JPWO2012161278A1 - Thermal storage material composition, thermal storage material, and thermal storage device - Google Patents

Abstract

[PROBLEMS] A composition for a heat storage material and a heat storage material that are excellent in fluidity at the time of molding, have a low bleed property of paraffin compounds even in a high temperature region and have excellent shape retention, and a heat storage device obtained by using the composition I will provide a. [Solution] The hydrogenated conjugated diene copolymer comprises (i) a hydrogenated conjugated diene copolymer, (ii) a paraffin compound, and (iii) a crystalline polyolefin different from the hydrogenated conjugated diene copolymer. The copolymer (i) includes a structural unit (a-1) derived from a conjugated diene compound, a polymer block (A) having a vinyl bond content of less than 30 mol%, and a structural unit derived from a conjugated diene compound ( a heat storage material, which is a polymer obtained by hydrogenating a block copolymer (i-1) having a polymer block (B) having a vinyl bond content of 30 to 95 mol%, including b-1) Composition.

Description

  The present invention relates to a heat storage material composition, a heat storage material, and a heat storage device.

  A heat storage material composed of a composition for a heat storage material is a material containing a substance having a large heat capacity, and heat can be stored in the substance and the heat can be taken out as needed. Various types of heat storage materials such as air conditioners in residences, hotels, airports, underground shopping areas, canisters for automobiles, electronic parts, refrigerators, thermos, etc. It is used in the field of

  Conventionally, a heat storage material using water is common. However, when water is used as the heat storage material, only sensible heat due to the specific heat of the substance is often used. For this reason, heat storage materials that can also use latent heat due to phase change have attracted attention.

  There is a paraffin compound as a compound that can utilize latent heat due to phase change. However, in order to maintain a form that does not leak when the paraffin compound is fluidized, it is necessary to store the paraffin compound in a sealed container or bag. In this case, if a container having sufficient strength is used, the cost increases, which is not practical. In addition, if a simple container or the like is used, the container or the like may be easily damaged, and the paraffin compound may leak or overflow, which causes a problem in long-term use.

  As a composition for a heat storage material that solves such a problem, a composition for a heat storage material mainly composed of a paraffin compound and a thermoplastic elastomer is disclosed (for example, see Patent Document 1). This heat storage material composition has a high level of latent heat with a heat of fusion of 30 kcal / kg or more (126 kJ / kg or more) measured in accordance with JIS K-7122 in the operating temperature range, and is a paraffin compound as a component No phase separation or paraffin compound bleed even above the melting point of the above, and it is not brittle even below the melting point of the paraffin compound (the paraffin compound presents a solid state), and it does not crack even when molded into a sheet form. Has flexibility.

  However, the composition for a heat storage material composed of a paraffin compound and a thermoplastic elastomer as disclosed in Patent Document 1 has a problem of poor fluidity during molding. This is because a styrene-ethylene / butylene-styrene copolymer is used as a thermoplastic elastomer having a function of immobilizing paraffin compounds. This is thought to be due to aggregation. If the fluidity at the time of forming the heat storage material is poor, it is difficult to make the heat storage material into a precise shape, or the productivity is deteriorated.

  Moreover, the composition for thermal storage materials which consists of a paraffin compound, hydrocarbon rubber, and crystalline polyolefin is disclosed as another thermal storage material composition (for example, refer patent document 2). This composition for a heat storage material is said to be able to achieve shape retention while having appropriate flexibility in combination with crystalline polyolefin and hydrocarbon rubber.

  However, even in the composition for a heat storage material including the crystalline polyolefin as disclosed in Patent Document 2, when a hydrocarbon rubber such as ethylene / propylene rubber is used, the paraffin compound bleeds. .

JP-A-3-66788 JP-A-3-66789

  An object of the present invention is obtained by using a composition and a heat storage material for a heat storage material that are excellent in fluidity at the time of molding, have low bleed properties of paraffin compounds even in a high temperature region, and have excellent shape retention, and the composition. The object is to provide a heat storage device.

  The present inventors diligently studied to solve the above problems. As a result, in the composition for a heat storage material containing a specific hydrogenated conjugated diene copolymer, a paraffin compound, and a crystalline polyolefin, the above problem is caused by the compatibility between the crystalline polyolefin and the hydrogenated conjugated diene copolymer. As a result, the present invention has been completed.

According to this invention, the composition for thermal storage materials, the thermal storage material, and the apparatus for thermal storage shown below are provided.
[1] containing (i) a hydrogenated conjugated diene copolymer, (ii) a paraffin compound, and (iii) a crystalline polyolefin different from the hydrogenated conjugated diene copolymer, The polymer (i) includes a structural unit (a-1) derived from a conjugated diene compound, a polymer block (A) having a vinyl bond content of less than 30 mol%, and a structural unit derived from a conjugated diene compound (b -1), a polymer obtained by hydrogenating a block copolymer (i-1) having a polymer block (B) having a vinyl bond content of 30 to 95 mol%, for a heat storage material Composition.
[2] The above-mentioned [1], wherein the crystalline polyolefin (iii) is a compound having a melting point equal to or higher than that of the paraffin compound (ii) when measured by a differential scanning calorimetry (DSC method). Composition for heat storage material.
[3] The mass conversion ratio ((A) / (B)) of the polymer block (A) and the polymer block (B) in the block copolymer (i-1) is 5/95 to 50-50. The composition for a heat storage material according to [1] or [2], which is / 50.
[4] In the block copolymer (i-1), the content ratio of the structural unit derived from the alkenyl aromatic compound is 30% by mass or less based on the block copolymer (i-1). The composition for heat storage materials as described in any one of 1] to [3].
[5] Any of [1] to [4], wherein the structural unit (a-1) in the polymer block (A) contains 95 to 100% by mass of a structural unit derived from 1,3-butadiene. The composition for heat storage materials according to one item.
[6] The melting point of the paraffin compound (ii) measured by differential scanning calorimetry (DSC method) is in the range of −30 to 130 ° C., according to any one of [1] to [5]. The composition for heat storage materials as described.
[7] The composition for a heat storage material according to any one of [1] to [6], wherein the crystalline polyolefin (iii) is crystalline polyethylene.
[8] The composition for a heat storage material according to any one of [1] to [7], further including a filler (iv).
[9] A heat storage material formed from the composition for heat storage material according to any one of [1] to [8].
[10] A heat storage device obtained by filling a container with the composition for a heat storage material according to any one of [1] to [8].

  According to the present invention, the heat storage material composition and the heat storage material, which are excellent in fluidity during molding, have low bleed properties of paraffin compounds even in a high temperature region and have excellent shape retention, and the composition, can be obtained. An apparatus for heat storage can be provided.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

I. Composition for heat storage material The composition for heat storage material of the present invention has different crystallinity from the hydrogenated conjugated diene copolymer (i), the paraffin compound (ii), and the hydrogenated conjugated diene copolymer (i). Containing polyolefin (iii).

  In the composition for a heat storage material of the present invention, since the hydrogenated conjugated diene copolymer (i) is compatible with the crystalline polyolefin (iii) having a high melting point, the paraffin compound (ii) can be used even in a high temperature region. Low bleeding and excellent shape retention. Moreover, since the composition for heat storage materials of this invention contains hydrogenated conjugated diene copolymer (i), it shows the fluidity | liquidity excellent in shaping | molding above melting | fusing point of crystalline polyolefin (iii). Here, the “high temperature region” is not particularly limited, but refers to a temperature region lower than the melting point of the crystalline polyolefin (iii) and higher than the melting point of the paraffin compound (ii), for example, 60 to 120 ° C., preferably 80 to 100 ° C. It is an area of the degree.

  Hereinafter, the contained components will be described.

1. Hydrogenated conjugated diene copolymer (i)
The hydrogenated conjugated diene copolymer (i) is obtained by hydrogenating the following block copolymer (i-1). Here, the block copolymer (i-1) specifically includes a structural unit (a-1) derived from a conjugated diene compound (hereinafter also simply referred to as “structural unit (a-1)”). And a polymer block (A) having a vinyl bond content of less than 30 mol% and a structural unit (b-1) derived from a conjugated diene compound (hereinafter also simply referred to as “structural unit (b-1)”). And a polymer block (B) having a vinyl bond content of 30 to 95 mol%.

  The hydrogenated conjugated diene copolymer (i) is a block copolymer having an olefin crystal block and an ethylene / α-olefin copolymer block as described later. The ethylene / α-olefin copolymer block is preferably an ethylene / butylene copolymer block.

  In the present specification, the “structural unit derived from a compound” usually means a structural unit based on the reaction of a polymerizable double bond moiety of the compound. Hydrogenation is also referred to as “hydrogenation”. The conjugated diene compound forming the structural unit (a-1) is also referred to as “first conjugated diene compound”, and the conjugated diene compound forming the structural unit (b-1) is also referred to as “second conjugated diene compound”. Say.

  The hydrogenated conjugated diene copolymer (i) having the above structure is highly compatible with the crystalline polyolefin (iii) as compared with the ethylene / propylene rubber and the styrene elastomer having styrene blocks at both ends, and Also, it has excellent fluidity when molding a heat storage material.

<Block copolymer (i-1)>
(1) Polymer block (A)
Examples of the first conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3. -Hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene. Among these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable in order to obtain a composition for a heat storage material that can be industrially used and has excellent physical properties. In addition, the 1st conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.

  The structural unit (a-1) is preferably a structural unit containing 95 to 100% by mass of a structural unit derived from 1,3-butadiene, and is a structural unit composed only of a structural unit derived from 1,3-butadiene. It is particularly preferred.

  The content ratio of the structural unit (a-1) in the polymer block (A) is preferably 95% by mass or more based on the polymer block (A) from the viewpoint of maintaining fluidity during the molding process of the heat storage material. More preferably, the combined block (A) is composed of only the structural unit (a-1).

  The vinyl bond content in the polymer block (A) is less than 30 mol%, preferably 20 mol, from the viewpoint of maintaining shape retention in a high temperature region when the heat storage material is formed using the composition for heat storage material. %, More preferably 18 mol% or less. The lower limit of the vinyl bond content in the polymer block (A) is not particularly limited.

  In this specification, “vinyl bond content” means a conjugate that is incorporated in a polymer block before hydrogenation in a 1,2-bond, 3,4-bond, or 1,4-bond bond mode. It is a total ratio (on a mol% basis) of conjugated diene compounds incorporated in a 1,2-bond and 3,4-bond bonding mode among diene compounds.

(2) Polymer block (B)
As the second conjugated diene compound, for example, the same compound as the first conjugated diene compound described above can be used, and preferred compounds are also the same. The second conjugated diene compound and the first conjugated diene compound may be the same or different.

  For example, when the first conjugated diene compound and the second conjugated diene compound are the same, the bonding state of each conjugated diene compound, that is, the bonding state of 1,2-bond or 3,4-bond, A polymer block (A) and a polymer block (B) having different vinyl bond contents can be formed by adjusting the bonding state of 4-bonds.

  The polymer block (B) is a polymer block containing the structural unit (b-1) derived from the second conjugated diene compound and obtains an effect of imparting softening to the composition for a heat storage material, or From the viewpoint of preventing crystallization of the combined block (B), a structural unit derived from an alkenyl aromatic compound (hereinafter referred to as “structural unit (b-2)”) within a range not impeding the fluidity of the composition for heat storage material. It may be a polymer block further comprising:

  The structural unit (b-1) is preferably a structural unit containing a total of 95 to 100 mass% of structural units derived from 1,3-butadiene and / or isoprene, and includes 1,3-butadiene and / or isoprene. More preferably, it is a structural unit consisting only of the derived structural unit.

  The content ratio of the structural unit (b-1) in the polymer block (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to the polymer block (B). .

  When the polymer block (B) further includes the structural unit (b-2), the content ratio of the structural unit (b-2) is determined from the viewpoint of maintaining fluidity during the heat processing of the heat storage material. ) Is preferably 50% by mass or less.

  The mass ratio of the structural unit (b-1) / structural unit (b-2) in the polymer block (B) is preferably 100/0 to 50/50, more preferably 100/0 to 70/30, and even more preferably. Is 100/0 to 80/20.

  Examples of the alkenyl aromatic compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, N, N-diethyl-p-aminostyrene, and vinylpyridine. Among these, styrene and α-methylstyrene are preferable. In addition, when the polymer block (B) is a copolymer block including the structural unit (b-1) and the structural unit (b-2), the distribution of the structural unit (b-1) is random and tapered. (The structural unit (b-1) increases or decreases along the molecular chain), a partial block shape, or any combination thereof.

  The vinyl bond content in the polymer block (B) is 30 to 95 mol%, preferably 30 to 85 mol%, more preferably 40 to 75 mol%. From the viewpoint of preventing bleeding of the paraffin compound (ii) when the heat storage material is formed using the composition for heat storage material, the vinyl bond content in the polymer block (B) is preferably 30 mol% or more.

(3) Polymer block (C)
The block copolymer (i-1) includes, in addition to the polymer block (A) and the polymer block (B), a structural unit derived from an alkenyl aromatic compound (hereinafter referred to as “structural unit (c-1)”). The polymer block (C) containing more than 50% by mass, preferably a polymer block (C) consisting only of the structural unit (c-1). In this case, the block copolymer (i-1) preferably has a block configuration of polymer block (A) -polymer block (B) -polymer block (C).

  Examples of the alkenyl aromatic compound in the structural unit (c-1) include the same compounds as the alkenyl aromatic compound in the structural unit (b-2), and preferred compounds are also the same.

(4) In the block constituent block copolymer (i-1), the mass conversion ratio ((A) / (B)) of the polymer block (A) and the polymer block (B) is usually 5/95. -50/50, preferably 10 / 90-40 / 60. From the viewpoint of securing shape retention in a high temperature region when the heat storage material is formed using the heat storage material composition, the ratio of the polymer block (A) is 5 or more, and the ratio of the polymer block (B) is 95. The following is preferable. On the other hand, from the viewpoint of preventing bleeding of the paraffin compound (ii) when the heat storage material is formed using the heat storage material composition, the ratio of the polymer block (A) is 50 or less, and the ratio of the polymer block (B). Is preferably 50 or more.

  When the block copolymer (i-1) further has a polymer block (C), the polymer block (A) and the ratio in terms of mass of the polymer block (B) and the polymer block (C) ({( A) + (B)} / (C)) is usually 80/20 to 99/1, preferably 85/15 to 95/5. From the viewpoint of maintaining workability during melting (fluidity during molding), the ratio of the polymer block (C) is preferably 20 or less.

  In the block copolymer (i-1), the content ratio of the structural unit derived from the alkenyl aromatic compound is relative to the block copolymer (i-1) from the viewpoint of maintaining fluidity during the molding process of the heat storage material. It is preferably 30% by mass or less, and more preferably 20% by mass or less. Here, the content ratio of the structural unit derived from the alkenyl aromatic compound is, for example, that of the structural unit (b-2) in the polymer block (B) and the structural unit (c-1) in the polymer block (C). Refers to the total content (of course, either may not be included).

  The block copolymer (i-1) may have any structure as long as it satisfies the above requirements, and examples thereof include structures represented by the following structural formulas (1) to (6).

Structural formula (1): ( _AB ) _n1
Structural formula (2): ( _AB ) _n2 -A
Structural formula (3): ( _BA ) _n3 -B
Structural formula (4): ( _ABC ) _n4
Structural formula (5): A- ( _BC ) _n5
Structural formula (6): ( _AB ) _n6 -C
In structural formulas (1) to (6), A represents a polymer block (A), B represents a polymer block (B), C represents a polymer block (C), and n1 to n6 are 1 or more. Indicates an integer.

  Here, in the block copolymers represented by the structural formulas (1) to (6), at least one of the polymer block (A), the polymer block (B), and the polymer block (C) is 2 or more. When present, each polymer block may be the same or different.

  The block copolymer (i-1) has a structure in which the copolymer block is extended via a coupling agent residue, such as the structures represented by the following structural formulas (7) to (12). Alternatively, it may be branched.

Structural formula (7): (AB) _m X
Structural formula (8): (BA) _m X
Structural formula (9): (ABA) _m X
Structural formula (10): (BAB) _m X
Structural formula (11): (ABC) _m X
Structural formula (12): (ABC) X (CB)
In structural formulas (7) to (12), A represents the polymer block (A), B represents the polymer block (B), C represents the polymer block (C), and m represents an integer of 2 or more. And X represents a coupling agent residue.

  The structure of the block copolymer (i-1) is represented by the structural formula (1), (2), (4) or (7) among the structures represented by the structural formulas (1) to (12). The structure is preferred. Since the shape retention in the composition for heat storage material and the heat storage material to be obtained is excellent and the bleedability of the paraffin compound (ii) is low, the block copolymer (i) having the polymer block (A) on the outer side or both ends (i) -1) is preferred.

  The coupling rate in the block copolymer (i-1) is preferably 50 to 90% in consideration of the workability of the heat storage material and the bleeding property of the paraffin compound (ii). In addition, let the ratio by which a molecule | numerator is connected through a coupling agent be a coupling rate.

  Examples of the coupling agent include 1,2-dibromoethane, methyldichlorosilane, dimethyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, benzene- 1,2,4-triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchlorosilane, 1,4 -Chloromethylbenzene, bis (trichlorosilyl) ethane.

  The block copolymer (i-1) can be produced, for example, by the methods described in Japanese Patent Nos. 3134504 and 3360411.

As the block copolymer (i-1), the above block copolymers can be used alone, or two or more block copolymers can be mixed and used. Examples of combinations of the block copolymers (i-1) include ABA / AB, (AB) _2- X / AB, and (AB) _4- X / A-. B, (AB) _4- X / (AB) _2- X / AB, (AB) _4- X / (AB) _3- X / (AB) _2- X / A-B, A-B-C / A-B, (A-B-C) ₂ / A-B, (A-B-C) ₂ -X / A-B (where A is a polymer block) (A), B represents a polymer block (B), C represents a polymer block (C), and X represents a coupling agent residue.

<Physical properties of hydrogenated conjugated diene copolymer (i)>
The hydrogenated conjugated diene copolymer (i) preferably has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of 10,000 to 700,000, and more preferably 100,000 to 500,000. , 200,000 to 500,000 is particularly preferable. In order to obtain required mechanical properties, Mw is preferably 10,000 or more, and Mw is preferably 700,000 or less in order to ensure fluidity for molding the heat storage material.

  The hydrogenated conjugated diene copolymer (i) preferably has a melting point measured by a differential scanning calorimetry (DSC method) in the range of 70 to 140 ° C, and preferably in the range of 80 to 120 ° C. More preferred. In addition, the melting point of the hydrogenated conjugated diene copolymer (i) in the present specification corresponds to the extrapolation melting start temperature (Tim) at the crystal melting peak when measured according to JIS K-7121.

  The value of the melt flow rate (hereinafter also referred to as “MFR”) of the hydrogenated conjugated diene copolymer (i) is not particularly limited, but is generally preferably 0.01 to 100 g / 10 min. In addition, in this specification, MFR of hydrogenated conjugated diene copolymer (i) is the value measured by 230 degreeC and the load of 10 kg based on JISK-7210.

The hydrogenated conjugated diene copolymer (i) can be used alone or in combination of two or more hydrogenated conjugated diene copolymers (i). Examples of combinations of the hydrogenated conjugated diene copolymer (i) include: A-B-A hydrogenated product / A-B hydrogenated product, (A-B) ₂ -X hydrogenated product / A- B hydrogenated product, (AB) ₄ -X hydrogenated product / AB hydrogenated product, (AB) ₄ -X hydrogenated product / (AB) ₂ -X water Additives / A-B hydrogenated products, (AB) ₄ -X hydrogenated products / (AB) ₃ -X hydrogenated products / (AB) ₂ -X hydrogenated products / A-B hydrogenated product, A-B-C hydrogenated product / A-B hydrogenated product, (ABC) ₂ hydrogenated product / A-B hydrogenated product, (A- B-C) _2- X hydrogenated product / AB hydrogenated product (where A represents the polymer block (A), B represents the polymer block (B), and C represents the polymer block ( C), and X represents a coupling agent residue.

  The polymer block (A) is a polymer block having a vinyl bond content of less than 30 mol%. Therefore, the polymer block (A) becomes a structure similar to polyolefin having good crystallinity by hydrogenation, that is, an “olefin crystal block”. For example, when the first conjugated diene compound is 1,3-butadiene, the structure is similar to polyethylene with good crystallinity.

  The polymer block (B) is a polymer block having a vinyl bond content of 30 to 95 mol%. Therefore, the polymer block (B) becomes a structure similar to an ethylene / α-olefin copolymer by hydrogenation, that is, an “ethylene / α-olefin copolymer block”. For example, when the second conjugated diene compound is 1,3-butadiene, it has a structure similar to a rubbery ethylene-butylene copolymer and becomes a soft polymer block.

  The resulting heat storage material composition and the heat storage material are excellent in shape retention, and the bleedability of the paraffin compound (ii) is reduced. Therefore, the hydrogenated conjugated diene copolymer having the olefin crystal block on the outer side or both ends (i ) Is preferred.

  For example, when the first and second conjugated diene compounds are 1,3-butadiene, the hydrogenated conjugated diene copolymer (i) has an olefin crystal-ethylene / butylene-olefin crystal block polymer structure. When the hydrogenated conjugated diene copolymer (i) having such a structure is used, the crystalline polyolefin (iii) and the hydrogenated conjugated diene copolymer (i) are compatible with each other. It is possible to provide a composition for a heat storage material capable of producing a heat storage material having excellent fluidity.

<Method for Producing Hydrogenated Conjugated Diene Copolymer (i)>
The production method of the hydrogenated conjugated diene copolymer (i) is not particularly limited. For example, after preparing the block copolymer (i-1), the prepared block copolymer (i-1) is prepared. It can be produced by hydrogenation. For example, the block copolymer (i-1) is obtained by subjecting the first conjugated diene compound to living anion polymerization using an organic alkali metal compound as a polymerization initiator in an inert organic solvent, and then the second conjugated diene compound and If necessary, it can be prepared by further adding an alkenyl aromatic compound and conducting living anionic polymerization.

  Examples of the inert organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; benzene, xylene, toluene, An aromatic hydrocarbon solvent such as ethylbenzene can be used.

  In addition, when introducing a coupling agent residue into the block copolymer, the second conjugated diene compound can be simply reacted by adding a coupling agent without performing an operation such as isolation after living anion polymerization. Can be introduced.

  In living anionic polymerization, the vinyl bond content of polymer block (A) and polymer block (B) is combined with ether compounds, tertiary amines, alkoxides of alkali metals (sodium, potassium, etc.), phenoxides, sulfonates, etc. And it can control easily by selecting the kind, usage-amount, etc. suitably.

  By hydrogenating the block copolymer (i-1), the hydrogenated conjugated diene copolymer (i) can be easily prepared. There are no particular limitations on the hydrogenation method and reaction conditions of the block copolymer (i-1), and it is usually carried out in the presence of a hydrogenation catalyst at 20 to 150 ° C. under a hydrogen pressure of 0.1 to 10 MPa. . In this case, the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time.

  Examples of the hydrogenation catalyst include JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, and JP-A-11-292924. JP 2000-37632 A, JP 59-133203 A, JP 63-5401 A, JP 62-218403 A, JP 7-90017 A, JP 43-19960 A, Examples thereof include the hydrogenation catalyst described in JP-B 47-40473. In addition, the said hydrogenation catalyst may be used only 1 type, and can also use 2 or more types together.

  The hydrogenation rate of the double bond derived from the conjugated diene compound (including the first conjugated diene compound and the second conjugated diene compound) in the hydrogenated conjugated diene copolymer (i) is determined by shape retention and mechanical properties. In order to satisfy | fill, it is preferable that it is 90% or more, and it is more preferable that it is 95% or more.

  After the hydrogenation, if necessary, the catalyst residue is removed, or a phenol-based or amine-based antioxidant is added, and then the hydrogenated conjugated diene is added from the solution containing the hydrogenated conjugated diene copolymer (i). Copolymer (i) is isolated. Isolation of the hydrogenated conjugated diene copolymer (i) can be carried out, for example, by adding acetone or alcohol to a solution containing the hydrogenated conjugated diene copolymer (i) and precipitating the solution, hydrogenated conjugated diene copolymer ( i) A solution containing i) is poured into hot water with stirring, and the solvent is distilled off. A hydrogenated conjugated diene copolymer (i) in which an appropriate amount of paraffin compound (ii) contained in the composition for a heat storage material is mixed in advance. ) Is added to hot water with stirring, and the solvent is distilled off.

2. Paraffin compound (ii)
Examples of the paraffin compound (ii) contained in the composition for a heat storage material of the present invention include a paraffin compound having 10 to 100 carbon atoms. In addition, paraffin compound (ii) may be used individually by 1 type, and may use 2 or more types together.

  As the paraffin compound (ii), a compound having an alkylene group having 12 to 30 carbon atoms is more preferable. Specifically, linear paraffin such as n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-icosane, and branched paraffin Can be mentioned.

  Petroleum wax can also be used as one embodiment of a paraffin compound having 10 to 100 carbon atoms. Examples of petroleum waxes include paraffin wax (a wax that is solid at room temperature, which is produced by separating and refining oil or natural gas as a raw material from a vacuum distillation distillate), and microcrystalline wax (a reduced pressure using petroleum as a raw material). Aliphatic hydrocarbons such as wax produced at a normal temperature by separation and purification from distillation residue oil or heavy distillate oil.

  As the paraffin wax, those having about 20 to 40 carbon atoms are preferable, and as the microcrystalline wax, those having about 30 to 60 carbon atoms are preferable in terms of heat of fusion and availability. Examples of paraffin wax products include “HNP-9”, “HNP-51”, “FNP-0090”, and “FT115” (all manufactured by Nippon Seiwa Co., Ltd.).

  The paraffin compound (ii) preferably has a melting point measured by differential scanning calorimetry (DSC method) in the range of −30 to 130 ° C. from the viewpoint of effective use of heat in the living temperature region and high temperature region. More preferably, it is in the range of -20 to 100 ° C. Further, the heat of fusion measured by the differential scanning calorimetry (DSC method) of the paraffin compound (ii) is desirably 100 kJ / kg or more from the viewpoint of utilizing latent heat due to the phase change in various fields. In addition, the melting point of the paraffin compound (ii) in the present specification corresponds to the extrapolated melting start temperature (Tim) at the crystal melting peak when measured according to JIS K-7121.

  The melting point and heat of fusion corresponding to the paraffin compound (ii) described above are shown in parentheses below. n-dodecane (-10 ° C, 185 kJ / kg), n-tetradecane (6 ° C, 230 kJ / kg), n-pentadecane (9 ° C, 165 kJ / kg), n-hexadecane (18 ° C, 230 kJ / kg), n -Heptadecane (21 ° C, 170 kJ / kg), n-octadecane (28 ° C, 240 kJ / kg), n-nonadecane (32 ° C, 170 kJ / kg), n-icosane (37 ° C, 250 kJ / kg), HNP-9 (73 ° C., 215 kJ / kg), HNP-51 (73 ° C., 215 kg / kj), FNP-0090 (80 ° C., 230 kJ / kg), FT115 (93 ° C., 245 kJ / kg).

  In the composition for a heat storage material of the present invention, the content of the paraffin compound (ii) is preferably 50 to 4000 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene copolymer (i). It is more preferably 3000 parts by mass, and still more preferably 400 to 2000 parts by mass. When the heat storage material is formed using the heat storage material composition, it is preferably 50 parts by mass or more in order to ensure sufficient latent heat, and the shape retention in the high temperature region is reduced, and the paraffin compound (ii) In order to prevent bleeding, it is preferably 4000 parts by mass or less.

3. Crystalline polyolefin (iii)
The crystalline polyolefin (iii) contained in the composition for heat storage material of the present invention will be described. In the present invention, the crystalline polyolefin (iii) and the hydrogenated conjugated diene copolymer (i) have compatibility by using the crystalline polyolefin (iii) and the hydrogenated conjugated diene copolymer (i). Thereby, the shape retainability in the high temperature area | region of the composition for thermal storage materials is improving.

  When measured by the differential scanning calorimetry (DSC method), the crystalline polyolefin (iii) has a melting point higher than that of the paraffin compound (ii) from the viewpoint of shape retention of the heat storage material in the high temperature region and bleed suppression. Preferably, it has a melting point that is 20 ° C. higher than the melting point of the paraffin compound (ii). From the same viewpoint, it is preferable to have a melting point higher than that of the hydrogenated conjugated diene copolymer (i). In addition, the melting point of the crystalline polyolefin (iii) in the present specification corresponds to the extrapolated melting start temperature (Tim) at the crystal melting peak when measured according to JIS K-7121.

  The crystalline polyolefin (iii) preferably has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of 1,000 to 10,000,000, preferably 10,000 to 5,000,000. It is more preferable that it is 10,000 to 1,000,000.

  In the description of the crystalline polyolefin (iii) in the present specification, “polyolefin” means a polymer obtained by polymerizing at least one olefin selected from ethylene and α-olefin. There is no restriction | limiting in particular about the polymerization method, For example, the polymer obtained by superposing | polymerizing by a conventionally well-known polymerization method (Example: high pressure method, low pressure method) etc. can be used.

  Examples of the α-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 3-ethyl- C3-C12 alpha olefins, such as 1-pentene, 1-octene, 1-decene, 1-undecene, are mentioned.

  Examples of the crystalline polyolefin (iii) include crystalline polyethylene, crystalline polypropylene, crystalline polybutene, and crystalline methylpentene. From the viewpoint of versatility, it is preferable to use crystalline polyethylene and crystalline polypropylene. It is particularly preferable to use crystalline polyethylene.

  Examples of crystalline polyethylene include low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene / propylene copolymer, and ethylene / octene copolymer. It is done. The crystalline polyethylene may also be biopolyethylene made from ethylene made from renewable (plant) resources.

  Examples of crystalline polypropylene include homopolypropylene, random polypropylene, propylene / α-olefin copolymer, propylene / ethylene copolymer, propylene / butene copolymer, and propylene / ethylene / butene copolymer.

  The melting point of the crystalline polyethylene measured by a differential scanning calorimetry (DSC method) is preferably 80 to 140 ° C, more preferably 90 to 140 ° C. Furthermore, crystalline polyethylene having a melting point equal to or higher than that of paraffin compound (ii) is preferred. Moreover, it is preferable that the heat of fusion measured by the differential scanning calorimetry (DSC method) of crystalline polyethylene is 50 kJ / kg or more from the viewpoint of shape retention of the heat storage material in a high temperature region.

  The melting point of crystalline polypropylene measured by differential scanning calorimetry (DSC method) is preferably 100 to 170 ° C, more preferably 120 to 170 ° C. Furthermore, crystalline polypropylene having a melting point equal to or higher than that of paraffin compound (ii) is preferred. Moreover, it is preferable that the heat of fusion measured by the differential scanning calorimetry (DSC method) of crystalline polypropylene is 50 kJ / kg or more from the viewpoint of shape retention of the heat storage material in a high temperature region.

  The melt flow rate (MFR) of crystalline polyethylene according to JIS K-7210 at a temperature of 190 ° C. and a load of 2.16 kg is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 80 g. / 10 minutes.

  The melt flow rate (MFR) of crystalline polypropylene according to JIS K-7210 at a temperature of 230 ° C. and a load of 2.16 kg is preferably 0.01 to 100 g / 10 minutes, more preferably 0.1 to 80 g. / 10 minutes.

  When the MFR of the crystalline polyethylene and the crystalline polypropylene is not less than the lower limit of the above numerical range, the moldability and the like are further improved. When the MFR is not more than the upper limit of the above numerical range, the bleed suppression of the paraffin compound (ii) is further improved.

Crystalline polyolefin (iii) may be used individually by 1 type, and may use 2 or more types together.
In the composition for a heat storage material of the present invention, the content of the crystalline polyolefin (iii) is preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene copolymer (i). 1 to 500 parts by mass, more preferably 1 to 100 parts by mass. When the content of the crystalline polyolefin (iii) is in the above range, it is preferable from the viewpoint of increasing the compatibility and suppressing bleeding of the paraffin compound (ii).

4). Other Components The composition for a heat storage material of the present invention may contain a filler (iv) within a range not impairing the effects of the present invention for the purpose of imparting a function according to the application. Examples of the filler (iv) include colorants such as titanium oxide and carbon black, metal powders such as ferrite, inorganic fibers such as glass fibers and metal fibers, organic fibers such as carbon fibers and aramid fibers, aluminum nitride, and boron nitride. , Aluminum hydroxide, Alumina, Magnesium oxide, Carbon nanotubes, Expanded graphite and other heat transfer agents, Glass beads, Glass balloons, Glass flakes, Glass fibers, Asbestos, Calcium carbonate, Magnesium carbonate, Potassium titanate whiskers, Zinc oxide whiskers And fillers such as inorganic whiskers such as talc, silica, calcium silicate, kaolin, diatomaceous earth, montmorillonite, graphite, pumice, evo powder, cotton floc, cork powder, barium sulfate, and fluororesin. From the viewpoint of heat conductivity, carbon fiber and expanded graphite are preferable. A filler (iv) may be used individually by 1 type, and may use 2 or more types together.

  In addition to the filler (iv), the composition for a heat storage material of the present invention is an antioxidant, an antioxidant, an antistatic agent, a weathering agent, an ultraviolet absorber, and an antiblocking agent as long as the effects of the present invention are not impaired. Crystal nucleating agents, flame retardants, vulcanizing agents, vulcanization aids, antibacterial / antifungal agents, dispersants, anti-coloring agents, foaming agents, rust preventing agents, and the like may be blended.

  The content of the filler (iv) varies depending on the type in order to impart the desired function, but from the viewpoint of maintaining the productivity at the time of filling the composition for a heat storage material, the composition for a heat storage material It is desirable that the content be such that the fluidity can be maintained above the melting point of the crystalline polyolefin (iii).

  The content of the filler (iv) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass with respect to 100% by mass of the heat storage material composition. 30% by mass is particularly preferred. From the viewpoint of imparting a desired function to the composition for a heat storage material, 1% by mass or more is particularly preferable. From the viewpoint of maintaining fluidity and maintaining productivity at the time of filling the composition for a heat storage material, 30 mass% or less is especially preferable.

  A compound such as silica or expanded graphite having pores is a filler (iv) from the viewpoint that the components contained in the composition for a heat storage material can penetrate into the pores and can provide a desired function with a small filling amount. As preferred.

Examples of the silica having pores include conventionally known foamed silica.
Expanded graphite having pores can be produced by a known method. For example, natural graphite, pyrolytic graphite or quiche graphite as a graphite material is immersed in a mixed acid of a strong acid such as concentrated sulfuric acid and a strong oxidizing agent such as a perchloric acid aqueous solution or nitric acid to form an intercalation compound, which is usually 100 It can be obtained by performing a heat treatment at a temperature of at least 500 ° C, preferably at least 500 ° C. Although the bulk density of expanded graphite can be adjusted by acid treatment conditions or heat treatment conditions after acid treatment, a high bulk density is obtained in advance, and this is adjusted to the desired bulk density by mechanical operation such as compression or crushing. It is also possible to do.

II. Thermal Storage Material The thermal storage material of the present invention is formed using the thermal storage material composition described in “I. Thermal Storage Material Composition”. Examples of the shape include various shapes such as a sheet shape, a granular shape, and a pellet shape. Although it does not specifically limit as a shaping | molding method of a thermal storage material, For example, it can carry out as follows.

  First, using a normal mixing / stirring machine such as a two-roll, extruder, twin-screw kneading extruder, stirring mixer, etc., hydrogenated conjugated diene copolymer (i), paraffin compound (ii) and crystallinity A composition for a heat storage material containing polyolefin (iii) is prepared. When using a stirrer, an additive such as a hydrogenated conjugated diene copolymer (i), a crystalline polyolefin (iii) and, if necessary, a filler (iv) is added to the paraffin compound (ii) in a molten state. In addition, stir. At this time, the hydrogenated conjugated diene copolymer (i) and the crystalline polyolefin (iii) are first melt mixed to obtain a mixture thereof, and then the paraffin compound (ii) is added to the mixture. A uniform heat storage material composition can be obtained. Moreover, workability | operativity will improve if hydrogenated conjugated diene copolymer (i) and crystalline polyolefin (iii) are made into a pellet form, a granular form, and a powder form before addition. The addition temperature is preferably not less than the melting point of the hydrogenated conjugated diene copolymer (i) and the crystalline polyolefin (iii), and is usually 100 to 200 ° C.

  Subsequently, the composition for a heat storage material in a solution state is molded as it is or slightly cooled. The molding may be performed by pouring into a mold to obtain a desired sheet shape or plate shape. Further, since the heat storage material is solidified when it becomes less than the melting point of the paraffin compound (ii), it may be cut into a sheet shape or a plate shape after being formed into a block shape. Further, the heat storage material composition may be attached, applied, or impregnated on a film, cloth, fiber or the like to form a sheet or plate. Further, it can be packed in a bag of polyethylene or the like and formed into a sheet shape, a plate shape, or a rod shape in the cooling process. On the other hand, if an extruder is used, it can be extruded into a sheet or plate. Further, it can be formed into a rod shape or a pipe shape by an extruder, and if a rod-like or pipe-like heat storage material is chopped, it becomes both granular and pellet-like.

III. Thermal Storage Device The thermal storage device of the present invention is obtained by filling a container with the thermal storage material composition described in “I. Thermal Storage Material Composition”. The apparatus is superior to other forms from the viewpoint of maintaining productivity, safety, and heat storage performance.

  As a container, it can select from a packaging container using a well-known material, a metal container, etc. suitably, or can use these in combination. The heat storage device of the present invention can be used in combination with known heat insulating members such as a vacuum heat insulating material, a urethane foam material, a phenol foam material, a polystyrene foam material, a glass wool material, and a rock wool material depending on the application.

  Examples of packaging container materials include films made of polyolefin resins such as polyethylene (PE) and polypropylene (PP) (polyolefin resin films), films made of polyester resins such as polyethylene terephthalate (PET) (polyester resin films), and stretching Base films known as packaging materials, such as films made of nylon (ONy), polyamide (PA), ethylene / vinyl alcohol copolymer (EVOH), etc .; metal foils for soaking, such as aluminum foil; A laminated film formed by laminating these base film and metal foil by a known laminating method is exemplified.

  As a layer structure of the packaging container, it is preferable to use a base film (heat seal layer) having heat-fusibility as the innermost layer. As a method of filling the composition for a heat storage material into a container, for example, a container containing a heat seal layer as an innermost layer is filled with the composition for a heat storage material using a known filling device, and this is then performed with a heat seal bar. A method of heat sealing and sealing (heat sealing method) is preferable in terms of productivity.

  The heat seal layer is preferably a polyolefin resin film (heat-sealable olefin layer) having heat-sealability, more preferably a PE film or PP film, and a linear low-density polyethylene (LLDPE) film from the viewpoint of productivity. Is particularly preferred.

  Since the PE film and PP film have low barrier properties against oil such as paraffin compound (ii), paraffin compound (ii) may ooze out (bleed) when a container composed of these single layers is used. is there.

  For this reason, as a form which is more preferably used in the container, a laminated film including the heat seal layer (innermost layer) and a layer (oil-resistant polar resin layer) made of an oil-resistant polar resin (oil-resistant polar resin) is provided. Can be mentioned.

  Examples of the oil-resistant polar resin layer in the laminated film include a PA film and a PET film. By covering the heat seal layer (innermost layer) with an oil-resistant polar resin layer, oil bleed can be further prevented.

  The film thickness of each layer of the heat seal layer and the oil-resistant polar resin layer is preferably 50 μm or more in the heat seal layer from the viewpoint of sufficiently exhibiting the functions of each layer and obtaining mechanical strength. Is 50 to 200 μm, and in the oil-resistant polar resin layer, it is preferably 10 μm or more, and more preferably 10 to 100 μm. Moreover, in order to give these layers further functionality, a heat-resistant resin film or a gas barrier resin film can be laminated.

  Specific examples include containers having the following layer structure. In the following examples of layer configuration, the outermost layer to the innermost layer are sequentially arranged from the left side, and the “film” may be omitted in the PE film or the like, and the base film shown in parentheses is The base film described on the left side can be used instead.

(1) PA / PE (PP)
The film thickness of each substrate film is preferably 50 μm or more in PE and PP, and preferably 10 μm or more in PA.

(2) PET / PA / PE (PP)
Depending on the use mode of the heat storage device of the present invention, the container may be required to have further heat resistance. When PA is used as a substrate film, it is preferable to further cover the outside with PET for the purpose of supplementing heat resistance. The film thickness of each substrate film is preferably 50 μm or more in PE and PP, preferably 10 μm or more in PA, and preferably 10 μm or more in PET.

(3) PET (PA) / EVOH / PA / PE (PP)
Among paraffin compounds (ii) that are components of the composition for a heat storage material of the present invention, a highly volatile material such as tetradecane may pass through the PA. In this case, the container uses EVOH as a gas barrier layer. It is preferable to further provide. The film thickness of each substrate film is preferably 50 μm or more for PE and PP, 10 μm or more for PA, 10 μm or more for EVOH, and preferably 10 μm or more for PET.

  In addition, when obtaining a container using the base film described in said (1)-(3), well-known methods, such as a co-extrusion method, a dry lamination method, and a heat seal method, are used.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. In addition, measurement methods for various physical properties and evaluation methods for various properties are shown below.

Physical Properties of Hydrogenated Conjugated Diene Copolymer (i) and Block Copolymer (i-1) [Ratio (%) of Polymer Block (A), Polymer Block (B), and Polymer Block (C)]: Each polymer block with respect to the total mass of a polymer block (A), a polymer block (B), and a polymer block (C) from the preparation amount of the raw material used when preparing a block copolymer (i-1). The mass of was calculated as a ratio.

  [Vinyl bond content (mol%) of polymer blocks (A) and (B)]: Using infrared analysis, the vinyl bond content (mol%) of the polymer blocks (A) and (B) is determined by the Hampton method. Calculated.

  [Weight average molecular weight]: Using gel permeation chromatography (GPC, trade name: HLC-8120GPC, manufactured by Tosoh Finechem, column: manufactured by Tosoh, GMH-XL), the weight average molecular weight was determined in terms of polystyrene. .

[Coupling rate (%)]: The waveform obtained by the above-mentioned gel permeation chromatography measurement was waveform-separated, and the coupling rate was calculated from the area ratio of the waveform.
[Hydrogenation rate (%)]: A hydrogenation rate (%) was calculated from a 270 MHz, ¹ H-NMR spectrum using a carbon tetrachloride solution.

[MFR (g / 10 min)]: MFR (g / 10 min) was measured at 230 ° C. under a load of 10 kg in accordance with JIS K-7210.
[Melting point (° C.)]: A sample was held at 200 ° C. for 10 minutes using a differential scanning calorimeter (DSC) in accordance with JIS K-7121, and then cooled to −80 ° C. at a rate of 10 ° C./min. Then, after maintaining at −80 ° C. for 10 minutes, the extrapolation melting start temperature (Tim) at the crystal melting peak when the temperature was raised at a rate of 10 ° C./min was defined as the melting point (° C.). The melting points of the paraffin compound (ii) and the crystalline polyolefin (iii) are also measured by the same method.

Physical properties of crystalline polyethylene [MFR (g / 10 min)]: MFR (g / 10 min) was measured at 190 ° C. under a load of 2.16 kg according to JIS K-7210.

Physical properties and various characteristics of the composition for heat storage material [Measurement of melting point (° C.) and latent heat (kJ / kg) of the composition for heat storage material]: The melting point and latent heat of the composition for heat storage material are measured by a differential scanning calorimeter. (DSC) was used for measurement. The measurement was performed by holding the sample at 140 ° C. for 10 minutes, cooling to −30 ° C. at a rate of 10 ° C./minute, holding at −30 ° C. for 10 minutes, and then increasing to 140 ° C. at a rate of 10 ° C./minute. This was performed by measuring the melting peak when warmed. In accordance with JIS K-7121, the extrapolated melting start temperature of the melting peak corresponding to the blended paraffin compound (ii) is the melting point of the heat storage material composition, and the heat of fusion is the latent heat amount of the heat storage material composition. . In addition, melting | fusing point of the composition for thermal storage materials which has a some melting peak was made into the extrapolated melting start temperature of the melting peak with a larger amount of heat of fusion, and the latent heat amount was made into the heat of fusion of the melting peak. When there were multi-peaks and individual melting peaks could not be distinguished, they were treated as one melting peak.

[Shape retention]: The composition for a heat storage material was formed into a sheet having a thickness of 2 mm, cut into a size of 40 mm × 40 mm, and three sheets thereof were stacked to obtain a test sample. The sample was put into a gear oven set to the test temperature described in Tables 1 and 2, and after 1 hour, the sample was taken out and cooled sufficiently, and then the thickness of the sample was measured. evaluated.
AA: The thickness of the sample after the test is more than 80% of the thickness of the sample before the test, and the shape retainability is particularly excellent.
BB: The sample thickness after the test holds 30 to 80% of the sample thickness before the test, and the shape retainability is excellent.
CC: The sample thickness after the test is less than 30% of the sample thickness before the test, and the shape retainability is poor.

[Bleed property]: A composition for a heat storage material is formed into a sheet having a thickness of 2 mm, cut into a size of 40 mm × 40 mm, and three sheets thereof are laminated together with a polyethylene film (inner layer) and a polyamide film (outer layer). A test sample was obtained by packaging with a laminated film consisting of The sample was put into a gear oven set to the test temperature described in Tables 1 and 2 and allowed to stand. One hour later, the sample was taken out and sufficiently cooled, and then visually confirmed whether or not the paraffin compound (ii) was separated, and the bleeding property was evaluated according to the following criteria.
AA: Almost no separation is observed, and no bleed is observed.
BB: A slight amount of bleed is observed, but there is no practical problem. CC: Separation is clearly confirmed, and there are many bleeds.

[Fluidity]: 50 g of the composition for a heat storage material was put in a 200 mL glass beaker and heated and dissolved in a gear oven set to the test temperature described in Tables 1 and 2 for 1 hour. After moving the beaker on the horizontal table, the beaker was tilted by 90 °, and the appearance of the composition was visually observed. The fluidity was evaluated according to the following criteria.
AA: Since the solution of the composition flows out from the edge of the beaker within 5 seconds, the fluidity is good.
BB: Since the solution of the composition does not flow out from the edge of the beaker within 5 seconds, the fluidity is poor.

Synthesis of Hydrogenated Conjugated Diene Copolymer (i) [Synthesis Example 1]: Preparation of Hydrogenated Conjugated Diene Copolymer (H1) Into a reaction vessel having an internal volume of 50 L purged with nitrogen, 24000 g of cyclohexane, 1.2 g of tetrahydrofuran, 1,3-butadiene 600 g and n-butyllithium 2.5 g were added, and polymerization was performed at a polymerization start temperature of 70 ° C. After completion of the reaction, the temperature was set to 40 ° C., 112 g of tetrahydrofuran was added, and then adiabatic polymerization was carried out while 2400 g of 1,3-butadiene was successively added. Thereafter, 2.0 g of methyldichlorosilane was added to the system and reacted for 30 minutes to prepare a block copolymer.

  The block copolymer includes a structural unit derived from 1,3-butadiene, a polymer block (A) having a vinyl bond content of 14 mol%, a structural unit derived from 1,3-butadiene, and a vinyl. It was a block copolymer having a polymer block (B) having a bond content of 46 mol%. In addition, the block copolymer had a weight average molecular weight of 280,000 and a coupling rate of 80%.

  Subsequently, the reaction solution containing the block copolymer is brought to 80 ° C., 2.0 g of bis (cyclopentadienyl) titanium furfuryloxychloride and 1.2 g of n-butyllithium are added, and the hydrogen pressure is maintained at 1.0 MPa. For 2 hours.

  After the reaction, the reaction solution was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain the desired hydrogenated conjugated diene copolymer (H1). . The hydrogenation rate of the hydrogenated conjugated diene copolymer (H1) was 98%, the MFR was 3.5 g / 10 min, and the melting point was 82.0 ° C.

[Synthesis Example 2]: Preparation of Hydrogenated Conjugated Diene Copolymer (H2) In Synthesis Example 1, the amount of 1,3-butadiene used in the polymerization reaction for forming the polymer blocks (A) and (B) was 900 g. And 2100 g, the amount of n-butyllithium was changed to 5.0 g, the amount of tetrahydrofuran used in the polymerization reaction for forming the polymer block (B) was changed to 125 g, and tetrachlorosilane was used instead of methyldichloromethane. Except for this, a block copolymer was prepared in the same manner as in Synthesis Example 1.

  The block copolymer includes a structural unit derived from 1,3-butadiene, includes a polymer block (A) having a vinyl bond content of 15 mol%, and a structural unit derived from 1,3-butadiene. It was a block copolymer having a polymer block (B) having a bond content of 48 mol%. The block copolymer had a weight average molecular weight of 320,000 and a coupling rate of 79%.

  Subsequently, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain the desired hydrogenated conjugated diene copolymer (H2). The hydrogenation rate of the hydrogenated conjugated diene copolymer (H2) was 98%, the MFR was 0.5 g / 10 min, and the melting point was 83.8 ° C.

[Synthesis Example 3]: Preparation of Hydrogenated Conjugated Diene Copolymer (H3) In Synthesis Example 1, the amount of 1,3-butadiene used in the polymerization reaction for forming the polymer blocks (A) and (B) was 1560 g. In the same manner as in Synthesis Example 1, except that the amount of n-butyllithium was changed to 3.0 g and the amount of tetrahydrofuran used in the polymerization reaction for forming the polymer block (B) was changed to 145 g. A block copolymer was prepared.

  The block copolymer includes a structural unit derived from 1,3-butadiene, includes a polymer block (A) having a vinyl bond content of 15 mol%, and a structural unit derived from 1,3-butadiene. It was a block copolymer having a polymer block (B) having a bond content of 50 mol%. Moreover, in the said block copolymer, the weight average molecular weight was 230,000 and the coupling rate was 78%.

  Subsequently, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain the desired hydrogenated conjugated diene copolymer (H3). The hydrogenation rate of the hydrogenated conjugated diene copolymer (H3) was 98%, the MFR was 0.1 g / 10 min, and the melting point was 94.5 ° C.

[Example 1]
50 parts of “H1” as the hydrogenated conjugated diene copolymer (i), 50 parts of “PO1” (Novatech LD LC600A manufactured by Nippon Polyethylene Co., Ltd.) as the crystalline polyolefin (iii), and n− as the paraffin compound (ii) A composition for a heat storage material was manufactured by heating and mixing 900 parts of dodecane and 5 parts of “AO-60” (manufactured by ADEKA Co., Ltd.) at 120 ° C. in a glass flask. The manufactured heat storage material composition has a melting point of −11 ° C., a latent heat amount of 155 kJ / kg, a shape retention evaluation of AA, a bleeding property evaluation of AA, and a fluidity evaluation of AA. Met.

[Examples 2 to 15, Comparative Examples 1 to 8]
In Example 1, the composition for heat storage materials of Examples 2 to 15 and Comparative Examples 1 to 8 was produced in the same manner as in Example 1 except that the distribution composition was changed as described in Tables 1 and 2. . The heating and mixing in Examples 9, 11 to 15, and Comparative Example 6 were performed at 140 ° C.
Each component used in the examples and comparative examples is as follows.

Hydrogenated conjugated diene copolymer (i), other elastomers:
H1: Hydrogenated conjugated diene copolymer (H1) obtained in Synthesis Example 1
H2: Hydrogenated conjugated diene copolymer (H2) obtained in Synthesis Example 2
H3: Hydrogenated conjugated diene copolymer (H3) obtained in Synthesis Example 3
・ SEBS: Clayton G1651 manufactured by Kraton Polymer
(Styrene content = 33 wt%, MFR (230 ° C., 5 kg load) = not flowing)
EPDM: JSR JSR EP103AF (ethylene content = 59 wt%, propylene content = 36.5 wt%, ethylidene norbornene (ENB) content = 4.5 wt%, Mooney viscosity [ML _{1 + 4} ¹²⁵ ° C.] = 87, density = 0.86g / cm ³ )

Crystalline polyolefin (iii)
PO1 ... Novatec LD LC600A manufactured by Nippon Polyethylene Co., Ltd. (low density polyethylene, melting point = 106 ° C., heat of fusion = 145 kJ / kg, MFR = 7.0 g / 10 min, density = 0.918 g / cm ³ )
-PO2 ... Novatec LL UJ990 manufactured by Nippon Polyethylene Co., Ltd. (linear low density polyethylene, melting point = 126 ° C., heat of fusion = 155 kJ / kg, MFR = 35 g / 10 min, density = 0.937 g / cm ³ )
PO3 ... Novatec HD HJ590N manufactured by Nippon Polyethylene Co., Ltd. (high density polyethylene, melting point = 133 ° C., heat of fusion = 220 kJ / kg, MFR = 40 g / 10 min, density = 0.960 g / cm ³ )
PO4 ... Novatec HD HY540 manufactured by Nippon Polyethylene Co., Ltd. (high density polyethylene, melting point = 135 ° C., heat of fusion = 220 kJ / kg, MFR = 1.0 g / 10 min, density = 0.960 g / cm ³ )

Paraffin compound (ii)
PA1: Reagent n-Dodecane PA2: Reagent n-Tetradecane PA3 ... Reagent n-Hexadecane PA4 ... Reagent n-Octadecane PA5 ... Reagent n-Icosan PA6 ... Nippon Seiwa Co., Ltd. HNP-9 (paraffin wax, Melting point = 73 ° C.)
・ PA7: Nippon Seiwa Co., Ltd. HNP-51 (paraffin wax, melting point = 73 ° C.)
・ PA8 ... Nippon Seiwa Co., Ltd. FNP-0090 (paraffin wax, melting point = 80 ° C.)
・ PA9: Nippon Seiwa Co., Ltd. FT115 (paraffin wax, melting point = 93 ° C.)

Anti-aging agent AO-60 ... Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation)

  The measurement results and evaluation results of the produced heat storage material composition are shown in Tables 1 and 2 together.

  The composition for a heat storage material of the present invention is excellent in fluidity at the time of molding, has low bleed property of paraffin compounds and excellent shape retention even in a high temperature region. Therefore, various fields such as air conditioning equipment for residences, hotels, airports, underground malls, canisters for automobiles, electronic parts, refrigerators, thermos and other home appliances, clothing fibers, thermal containers for organ transport, curve mirrors, concrete materials for bridges, etc. In particular, it can be used in facilities that require a heat source in a high temperature region, such as a heat storage mechanism that uses a motor or compressor as a heat source.

Claims (10)

(I) a hydrogenated conjugated diene copolymer;
(Ii) paraffinic compounds;
(Iii) containing a crystalline polyolefin different from the hydrogenated conjugated diene copolymer,
The hydrogenated conjugated diene copolymer (i) includes a structural unit (a-1) derived from a conjugated diene compound, a polymer block (A) having a vinyl bond content of less than 30 mol%, and a conjugated diene compound. A polymer obtained by hydrogenating a block copolymer (i-1) containing a derived structural unit (b-1) and a polymer block (B) having a vinyl bond content of 30 to 95 mol% A composition for a heat storage material.   The heat storage material according to claim 1, wherein the crystalline polyolefin (iii) is a compound having a melting point equal to or higher than that of the paraffin compound (ii) when measured by a differential scanning calorimetry (DSC method). Composition.   The mass conversion ratio ((A) / (B)) between the polymer block (A) and the polymer block (B) in the block copolymer (i-1) is 5/95 to 50/50. The composition for heat storage materials according to claim 1 or 2.   The said block copolymer (i-1) WHEREIN: The content rate of the structural unit derived from an alkenyl aromatic compound is 30 mass% or less with respect to the said block copolymer (i-1). The composition for heat storage materials as described in any one of these.   The thermal storage according to any one of claims 1 to 4, wherein the structural unit (a-1) in the polymer block (A) contains 95 to 100 mass% of a structural unit derived from 1,3-butadiene. Material composition.   The composition for a heat storage material according to any one of claims 1 to 5, wherein a melting point of the paraffin compound (ii) measured by a differential scanning calorimetry (DSC method) is in a range of -30 to 130 ° C. object.   The composition for heat storage materials according to any one of claims 1 to 6, wherein the crystalline polyolefin (iii) is crystalline polyethylene.   The composition for heat storage materials according to any one of claims 1 to 7, further comprising a filler (iv).   The heat storage material formed from the composition for heat storage materials as described in any one of Claims 1-8.   The thermal storage apparatus obtained by filling the container for thermal storage materials as described in any one of Claims 1-8 in a container.