change can be reduced.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The heat storage composition of the present invention includes a temperature adjusting agent and a thermoplastic resin.

The temperature adjusting agent used in the present invention is a polymer, oligomer or oligomer crosslinked product having a melting point of −10 to 100 ° C. and a latent heat of 30 j / g or more. The temperature-controlling agent has a weight average molecular weight (Mw) of 5,000 to 65,000. In the present invention, by using a temperature adjusting agent having Mw in the above range, the temperature adjusting agent is highly dispersed in the thermoplastic resin. This makes spinning The thread breakage at the time can be effectively prevented. Note that if the Mw is less than 5,000, the temperature adjusting agent may bleed on the surface of the yarn and become liquefied during use, which may cause stickiness. On the other hand, if it exceeds 65,000, the dispersibility as a temperature adjusting agent deteriorates, so that the spinning and molding processability may be lowered. Mw is preferably <5,000 to 30,000, more preferably <5,000 to 20,000.

[0009] Examples of the temperature adjusting agent that is a polymer, an oligomer and a crosslinked product of the oligomer include the following (A) to (C).

[0010] (A) A polymer composed of a main chain part X, a bond part Y and a side chain Z represented by the formula (1), wherein the side chain Z can be crystallized together. Or oligomer

[Chemical 1]

[0011] (B) a polymer comprising a main chain component composed of a main chain part X, a bond part Y and a side chain Z represented by the above formula (1), wherein the side chain Z can be crystallized with each other; Oligomer bridge (crosslinking temperature regulator).

[0012] (C) A polymer or oligomer (polyether temperature adjusting agent) having as a main component a unit having a main chain that is a polyether and side chains that can be crystallized with each other.

[0013] These temperature adjusting agents are in the desired temperature range! In the temperature adjusting agents (A) and (B), the phase change (melting, solidification) is caused by non-crystallization or crystallization of the side chain Z. In addition, in the case of the temperature adjusting agent (C), the phase change (melting and solidification) occurs due to the aggregation and dissociation of the side chain, and at that time, large latent heat is released or absorbed. Therefore, these temperature regulators absorb and melt heat when the outside air temperature rises, and release and heat solidify when the outside air temperature falls, so that fluctuations in the outside air temperature are moderated and a constant temperature is easily maintained. It functions as a temperature regulator. In addition, in the temperature adjusting agents (A) and (B), the main chain portion X of the formula (1) does not melt in the above temperature range, and in the temperature adjusting agent (B), a three-dimensional network structure is formed by crosslinking. So the shape is maintained without the whole material flowing out. It is. Moreover, these temperature control agents (A), (B) and (C) can easily adjust the melting point by adjusting the length of the side chain.

[0014] First, the temperature adjusting agents (A) and (B) will be described.

In the temperature adjusting agents (A) and (B), the main chain portion X of the formula (1) is not particularly limited as long as it does not have a structure that inhibits the crystallization of the side chain Z.

[Chemical 2]

They are at least one type selected.

The bond part Y is a part that connects the main chain part X and the side chain Z, and means a one-atom unit. The side chain Z is not particularly limited as long as it can be crystallized, but preferably includes a hydrocarbon group having 9 or more carbon atoms, and more preferably includes a linear alkyl group having 9 or more carbon atoms.

Bond and chain J chain Y—Z is preferably at least one selected from CO—O—R, 1 O—CO—R, 1 O—R, 1 CHR force, and R is 9 carbon atoms. With more hydrocarbon groups

2

More preferably a linear alkyl group having 9 or more carbon atoms.

[0015] Particularly preferably, the crystalline unit comprising the main chain part X, the bonding part Y and the side chain Z is shown in the following, polymetatalylate type, polyatarylate type, polybule ester type, polyvinyl ether type. Or it is a hydrocarbon type.

Methacrylate system Atallate system

Z Z

R: C 14 or more linear alkyl group R: C 12 or more linear alkyl group Pinyl ester type vinyl ether type

Z

R: C 9 or more linear alkyl group R: C 10 or more linear alkyl group Hydrocarbon

z

R: linear alkyl group of C 9 or more Preferred examples of the temperature control agent (A) include polydocosyl methacrylate, polyheneicosyl methacrylate, polyeicosyl acrylate, polynonadecyl acrylate, polyheptadecyl Tallylate, polypalmityl acrylate, polypentadecyl acrylate, polystearyl acrylate, polylauryl acrylate, polymyristyl acrylate, polymyristyl methacrylate, polypentadecyl methacrylate, polypalmityl methacrylate Polyheptadecyl Metatalylate, Polynonadecyl Metatalylate, Polyeicosyl Metatalylate, Polystearyl Metatalylate, Poly (palmityl z-stearyl) Metatalylate, Polybulurlaurate, Polyvinylmyristate, Polyvinylpalmitate, Polybulstear Examples thereof include rate, polylauryl vinyl ether, polymyristyl vinyl ether, polypalmityl vinyl ether, polysteryl butyl ether, poly higher α-olefin. Particularly preferred is a poly high-grade aolefin. Here, the higher a-olefin is an a-olefin having 10 or more carbon atoms, more preferably an α-olefin having 16 to 18 carbon atoms. Poly-high α-olefins may be higher α-olefin homopolymers or copolymers that contain structural units derived from higher α-olefins, and copolymers with ethylene, propylene and other olefins. It may be combined.

The content of the higher α Orefin units in poly higher α Orefin particularly preferably preferably be 50 mol ^_0/0 or instrument is 100 mol%. When the content of the higher α-olefin unit is 50 mol% or more, the crystallinity increases, so that the ability as an efficient heat storage material can be obtained.

[0017] Further, examples of preferred U and temperature adjusting agent (Β) include the cross-linked products of specific examples of the above temperature adjusting agent (Α).

[0018] Preferably, the weights of the main chain portion X, the binding portion ridge, and the side chain ridge satisfy the following formula.

Z / (X + Y + Z) ≥0.75

That is, the proportion of the side chain residues in the crystalline unit is 75% by weight or more. If it is less than 75% by weight, side chain ridges cannot be crystallized, and temperature control may not be achieved.

[0019] The temperature adjusting agents (Α) and (Β) do not impair their properties! / And can include other units within a range to exhibit a desired function.

For example, the temperature control agents (Α) and (Β) can contain hydrophilic units. These temperature adjusting agents have a high hydrophobicity because they have a long-chain hydrocarbon group as a side chain, but their hydrophilicity can be enhanced by including a hydrophilic unit. In addition, these temperature control agents When used in combination with other substances, adhesion to other substances is improved.

[0020] Monomers that form such a hydrophilic unit are not particularly limited, and include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like. The hydrophilic unit formed from 2-hydroxyethyl methacrylate is represented by the following formula (4). Further, the hydrophilic unit formed from 2-hydroxychetyl acrylate is represented by the following formula (5).

[Chemical 4]

(4) (5)

[0021] The content of the hydrophilic unit is preferably 50% by weight or less, and more preferably 30% by weight or less. If it exceeds 50% by weight, the crystallinity of the side chain Z may be lowered.

[0022] The method for producing the temperature adjusting agents (A) and (B) is not particularly limited!

For example, the temperature adjusting agent (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.

The above-described poly-higher α-olefin is preferably synthesized with a homogeneous catalyst called a so-called meta-catacene catalyst. For example, the metallocene catalyst is described in International Publication No. W 003/070790. Among them, it is particularly preferable to use a C2 symmetric and C1 symmetric transition metal compound that can synthesize a isotactic polymer. Specifically, a catalyst containing the following (a) and (b) is preferred.

(a) Bi-bridged transition metal compound

(b): (b—1) a compound capable of reacting with the transition metal compound of the above component (a) or a derivative thereof to form an ionic complex, and (b-2) at least one selected from aluminoxane force component In the presence of a polymerization catalyst, higher α-olefins with 10 or more carbon atoms are polymerized.

[0023] The above-mentioned bibridged transition metal compound is a transition metal compound having a double-bridged biscyclopentaenyl derivative as a ligand, and includes silicon in the bridging group between the ligands. Preferred examples include (1, 2, 1-dimethylsilylene) (2, 1, -dimethylsilylene) bis (3-trimethylsilylmethylindul) zirconium dichloride.

Examples of the component (b-1) include dimethylamine-tetrakispentafluorophenolate.

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

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

[0024] The temperature adjusting agent (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 together with a crosslinking agent. Examples of the cross-linking agent (monomer) that forms cross-links include polyethylene glycol (1000) diatalate, polyethylene glycol (1000) dimetatalate, ethylene glycol diatalate, ethylene glycol dimetatalate, and preferably polyethylene. Glycol

(1000) dimetatalate, ethylene glycol dimetatalate.

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. 0

If it is less than 1% by weight, the crosslinking effect hardly appears. On the other hand, even if it exceeds 20% by weight, there is almost no difference in effect.

[0025] Next, the temperature adjusting agent (C) will be described.

As described above, the temperature adjusting agent (C) is a polymer or oligomer having as a main component a unit having a main chain that is a polyether and side chains that can be crystallized with each other.

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

Specific examples of the temperature adjusting agent (C) include a polyglycerin system having a unit represented by the formula (2) or a polyalkylene glycol system having a unit represented by the formula (3).

[0026] [Chemical 5]

(twenty three)

(In the formula, R ¹ is at least one kind of hydrocarbon group having 11 or more carbon atoms, which is also selected,

R ² is at least one selected from hydrocarbon base forces having 14 or more carbon atoms. )

[0027] R ¹ or R ² is preferably a linear alkyl group having the above carbon number. Specific examples include undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group and the like. .

Particularly preferred are tridecyl group (C13), pentadecyl group (C15), heptadecyl group (

C17), heneicosyl group (C21).

[0028] For example, when R ¹ is a tridecyl group having 13 carbon atoms and R ² is a tetradecyl group having 14 carbon atoms, the temperature control agent of the present invention has units represented by formula (6) or formula (7), respectively. Have.

[0029] [Chemical 6]

[0030] In the above configuration, at a predetermined temperature, the main chain does not crystallize, but long side chains can crystallize with each other.

[0031] Examples of polyglycerin-based temperature control agents include decaglycerin lauric acid (C12) reaction product, strong glycerin-myristic acid (C14) reaction product, decaglycerin-normitic acid (C16) reaction product, decaglycerin-stearin Acid (C18) reaction product, decaglycerin-behenic acid (C22) reaction product, and the like. Among these, preferred are a decaglycerin myristic acid reaction product, a decaglycerin palmitic acid reaction product, a decaglycerin-stearic acid reaction product, and a decadalylserine-behenic acid reaction product.

[0032] Examples of the polyalkylene glycol-based temperature adjusting agent include polymers of alkylene oxides such as dodecylene oxide, tetradecylene oxide, hexadecylene oxide, and octadecylene oxide. Of these, hexadecylene oxide is preferable, Polymers such as octadecylenoxide.

[0033] The temperature adjusting agent (C) can also exhibit a desired function by changing the functional group of the side chain as long as its properties are not impaired.

For example, although the temperature adjusting agent (C) has a long chain hydrocarbon group as a side chain, it is highly hydrophobic.

By including a hydrophilic functional group such as alcohol, hydrophilicity can be enhanced. As a result, when the temperature adjusting agent is applied to a substrate or the like, adhesion to the substrate or the like is improved.

[0034] The temperature adjusting agent (C) usually has a 5% weight loss temperature in air measured by a TG-DTA measuring device, preferably 200 ° C or higher, more preferably 240 ° C or higher. Below 200 ° C, it may evaporate during the heating process. The 5% weight loss temperature is the temperature at which 5% by weight of the total temperature is reduced by heating the temperature adjustment agent (C).

[0035] The method for producing the temperature adjusting agent (C) is not particularly limited. For example, a polyglycerin-based temperature control agent uses a known esterification reaction between a hydroxyl group present in polyglycerin (polyether main chain) and a carboxyl group of rubonic acid (side chain) having a linear alkyl group. It can be manufactured from Kako.

On the other hand, the polyalkylene glycol temperature adjusting agent can be produced by ring-opening polymerization of an alkylene oxide.

[0036] In the temperature adjusting agents (A) to (C) described above, the side chain undergoes reversible crystallization and non-crystallization phase transition with a large latent heat in a predetermined temperature range, but the main chain has a force. There is no such phase transition. For this reason, it is difficult to cause bleed-out compared to wax or the like, so there is no need to use microcapsules.

[0037] The melting point of the temperature adjusting agent used in the present invention is -10 to: LOO ° C. The lower limit of this range is preferably 0 ° C, more preferably 10 ° C. The upper limit of this range is preferably 80 ° C, more preferably 50 ° C, particularly preferably 40 ° C.

When the melting point exceeds 100 ° C, these temperature adjusting agents always exist in a solid state under the daily use atmosphere, and therefore, the property of absorbing the heat of crystallization at the time of temperature rise cannot be used! , It will be difficult to fully function as a temperature regulator.

In addition, if the melting point is less than 10 ° C, these temperature adjusting agents always exist in a liquid state under the daily use atmosphere, and therefore, the property of releasing heat during solidification cannot be used. It becomes difficult to sufficiently function as a temperature control agent.

[0038] The difference between the melting point and the freezing point of the temperature adjusting agent is usually preferably within 15 ° C. When the temperature is higher than 15 ° C, the interval between heat absorption and heat dissipation is wide, so that it becomes difficult to function as a temperature adjusting agent in a desired narrow temperature range.

[0039] The latent heat of the temperature adjusting agent is 30 jZg or more, preferably 50 jZg or more, more preferably 70 jZg or more, within the above melting point range. If the latent heat is less than 30jZg, the effect as a temperature control agent may be insufficient.

[0040] In the present application, the melting point, freezing point, and latent heat are measured by differential scanning calorimetry (DSC), respectively, the melting point means the temperature at the top of the melting peak, and the freezing point means the temperature at the top of the crystallization peak. CFIS K 7121). Here, the melting point is the temperature at the top of the melting peak obtained when the temperature is once heated to a temperature higher than the end of the melting peak, cooled to a predetermined temperature, and then heated again.

[0041] The thermoplastic resin constituting the heat storage composition of the present invention preferably has a melting point of 100 ° C or higher. Specifically, polyurethane resin, acrylic resin, polyamide resin, polysalt resin resin (PVC resin), polypropylene resin, polyethylene resin, polystyrene resin, polyester resin (for example, , PET), polycarbonate resin, ethylene butyl alcohol copolymer resin, thermoplastic elastomer resin, polyphenylene sulfide resin, ABS resin and the like. Of these, polypropylene resin, polyethylene resin, polyester resin, polystyrene resin, polyamide resin, ABS resin, polycarbonate resin and ethylene vinyl alcohol copolymer resin are preferable. These may be used alone or in combination of two or more.

The thermoplastic resin may be a resin specific to wet spinning (for example, rayon).

[0042] In the heat storage composition of the present invention, the temperature adjusting agent is highly dispersed in the thermoplastic resin.

Specifically, it is preferable that the average particle diameter of the temperature adjusting agent is dispersed to less than 13 m. In the present invention, the temperature adjusting agent can be highly dispersed in the thermoplastic resin by using a temperature adjusting agent having a relatively low weight average molecular weight. As a result, yarn breakage during spinning can be greatly reduced. If the average particle size of the temperature control agent is 13 m or more, thread breakage may occur during spinning. Here, the average particle diameter of the temperature adjusting agent is a random selection of the long diameters of a plurality of dispersed temperature adjusting agents by observing the composition cross section with a transmission electron microscope of the composition (for example, pellets) before spinning. Measured and averaged. In addition, when the temperature adjustment agent is further highly dispersed and compatible with each other, the average particle size may not be measured.

[0043] The average particle diameter of the temperature adjusting agent dispersed in the heat storage composition of the present invention is more preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 0.5 μm or less. is there.

The average particle size of the temperature adjusting agent can be adjusted by controlling the molecular weight of the temperature adjusting agent, the molecular weight of the thermoplastic resin, and the like.

[0044] The ratio of the temperature adjusting agent and the thermoplastic resin in the heat storage composition of the present invention is preferably the temperature adjusting agent Z thermoplastic resin (mass%): 5Z95 to 70Z30. If the temperature adjusting agent is less than 5% by mass, the temperature control function may not be sufficiently exerted, and if it exceeds 70% by mass, sufficient dispersion may not be obtained. More preferably, it is 5-50 mass%.

[0045] The heat storage composition of the present invention may contain an epoxy group-containing acrylic polymer, a aryl ether copolymer, or the like as a compatibility improver. As a result, the compatibility between the thermoplastic resin and the temperature adjusting agent is improved, and the blending amount of the temperature adjusting agent can be increased. Further, the heat storage composition of the present invention includes various additives such as an antioxidant, a light-resistant agent, an inorganic filler (calcium carbonate, talc, etc.), a foaming agent (chemical foaming) as long as the characteristics are not impaired. Materials), anti-aging agents, antibacterial agents, antifungal agents, colorants, pigments, antistatic agents, flame retardants, processing aids, stabilizers, plasticizers, crosslinking agents, reaction accelerators, etc. it can.

[0046] The latent heat of the heat storage composition of the present invention is usually from -10 to: LOO ° C, preferably from UZg or more, more preferably from 5 jZg or more, in terms of heat storage function. If the latent heat is less than UZg, the heat storage effect may not be sufficient. Further, it is preferably −10 to 80 ° C., more preferably 0 to 50 ° C., preferably UZg or more, more preferably 5 jZg or more. Due to this characteristic, the temperature control function can be sufficiently exerted with respect to the outside air temperature and the like.

[0047] The heat storage composition of the present invention can be produced by kneading the temperature adjusting agent and the thermoplastic resin with a known method, for example, a kneading extruder.

Moreover, a heat storage fiber can be manufactured by melt-spinning the heat storage composition of this invention with a well-known etastruder type compound spinning machine. The heat storage fiber of the present invention is preferably a core sheath Structure.

In the case of the core-sheath structure, the resin constituting the sheath part is polyamide resin, polyester resin, polyurethane resin, ethylene vinyl acetate copolymer, polysalt vinylidene resin, polychlorinated resin resin. Acrylic resin, polyethylene resin, polypropylene resin, etc. can be used.

[0048] Usually, when spinning, the particle diameter of the temperature adjusting agent is preferably 1Z3 or less, more preferably 1Z5 or less, with respect to the yarn diameter (in the core-sheath structure, the diameter of the core portion).

The spinning temperature varies depending on the fiber raw material used, but is usually about 180 to 350 ° C.

[0049] It should be noted that when the above heat-storable fibers are produced, the characteristics thereof are not impaired! /, As long as the range is appropriate, a hygroscopic agent, a wetting agent, a colorant, a stabilizer, a flame retardant, an electrostatic agent Antiaging agents, antioxidants, antibacterial agents, antifungal agents, pigments, antistatic agents, flame retardants, processing aids, plasticizers, crosslinking agents, reaction accelerators, foaming agents, and the like can be added.

Further, the cross-sectional shape of the heat storage fiber is not limited to a circular shape, and may be an irregular cross-section such as a triangle or a quadrangle.

[0050] In the present invention, the temperature adjusting agent used for producing the heat storage fiber has a relatively high molecular weight as compared with the wax and the monomer, so there is no problem of evaporation or leakage. In addition, since it is an oligomer or polymer, it can be kneaded and fiberized, and can be easily processed by continuous spinning and weaving. That is, the heat storage fiber of the present invention is excellent in spinnability and easy to manufacture.

[0051] Since the core part of the heat storage fiber includes the above-mentioned temperature adjusting agent! /, The heat storage fiber generates latent heat at the melting point of the temperature adjusting agent. That is, −10˜: At LOO ° C., latent heat of preferably lj / g or more, more preferably 5jZg or more is generated. If the latent heat is less than UZg, the heat storage effect may not be sufficient. Further, it preferably generates a latent heat of −10 to 80 ° C., more preferably 0 to 50 ° C., preferably UZg or more, more preferably 5 jZg or more. With this characteristic, the temperature adjustment function can be sufficiently exerted with respect to the outside air temperature or the like.

Further, by using the above-mentioned temperature adjusting agent or thermoplastic resin as the core, the temperature adjusting agent can be uniformly dispersed in the fiber, and the variation in spinning diameter and tensile strength can be suppressed. In addition, by using the above-mentioned thermoplastic resin as the sheath, the surface of the fiber can be made the same as a conventional synthetic fiber, and processing or dyeing into a woven or knitted fabric can be performed in the same manner as before. , Easy to handle.

[0052] A 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 film mold. In the heat storage composition of the present invention, since the temperature adjusting agent is highly dispersed as described above, fogging (white turbidity) due to poor dispersion of the temperature adjusting agent is unlikely to occur.

[Example]

[0053] Hereinafter, the present invention will be described more specifically with reference to Examples.

Example 1

(1) Preparation of heat storage composition

1-Hexadecene / 1-octadecene copolymer [(C Η)-(C Η)

16 32 m 18 36 n

] (Mw = 8500) 30 wt ^_0/0, as the thermoplastic榭脂, polypropylene (Prime Polymer Co., Y2005GP) 70 wt%, was charged into an extrusion granulator (manufactured by Ikegai, Ltd.), and melt-kneading A pellet-like composition was obtained. The granulation temperature at this time was 280 ° C.

In this composition, when the dispersion state of the temperature adjusting agent was observed with a transmission electron microscope (TEM), the average particle size of the temperature adjusting agent was 0.3 m.

[0054] (2) Spinnability evaluation

The composition produced in (1) above was melted and extruded into a strand form from a mold using a kneading extruder (KCK-80, manufactured by Casey Engineering Co., Ltd.). Extrusion was performed at 240 ° C, and a strand of 2 m in height was allowed to flow down the floor. We observed whether or not this strand was broken. Evaluation was performed according to the following criteria. The results are shown in Table 1. The yarn diameter means the diameter of the cured strand. As shown in Table 1, the yarn diameter was changed from 7 μm to 1000 μm for evaluation. The yarn diameter was adjusted by adjusting the discharge rate of the extruder (screw speed, etc.).

〇: When there is no breakage in 1 minute

△: When there are less than 10 breaks per minute

X: When there are 10 or more breaks per minute

[0055] (3) Evaluation of sheet

A 500 m thick sheet was formed using a multi-layer extruder (2 types, 3 layers molding machine) (manufactured by Tanabe Plastics Machinery Co., Ltd.). Using the composition prepared in (1) above as the core oil, Polypropylene (manufactured by Prime Polymer Co., Ltd., E-203GV) was used as the resin. The molding temperature was 200 ° C, the thickness of the core was 300 µm, and the thickness of the surface layer was 150 µm. About this sheet | seat, the surface was observed visually and the following references | standards evaluated. The results are shown in Table 1.

◯: When the 10cm square sheet is clear and not cloudy

△: When there is less than 5 fog on a 10cm square sheet

X: When there are more than 6 fogs on a 10cm square sheet

[0056] Examples 2-6 Comparative Example 1

A heat storage composition was prepared and evaluated in the same manner as in Example 1 except that the molecular weight Mw of the temperature adjusting agent was changed as shown in Table 1. The results are shown in Table 1. Table 2 shows the physical properties of the temperature control agent used in each example and the average particle size in the pellet-like composition.

[0057] [Table 1]

[0058] [Table 2] Molecular weight (Mw) Melting point C) Latent heat (J / g) Average particle size (歸) Example 1 8500 27 to 29 70 0. 3 Example 2 10000 27 to 29 70 0.5 Example 3 15000 27-29 70 0 75 Example 4 20000 27-29 70 1.04 Example 5 40000 27-29 70 5. 2 Example 6 65000 27-29 70 6. 1 Comparative Example 1 100000 27-29 70 8. 2

[0059] Evaluation of the temperature adjusting agent was performed by the following method.

(1) Melting point, latent heat

Using a differential scanning calorimeter (DSC-7: manufactured by PerkinElmer Japan Co., Ltd.), the sample amount was 3 mg, the temperature was raised and the temperature was lowered at a rate of 10 minutes and Z minutes.

(2) Molecular weight (Mw)

It measured with the GPC measuring apparatus (made by JASCO Corporation).

'Column: TOSO GMHHR— H (S) HT

'Detector: RI detector for liquid chromatogram WATERS 150C

'Measurement temperature: 145 ° C

'Solvent: 1, 2, 4 Trichlorobenzene

• Sample concentration: 2.2mg / ml

As the weight average molecular weight (Mw), a polystyrene conversion value obtained from a standard polystyrene calibration curve was used.

(3) Average particle size of temperature control agent

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

[0060] [Production Example]

Hereinafter, the production method of the poly higher OC olefin fin temperature adjusting agent (1 hexadecene 1-year-old kutadecene copolymer) used in the above Examples and Comparative Examples will be shown.

Synthesis Example 1 “(1,2, -Dimethylsilylene) (2,1, -dimethylsilylene) bis (3 trimethylsilane” Production of (rulymethylindul) zirconium chloride (hereinafter referred to as 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. After cooling to -78 ° C and adding 9.0 ml (14.8 mmol) of n-butyllithium (n-BuLi) in hexane (1.60 mol Z liter), stirring at room temperature for 12 hours did. The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane and dried under reduced pressure to obtain lithium (1,2, -dimethylsilylene) (2,1, -dimethylsilylene) bis (indene). The salt was obtained quantitatively as a white solid.

6. 97 mmol of the resulting lithium salt is dissolved in 50 ml of THF (tetrahydrofuran) in a Schlenk bottle, and 2.1 ml (14.2 mmol) of odomethyltrimethylsilane is slowly added dropwise at room temperature, Stir for 12 hours.

The solvent was distilled off, and 50 ml of ether was added and washed with a saturated aqueous ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was distilled off to obtain (1, 2'-dimethylsilylene) (2,1, monodimethylsilylene) bis (3-trimethylsilylmethylindene) 3.04 g (5. 9 mmol) was obtained (84% yield).

Next, in a nitrogen stream, (1, 2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) 3.04 g (5.9 mmol) obtained above was obtained. I put 50 ml of one ter in a Schlenk bottle. — Cool to 78 ° C, add 7.4 ml (11.8 mmol) of n-butyllithium (n-BuLi) in hexane (1.68 mol Z liter), then stir at room temperature for 12 hours .

The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to obtain 3.06 g of a lithium salt as an ether-attached body. When the ¹ H-NMR was determined, the following results were obtained.

— NMR (90 MHz, THF— d8): δ 0.04 (s, — SiMe, 18H), 0.48 (s, — M

Three

e Si-, 12H), 1. 10 (t, — CH, 6H), 2. 59 (s, — CH-, 4H), 3. 38 (q, — C

2 3 2

H-, 4H), 6. 2- 7. 7 (m, Ar— H, 8H)

2

Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 ml of toluene. Cool this down to -78 ° C, and then add 20 ml of toluene in another Schlenk bottle Suspension and 1.2 g (5.1 mmol) of tetrachloride-zirconium previously cooled to −78 ° C. were added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours.

After the solvent of the reaction solution was distilled off, the residue was recrystallized with dichloromethane to obtain (1, 2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindul) zirconium chloride ( 0.9 g (l. 33 mmol) of yellow fine crystals of catalyst A) were obtained (yield 26%). When ¹ H-NMR was obtained, the following results were obtained.

— NMR (90MHz, CDC1): δ 0. 0 (s, — SiMe, 18H), 1.02, 1.12 (s,-

3 3

Me Si-, 12H), 2. 51 (dd, — CH-, 4H), 7. 1— 7. 6 (m, Ar— H, 8H)

twenty two

[0063] Production Example 1

1-hexadecene (C16) 180ml, 1-year-old Kutadecene (C18) 20midgenore, 200-200g 2 micromoles of A, 4 micromoles of dimethyl-arium tetrakispentafluoroborate, 0.8 MPa of hydrogen were further introduced, and polymerization was performed for 2 hours. After the completion of the polymerization reaction, the reaction product was precipitated with acetone and then dried under heating and reduced pressure to obtain 260 g of a higher α-olefin polymer. Mw of the obtained polymer was 8500 o

[0064] Production Example 2

Add 1 ml of hexadecene (C16) 360 ml and 1-octadecene (C18) 40 ml to a heat-dried 1 liter autoclave, bring the polymerization temperature to 120 ° C, and then add 2.0 mmol of triisobutylaluminum and 2 of catalyst A. Micromol, dimethylaureum tetrakis pentafluoroborate were added in 4 micromol, hydrogen was further introduced at 0.8 MPa, and polymerization was carried out for 2 hours. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 250 g of a higher α-olefin polymer. M w of the obtained polymer was 10,000.

[0065] Production Example 3

Add 1 ml of hexadecene (C16) 360 ml and 1-octadecene (C18) 40 ml to a heat-dried 1 liter autoclave and bring the polymerization temperature to 110 ° C. Tetrakis pentafunoleborate 4 micro monolayer In addition, hydrogen was further introduced at 0. IMPa and polymerized for 2 hours. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 290 g of a higher α-olefin polymer. Mw of the obtained polymer was 15000.

[0066] Production Example 4

Add 1 ml of hexadecene (C16) 360 ml and 1-octadecene (C18) 40 ml to a heat-dried 1 liter autoclave, bring the polymerization temperature to 100 ° C, then add 2 μmol of catalyst A, dimethylenorea-linium. Tetrakispentafluororeborate was added in 4 micromonolayers, hydrogen was further introduced at 0.3 MPa, and polymerization was carried out for 2 hours. After the completion of the polymerization reaction, the reaction product was precipitated with aceton and then dried under heating and reduced pressure to obtain 255 g of a higher α-olefin polymer. Mw of the obtained polymer was 20000.

[0067] Production Example 5

Add 1 ml of hexadecene (C16) 360 ml and 1-octadecene (C18) 40 ml to a heat-dried 1 liter autoclave, bring the polymerization temperature to 90 ° C, then add 2.0 mmol of triisobutylaluminum and 2 of catalyst A. Four micromoles of micromolar and dimethylaureum tetrakis benzofluoroborate were added, 0.15 MPa of hydrogen was further introduced, and polymerization was performed for 2 hours. After the completion of the polymerization reaction, the reaction product was precipitated with acetone and then dried under heating and reduced pressure to obtain 280 g of a higher α-olefin polymer. Mw of the obtained polymer was 40000.

[0068] Production Example 6

Add 1 ml of hexadecene (C16) 360 ml and 1-octadecene (C18) 40 ml to a heat-dried 1 liter autoclave to bring the polymerization temperature to 80 ° C, then add catalyst A to 2 micromoles of dimethylmetallium. Tetrakispentafluoroborate was added at 4 micromolar, and hydrogen was further introduced at 0.2 MPa, followed by polymerization for 2 hours. After completion of the polymerization reaction, the reaction product was precipitated with acetone, and then dried under heating and reduced pressure to obtain 210 g of a higher α-olefin polymer. It was Mw 65,000 of the obtained polymer.

[0069] Production Example 7

Add 1 ml of hexadecene (C16) 360 ml and 1-octadecene (C18) 40 ml to a 1 liter autoclave that has been dried by heating, and bring the polymerization temperature to 75 ° C. 2.0 millimoles of aluminum, 2 micromoles of catalyst A, 4 micromoles of dimethylaureum tetrakis benzofluoroborate, 0.05 ppm of hydrogen were further introduced, and polymerization was conducted for 2 hours. After completion of the polymerization reaction, the reaction product was precipitated with acetone and then dried under heating and reduced pressure to obtain 220 g of a higher α-olefin polymer. Mw of the obtained polymer was 100,000.

Industrial applicability

Since the heat storage composite fiber obtained from the heat storage composition of the present invention has a temperature adjustment function, it is suitable for temperature adjustment with respect to body temperature by using it in contact with or non-contact with the surroundings of the body.

Specifically, sports clothing such as skiwear and rainwear, winter clothing, socks, pantyhose, shirts, suits such as suits, bedding such as batting, gloves, shoes, furniture, artificial leather for automobiles, It can be used for food packaging materials, building materials, etc. that are required to be kept warm and cold, and particularly suitable for textile products, furniture, and leather products for automobiles.

Claims

The scope of the claims

[1] A heat storage composition comprising a temperature adjusting agent and a thermoplastic rosin,

The temperature adjusting agent is a polymer, an oligomer or a cross-linked oligomer,

The temperature adjusting agent has a melting point of 10 to 100 ° C., a latent heat of 30 jZg or more, and a weight average molecular weight of 5, 0.

Thermal storage composition that is 00-65,000.

[2] The heat storage composition according to claim 1, wherein the temperature adjusting agent is present dispersed in a thermoplastic resin, and the average particle size of the temperature adjusting agent is less than 13 m.

[3] The heat storage composition according to claim 1 or 2, wherein the ratio of the temperature adjusting agent 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 claims 1 to 3, wherein the temperature-controlling agent has a weight average molecular weight of 5,000 to 30,000.

[5] 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 heat storage composition according to any one of claims 1 to 4, which is a seed.

[6] Claims 1-5! A heat storage fiber formed by melt spinning the heat storage composition according to any one of the above.

[7] A sheet or film comprising the heat storage composition according to any one of claims 1 to 5.