JPH0442437B2 - - Google Patents
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- Publication number
- JPH0442437B2 JPH0442437B2 JP58015401A JP1540183A JPH0442437B2 JP H0442437 B2 JPH0442437 B2 JP H0442437B2 JP 58015401 A JP58015401 A JP 58015401A JP 1540183 A JP1540183 A JP 1540183A JP H0442437 B2 JPH0442437 B2 JP H0442437B2
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- density polyethylene
- heat
- storage material
- melting point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Description
【発明の詳細な説明】
本発明は潜熱型多層蓄熱材に関する。更に詳し
くは高密度ポリエチレンを中芯とし、外層を高密
度ポリエチレンより高融点の樹脂で被覆した形状
安定性に優れた潜熱型多層蓄熱材に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a latent heat type multilayer heat storage material. More specifically, the present invention relates to a latent heat type multilayer heat storage material having excellent shape stability and having a core made of high-density polyethylene and an outer layer coated with a resin having a higher melting point than high-density polyethylene.
蓄熱材には、物質の熱容量を利用する顕熱型蓄
熱材と物質の融解、凝固あるいは結晶転移などの
潜熱を利用する潜熱型蓄熱材とがある。潜熱型蓄
熱材は単位体積当たりの蓄熱容量が顕熱型に比べ
て大きいので、蓄熱器の容量を小型化出来る利点
があり、太陽熱利用を目的として主として無機塩
水和物を用いた蓄熱システムの開発が検討されて
いる。しかしながら無機塩水和物は、溶融状態か
ら次第に降温させた時に、本来の相変化の温度を
過ぎても固化（結晶化）せず、放熱しないという
過冷却現象を生じ、同時に不溶性物質の晶出が融
解時に起こり、融解−固化のヒートサイクルを繰
り返すことにより不溶性物質が増加し続け延いて
は、相分離現象を呈すなどの問題を生じる。この
ため、蓄熱しても長時間に亙り所定の温度で安定
して熱を取り出すことができないという実用上の
不都合を生じさせている。 Heat storage materials include sensible heat storage materials that utilize the heat capacity of substances and latent heat storage materials that utilize latent heat such as melting, solidification, or crystal transition of substances. Latent heat type heat storage materials have a larger heat storage capacity per unit volume than sensible heat types, so they have the advantage of being able to downsize the heat storage capacity.Development of heat storage systems mainly using inorganic salt hydrates for the purpose of solar heat utilization. is being considered. However, when the temperature of an inorganic salt hydrate is gradually lowered from its molten state, it does not solidify (crystallize) or dissipate heat even after the original phase change temperature, resulting in a supercooling phenomenon, and at the same time, the crystallization of insoluble substances occurs. This occurs during melting, and as the heat cycle of melting and solidification is repeated, the amount of insoluble substances continues to increase, resulting in problems such as a phase separation phenomenon. For this reason, even if heat is stored, the heat cannot be extracted stably at a predetermined temperature for a long period of time, which is a practical disadvantage.
一方、無機塩水和物に代わる相分離現象を呈し
ない潜熱型蓄熱材として低分子量結晶性ポリオレ
フイン（特開昭50−146577号公報）あるいは結晶
性ポリオレフインを使用することが提案されてい
る。これらは熱的に安定で腐蝕性や毒性もなく、
潜熱も比較的大きいが、融解時の粘度が高く通常
の液体のように対流による流動が起こらずまた熱
伝導率も低いので、大きなブロツクとしては使用
できない欠点がある。これらの欠点をなくすに
は、ペレツト、ストランド、フイルム等の形状で
使用することが望ましいが、そのままでは溶解時
に形状が保持できない。そこで形状を保持する方
法として、結晶性ポリオレフインを架橋処理する
方法が提案されているが、架橋処理により結晶性
が低下するので、蓄熱材としての特性が低下する
という欠点がある。 On the other hand, it has been proposed to use low molecular weight crystalline polyolefin (Japanese Unexamined Patent Publication No. 146577/1982) or crystalline polyolefin as a latent heat type heat storage material that does not exhibit a phase separation phenomenon in place of inorganic salt hydrates. These are thermally stable, non-corrosive, and non-toxic.
Although it has a relatively large latent heat, it has a high viscosity when melted, does not flow by convection like a normal liquid, and has low thermal conductivity, so it has the disadvantage that it cannot be used as a large block. In order to eliminate these drawbacks, it is desirable to use it in the form of pellets, strands, films, etc., but if it is used as is, it cannot maintain its shape when melted. Therefore, a method of crosslinking crystalline polyolefin has been proposed as a method for maintaining the shape, but this has the drawback that the crosslinking treatment reduces crystallinity, resulting in a decrease in properties as a heat storage material.
かかる現状に鑑み、本発明者らは蓄熱性に優
れ、しかも溶融時の形状安定性にも優れた潜熱型
蓄熱材の開発について種々検討した結果、高密度
ポリエチレンを中芯として外層を高密度ポリエチ
レンより高融点であつて、かつ該高密度ポリエチ
レンを溶融させて蓄熱するときの加熱温度よりも
高い融点を有する樹脂で被覆することにより、上
記目的が達成できることが分かり、本発明を完成
するに至つた。 In view of this current situation, the present inventors conducted various studies on the development of a latent heat type heat storage material that has excellent heat storage properties and also has excellent shape stability when melted. It was found that the above object could be achieved by coating with a resin that has a higher melting point and a higher melting point than the heating temperature at which the high-density polyethylene is melted and stored, and this led to the completion of the present invention. Ivy.
すなわち、本発明は、少なくとも密度が0.960
ｇ／cm3以上の高密度ポリエチレン(A)を中芯とし、
外層を高密度ポリエチレン(A)より高融点の樹脂で
あつて、高密度ポリエチレン(A)を溶融させて蓄熱
するときの加熱温度よりも高い融点を有する樹脂
(B)で被覆したことを特徴とする蓄熱性及び形状安
定性に優れた潜熱型多層蓄熱材を提供するもので
ある。 That is, the present invention has a density of at least 0.960.
High-density polyethylene (A) of g/cm 3 or more is used as the core,
The outer layer is made of a resin that has a higher melting point than high-density polyethylene (A), and has a higher melting point than the heating temperature when melting high-density polyethylene (A) and storing heat.
The present invention provides a latent heat type multilayer heat storage material characterized by being coated with (B) and having excellent heat storage properties and shape stability.
本発明に用いる高密度ポリエチレン(A)とは、密
度が少なくとも0.960ｇ／cm3以上、好ましくは
0.970ｇ／cm3以上、好ましくはＸ線による結晶化
度が80％以上のものであり、分子量はとくに限定
されず、低分子量でワツクス状のものからデカリ
ン溶媒135℃中での極限粘度〔η〕が３dl／ｇ程
度のものまで使用できる。中でも分子量が1000な
いし100000の範囲のものが融解し易く、それに伴
い融解熱量も大きいので好ましい。密度が0.960
ｇ／cm3未満のものは、融解熱量が小さいので、蓄
熱材としては不適である。 The high-density polyethylene (A) used in the present invention has a density of at least 0.960 g/cm 3 or more, preferably
0.970 g/cm 3 or more, preferably 80% or more crystallinity by X-rays, and the molecular weight is not particularly limited, ranging from low molecular weight and wax-like to decalin solvent with an intrinsic viscosity of 135°C [η ] can be used up to about 3 dl/g. Among these, those with a molecular weight in the range of 1,000 to 100,000 are preferred because they are easy to melt and have a large heat of fusion. Density is 0.960
If it is less than g/cm 3 , the heat of fusion is small, so it is not suitable as a heat storage material.
前記芯材となる高密度ポリエチレン(A)の外層を
被覆する樹脂(B)は、高密度ポリエチレン(A)より高
融点であつて、高密度ポリエチレン(A)を溶融させ
て蓄熱するときの加熱温度よりも高い融点を有す
る樹脂であり、具体的には、例えばポリプロピレ
ン、ポリー４−メチル−１−ペンテン等のポリオ
レフイン、ポリエチレンテレフタレート、ポリブ
チレンテレフタレート等のポリエステル、ナイロ
ン６、ナイロン66、ナイロン610、ナイロン11等
のポリアミド等である。 The resin (B) that covers the outer layer of the high-density polyethylene (A), which is the core material, has a higher melting point than the high-density polyethylene (A), and has a higher melting point than the high-density polyethylene (A) when heated to store heat by melting the high-density polyethylene (A). It is a resin that has a melting point higher than the temperature, and specifically includes polyolefins such as polypropylene and poly4-methyl-1-pentene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, nylon 6, nylon 66, nylon 610, Polyamide such as nylon 11.
本発明の潜熱型多層蓄熱材は前記高密度ポリエ
チレン(A)を中芯とし、外層を高密度ポリエチレン
(A)より高融点であつて、高密度ポリエチレン(A)を
溶融させて蓄熱するときの加熱温度よりも高い融
点を有する樹脂(B)で被覆してなるが、かかる構造
の蓄熱材は、例えば共押出成形、多層射出成形、
押出被覆成形により得られる。本発明の潜熱型多
層蓄熱材は、前記成形により中芯を高密度ポリエ
チレン(A)とした三層フイルム、三層シート、スト
ランド、ロツド、プロフアイル（異形押出品）等
の形状として用いられる。 The latent heat type multilayer heat storage material of the present invention has the above-mentioned high-density polyethylene (A) as the core, and the outer layer is made of high-density polyethylene.
(A) and is coated with a resin (B) that has a higher melting point than the heating temperature at which high-density polyethylene (A) is melted and stored, but a heat storage material with such a structure is For example, coextrusion molding, multilayer injection molding,
Obtained by extrusion coating. The latent heat type multilayer heat storage material of the present invention is used in the form of a three-layer film, a three-layer sheet, a strand, a rod, a profile (shaped extrusion product), etc. whose core is made of high-density polyethylene (A) by the above-mentioned molding.
本発明の潜熱型多層蓄熱材は、溶融時にもその
形状が変化しないので、繰り返し使用しても熱効
率が低下せずまた高密度ポリエチレン(A)の融解・
結晶化の温度範囲が140ないし100℃であるので、
水、エチレングリコール、シリコンオイル等と組
み合わせて、太陽熱蓄熱装置等として好適に使用
される。 The latent heat type multilayer heat storage material of the present invention does not change its shape even when melted, so its thermal efficiency does not decrease even when used repeatedly.
Since the crystallization temperature range is 140 to 100℃,
In combination with water, ethylene glycol, silicone oil, etc., it is suitably used as a solar heat storage device.
実施例 １
三井石油化学工業(株)製ポリプロピレン三井石油
化学ポリプロ
B200（融点＝165℃、メルトフロ
ーレート0.5ｇ／10分）の薄肉チユーブ（外径６
mmφ×肉厚0.5mm）を外層とし、中芯として、三
井石油化学工業(株)製高密度ポリエチレンワツクス
商品名三井ハイワツクス400P（密度0.97ｇ／cm3、
融点126℃、分子量4000、結晶化度＝85％）をポ
リプロチユーブに封入した。Example 1 A thin-walled tube (outer diameter 6
mmφ x wall thickness 0.5 mm) as the outer layer, and high-density polyethylene wax manufactured by Mitsui Petrochemical Industries, Ltd. (trade name: Mitsui Hiwax 400P) (density 0.97 g/cm 3 ,
(melting point 126°C, molecular weight 4000, crystallinity = 85%) was encapsulated in a polyprotube.
こうして得た２層の蓄熱材を多数140℃のエチ
レングリコールを入れた蓄熱槽に入れ、蓄熱材の
溶融状態を調べた。その結果内層のワツクスのみ
溶融し、外層のポリプロピレンチユーブは溶融せ
ずその形状を保持し、チユーブ同志が融着するこ
とはなかつた。蓄熱材の固化潜熱量を測定したと
ころ、外層チユーブの影響はほとんどなく、十分
な熱量であつた。尚該蓄熱材の固化潜熱量は
54cal／ｇ、結晶化温度115〜117℃であつた。 A large number of the two-layer heat storage materials thus obtained were placed in a heat storage tank containing ethylene glycol at 140°C, and the molten state of the heat storage materials was examined. As a result, only the wax in the inner layer was melted, and the polypropylene tubes in the outer layer did not melt and retained their shape, and the tubes were not fused together. When the latent heat of solidification of the heat storage material was measured, there was almost no influence from the outer tube, and the amount of heat was sufficient. The amount of latent heat of solidification of the heat storage material is
The crystallization temperature was 115-117°C.
実施例 ２
実施例１のワツクスの代りに中芯として三井石
油化学工業(株)製高密度ポリエチレンハイゼツクス
ＯＲ
2200J（密度0.968ｇ／cc、融点132℃、メルトフ
ローレート５ｇ／10分、分子量＝65000、結晶化
度85％）を使用し、外層の実施例１で用いたポリ
プロピレンと共に共押出成形を行い、直径５mmφ
の２層ロツドを得た。このロツドの両端をヒート
シールし蓄熱材とし、実施例１と同様に評価した
ところ、融着、変形は全くみられなかつた。尚、
該ロツドの固化潜熱量は50cal／ｇ、結晶化温度
は120〜122℃であつた。Example 2 As a core instead of the wax in Example 1, high-density polyethylene Hi-Zex OR 2200J manufactured by Mitsui Petrochemical Industries, Ltd. (density 0.968 g/cc, melting point 132°C, melt flow rate 5 g/10 min, molecular weight = 65000, crystallinity 85%) and coextruded with the polypropylene used in Example 1 for the outer layer to form a diameter of 5 mmφ.
A two-layer rod was obtained. Both ends of this rod were heat-sealed to form a heat storage material, and when evaluated in the same manner as in Example 1, no fusion or deformation was observed. still,
The latent heat of solidification of the rod was 50 cal/g, and the crystallization temperature was 120-122°C.
実施例 ３
実施例２の外層として三井PET樹脂製造販売
(株)製ポリエチレンテレフタレート樹脂、商品名三
井PET Ｊ−055（I.V＝1.3dl／ｇ、融点＝260℃）
を用い、実施例２と同様に成形にして２層ロツド
を得た。該蓄熱材を実施例１と同様に評価したと
ころ、融着変形は全くみられなかつた。Example 3 Mitsui PET resin manufactured and sold as the outer layer of Example 2
Polyethylene terephthalate resin manufactured by Co., Ltd., product name Mitsui PET J-055 (IV = 1.3 dl/g, melting point = 260°C)
A two-layer rod was obtained by molding in the same manner as in Example 2. When the heat storage material was evaluated in the same manner as in Example 1, no fusion deformation was observed.
Claims (1)
ポリエチレン(A)を中芯とし、外層を高密度ポリエ
チレン(A)より高融点の樹脂であつて、高密度ポリ
エチレン(A)を溶融させて蓄熱するときの加熱温度
よりも高い融点を有する樹脂(B)で被覆したことを
特徴とする潜熱型多層蓄熱材。1 The center core is high-density polyethylene (A) with a density of at least 0.960 g/cm 3 or more, the outer layer is a resin with a higher melting point than the high-density polyethylene (A), and the high-density polyethylene (A) is melted to store heat. 1. A latent heat type multilayer heat storage material characterized by being coated with a resin (B) having a melting point higher than the heating temperature at which the latent heat storage material is heated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58015401A JPS59142276A (en) | 1983-02-03 | 1983-02-03 | Latent heat type multi-layer heat storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58015401A JPS59142276A (en) | 1983-02-03 | 1983-02-03 | Latent heat type multi-layer heat storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59142276A JPS59142276A (en) | 1984-08-15 |
| JPH0442437B2 true JPH0442437B2 (en) | 1992-07-13 |
Family
ID=11887702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58015401A Granted JPS59142276A (en) | 1983-02-03 | 1983-02-03 | Latent heat type multi-layer heat storage material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59142276A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5053446A (en) * | 1985-11-22 | 1991-10-01 | University Of Dayton | Polyolefin composites containing a phase change material |
| US4908166A (en) * | 1985-11-22 | 1990-03-13 | University Of Dayton | Method for preparing polyolefin composites containing a phase change material |
| US5254380A (en) * | 1985-11-22 | 1993-10-19 | University Of Dayton | Dry powder mixes comprising phase change materials |
| US5106520A (en) * | 1985-11-22 | 1992-04-21 | The University Of Dayton | Dry powder mixes comprising phase change materials |
| US4711813A (en) * | 1985-11-22 | 1987-12-08 | University Of Dayton | Polyethylene composites containing a phase change material having a C14 straight chain hydrocarbon |
| JPH0737610B2 (en) * | 1989-04-07 | 1995-04-26 | 株式会社田熊総合研究所 | Latent heat storage type heating device and solid-liquid two-phase heat medium |
| US5211949A (en) * | 1990-01-09 | 1993-05-18 | University Of Dayton | Dry powder mixes comprising phase change materials |
| JPH0781135B2 (en) * | 1991-02-26 | 1995-08-30 | 積水化成品工業株式会社 | Latent heat storage material and its manufacturing method |
| US6652771B2 (en) | 2001-07-11 | 2003-11-25 | Ronald M. Carn | Phase change material blend, method for making, and devices using same |
-
1983
- 1983-02-03 JP JP58015401A patent/JPS59142276A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59142276A (en) | 1984-08-15 |
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