TW201831856A - Heat storage layer forming composition - Google Patents
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- TW201831856A TW201831856A TW106142531A TW106142531A TW201831856A TW 201831856 A TW201831856 A TW 201831856A TW 106142531 A TW106142531 A TW 106142531A TW 106142531 A TW106142531 A TW 106142531A TW 201831856 A TW201831856 A TW 201831856A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
Description
本發明係關於蓄熱層形成用組成物。The present invention relates to a composition for forming a heat storage layer.
所謂蓄熱材料係具有可暫時性地蓄熱的性質，一般而言，指可利用物質之相變化或化學反應而控制熱之出入的物質或包含該物質的材料。蓄熱材料係按照使用用途而填充於各種裝置、機器之特定之空間(容器)，作為蓄熱系統，在船舶、車輛、空調等之各種熱交換器等廣泛地利用(例如，專利文獻1、專利文獻2)。 作為蓄熱材料係大致區分為利用材料之熱容量(溫度變化)的顯熱蓄熱材料、利用物質之相變化的潛熱蓄熱材料、利用化學反應熱的化學蓄熱材料。The heat storage material has a property of temporarily storing heat, and generally refers to a substance that can control the ingress and egress of heat by a phase change or a chemical reaction of a substance or a material containing the substance. The heat storage material is used in a specific space (container) of various devices and equipments, and is widely used as a heat storage system in various heat exchangers such as ships, vehicles, and air conditioners (for example, Patent Document 1 and Patent Literature). 2). The heat storage material is roughly classified into a sensible heat storage material using a heat capacity (temperature change) of the material, a latent heat storage material using a phase change of the material, and a chemical heat storage material using chemical reaction heat.
近年來，報告有其目的為更有效率的利用熱或系統之省空間化，將蓄熱材料直接塗佈於金屬等之基材等之技術。 例如在專利文獻2係開示有為了使熱交換型反應器之熱交換效率提昇，所以於熱交換面塗佈已分散氧化鈣粒子的塗佈液，形成包含化學蓄熱材料的熱交換構造體的技術。 於專利文獻3係提案有設為可成形為任意之形狀的化學蓄熱材料形成用組成物，例如報告有藉由將該組成物塗佈於金屬基板後進行燒結，可得到能吸收藉由自身之體積之增減而產生的形狀之應變之多孔質之化學蓄熱材料之點。In recent years, there has been reported a technique for more efficiently utilizing heat or space saving of a system, and directly applying a heat storage material to a substrate such as a metal. For example, Patent Document 2 discloses a technique in which a coating liquid containing dispersed calcium oxide particles is applied to a heat exchange surface to improve a heat exchange efficiency of a heat exchange type reactor, and a heat exchange structure including a chemical heat storage material is formed. . Patent Document 3 proposes a chemical heat storage material forming composition which can be formed into an arbitrary shape. For example, it is reported that the composition can be absorbed by itself after being applied to a metal substrate and then sintered. The point of the porous chemical chemical storage material in which the shape is strained by the increase or decrease in volume.
另一方面，有將多孔質的機能性材料(吸濕性材料)，使用有機黏合劑而設為薄片狀的提案(專利文獻4)、或作為鋰二次電池之電極活性物質及導電助劑之黏合劑，利用已微細化的纖維素纖維的提案(專利文獻5)。 [先前技術文獻] [專利文獻]On the other hand, there is a proposal that a porous functional material (hygroscopic material) is formed into a sheet shape using an organic binder (Patent Document 4), or an electrode active material and a conductive auxiliary agent for a lithium secondary battery. The binder is a proposal of using a cellulose fiber which has been refined (Patent Document 5). [Prior Technical Literature] [Patent Literature]
[專利文獻1] 日本特開2015 -215155號公報 [專利文獻2] 日本特開2012 -127588號公報 [專利文獻3] 日本特開2015 -098582號公報 [專利文獻4] 日本特開2013 -202505號公報 [專利文獻5] 國際公開第2013/0427720號[Patent Document 1] Japanese Laid-Open Patent Publication No. 2012-127588 (Patent Document 3) JP-A-2015-098582 (Patent Document 4) JP-A-2013-202505 No. [Patent Document 5] International Publication No. 2013/0427720
[發明所欲解決之課題][Problems to be solved by the invention]
如上述，蓄熱材料係不僅有先前之向特定之空間(容器)之填充所致之利用，而且研討藉由向基材之塗佈等而得到的薄片狀物之在任意之形狀(成形物)之利用。在此情況，在已得到的蓄熱材料之成形物，要求保持所期望之形狀。 但是，在專利文獻2所開示的技術係未進行任何考慮關於在包含化學蓄熱材料的氧化鈣的熱交換構造體，藉由化學蓄熱材料之化學反應，亦即化學蓄熱材料與水蒸氣之可逆反應而會產生的蓄熱材料之體積增減。 又，在專利文獻3係雖然藉由於化學蓄熱材料設置多孔質的形狀，謀求吸收因體積增減所致的形狀之應變，但是因此係需要高溫(680℃以上)所致的燒結，可使用的基材被限制。 又，於專利文獻4及專利文獻5係未研討將記載於該文獻之有機黏合劑或纖維素纖維，設為蓄熱材料之黏合劑。As described above, the heat storage material is not only used for the filling of a specific space (container), but also the shape of the sheet obtained by coating the substrate or the like in any shape (formed product). Use. In this case, it is required to maintain a desired shape in the molded product of the obtained heat storage material. However, the technique disclosed in Patent Document 2 does not make any consideration regarding the heat exchange structure of calcium oxide containing a chemical heat storage material, and the chemical reaction of the chemical heat storage material, that is, the reversible reaction of the chemical heat storage material with water vapor. The volume of heat storage material that will be produced increases or decreases. In addition, in the case of the patent document 3, since the chemical heat storage material is provided with a porous shape, it is required to absorb the strain due to the increase and decrease of the volume. However, it is necessary to use a high temperature (at 680 ° C or higher) for sintering. The substrate is limited. Further, in Patent Document 4 and Patent Document 5, the organic binder or the cellulose fiber described in the document is not examined as a binder of the heat storage material.
本發明係目的為提供一種蓄熱層形成用組成物，其係藉由塗佈之簡便的方法而可形成膜，然後藉由使該膜以100℃前後之較柔和的溫度乾燥，可得到均勻的膜狀之蓄熱層。 又，本發明係目的為提供一種蓄熱層形成用組成物，其係在已得到的膜狀之蓄熱層，無大幅地損及所使用的蓄熱材料之蓄熱性能，可發揮同等之性能。 [用以解決課題之手段]It is an object of the present invention to provide a composition for forming a heat storage layer which can be formed into a film by a simple method of coating, and then obtained by uniformly drying the film at a gentle temperature before and after 100 ° C. Membrane heat storage layer. Further, an object of the present invention is to provide a heat storage layer-forming composition which is obtained in a film-like heat storage layer without significantly impairing the heat storage performance of the heat storage material to be used, and exhibits equivalent performance. [Means to solve the problem]
本發明者係為了達成上述目的而重覆專心致力研討的結果，發現已調配蓄熱材料、已微細化的纖維素纖維及水溶性高分子的組成物，藉由塗佈此且使其乾燥，可得到無破裂等，均勻的膜狀之層，亦即可得到蓄熱層，而且該蓄熱層可得到與原材料的蓄熱材料之蓄熱性能幾乎同等之性能，完成本發明。In order to achieve the above object, the inventors of the present invention have repeatedly focused on the results of the research and found that the composition of the heat storage material, the finely divided cellulose fibers, and the water-soluble polymer has been prepared, and the coating is dried and dried. The heat storage layer can be obtained by obtaining a uniform film-like layer without cracking or the like, and the heat storage layer can obtain almost the same performance as the heat storage property of the heat storage material of the raw material, and the present invention has been completed.
亦即本發明係作為第1觀點，關於一種蓄熱層形成用組成物，其特徵為含有 (A) 蓄熱材料100質量份、 (B) 已微細化的纖維素纖維0.01～100質量份、以及 (C) 水溶性高分子0.01～100質量份。 作為第2觀點，關於如第1觀點之蓄熱層形成用組成物，其中，前述(B) 已微細化的纖維素纖維係表示使用雷射繞射．散射式粒度分布計且在將水作為分散媒而測定的纖維中位尺寸的在體積累計50%之粒徑為0.01～40μm。 作為第3觀點，關於如第1觀點或第2觀點之蓄熱層形成用組成物，其中，前述(A) 蓄熱材料係成為具有10nm～100μm之平均粒徑的粉體之形態的化合物。 作為第4觀點，關於如第1觀點至第3觀點中任一項之蓄熱層形成用組成物，其中，前述(A) 蓄熱材料為潛熱蓄熱材料。 作為第5觀點，關於如第4觀點之蓄熱層形成用組成物，其中，前述(A) 蓄熱材料為由無機鹽水合物、烴(石蠟)、脂肪酸、脂肪酸酯、脂肪族酮、脂肪族醇、脂肪族醚、包接水合物及強關聯電子系統(Strongly correlated electronic systems)物質所構成的群中選擇至少一種。 作為第6觀點，關於如第1觀點至第3觀點中任一項之蓄熱層形成用組成物，其中，前述(A) 蓄熱材料為化學蓄熱材料。 作為第7觀點，關於如第6觀點之蓄熱層形成用組成物，其中，前述(A) 蓄熱材料為由鋁矽酸鹽、苯基膦酸化合物金屬鹽及芳香族羧酸化合物金屬鹽所構成的群中選擇至少一種。 作為第8觀點，關於如第1觀點至第7觀點中任一項之蓄熱層形成用組成物，其中，前述(C) 水溶性高分子為由聚乙烯醇、改質聚乙烯醇、聚乙烯吡咯啶酮、聚乙二醇、聚丙烯酸鹽之部分中和物、陽離子化纖維素、甲基纖維素、乙基纖維素、羧甲基纖維素、(羧甲基)(乙基)纖維素、羥乙基纖維素、(羥乙基)(甲基)纖維素、(乙基)(羥乙基)纖維素、羥丙基纖維素、(羥丙基)(甲基)纖維素、陽離子化澱粉所構成的群中選擇至少一種。 作為第9觀點，關於如第8觀點之蓄熱層形成用組成物，其中，前述(C) 水溶性高分子為聚乙烯醇。 作為第10觀點，關於一種蓄熱層，其特徵為由如第1觀點至第9觀點中任一項之蓄熱層形成用組成物所製作。 作為第11觀點，關於一種蓄熱層，其係含有蓄熱材料、已微細化的纖維素纖維及水溶性高分子的蓄熱層，其特徵為前述蓄熱層係具有0.1～5,000μm之厚度的層，前述蓄熱材料係該等為相互藉由前述纖維素纖維及前述水溶性高分子捕捉，形成膜形狀而成。 作為第12觀點，關於一種熱交換器，其特徵為如第10觀點或第11觀點之蓄熱層形成於熱傳導性基材之表面。 作為第13觀點，關於如第12觀點之熱交換器，其中，前述熱傳導性基材為熱媒體流通的流路之隔壁，於與該隔壁之熱媒體流通側相反側之面形成前述蓄熱層。 作為第14觀點，關於如第13觀點之熱交換器，其中，前述熱媒體為原動機之冷卻水。 作為第15觀點，關於如第13觀點或第14觀點之熱交換器，其中，裝載於車輛。 [發明之效果]In other words, the present invention relates to a composition for forming a heat storage layer, which comprises (A) 100 parts by mass of the heat storage material, and (B) 0.01 to 100 parts by mass of the cellulose fibers which have been refined, and C) The water-soluble polymer is 0.01 to 100 parts by mass. According to a second aspect, the composition for forming a heat storage layer according to the first aspect, wherein the (B) microfibrillated cellulose fiber indicates that a laser diffraction is used. The scattering type particle size distribution meter has a particle diameter of 50% of the median size of the fiber measured by using water as a dispersion medium, and is 0.01 to 40 μm. In the heat storage layer forming composition according to the first aspect or the second aspect, the heat storage material (A) is a compound having a powder having an average particle diameter of 10 nm to 100 μm. The composition for forming a heat storage layer according to any one of the first aspect to the third aspect, wherein the heat storage material (A) is a latent heat storage material. The heat storage layer forming composition according to the fourth aspect, wherein the (A) heat storage material is an inorganic salt hydrate, a hydrocarbon (paraffin), a fatty acid, a fatty acid ester, an aliphatic ketone, or an aliphatic group. At least one selected from the group consisting of alcohols, aliphatic ethers, inclusion hydrates, and strongly correlated electronic systems. The composition for forming a heat storage layer according to any one of the first aspect to the third aspect, wherein the heat storage material (A) is a chemical heat storage material. According to a seventh aspect of the invention, the heat storage layer forming composition according to the sixth aspect, wherein the (A) heat storage material is composed of an aluminosilicate, a phenylphosphonic acid compound metal salt, and an aromatic carboxylic acid compound metal salt. Select at least one of the groups. The composition for forming a heat storage layer according to any one of the first aspect to the seventh aspect, wherein the (C) water-soluble polymer is a polyvinyl alcohol, a modified polyvinyl alcohol, or a polyethylene. Pyrrolidone, polyethylene glycol, partial neutralizer of polyacrylate, cationized cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, (carboxymethyl) (ethyl) cellulose , hydroxyethyl cellulose, (hydroxyethyl) (methyl) cellulose, (ethyl) (hydroxyethyl) cellulose, hydroxypropyl cellulose, (hydroxypropyl) (methyl) cellulose, cation At least one selected from the group consisting of starch. According to a ninth aspect, the composition for forming a heat storage layer according to the eighth aspect, wherein the (C) water-soluble polymer is polyvinyl alcohol. According to a tenth aspect, the heat storage layer is produced by the heat storage layer formation composition according to any one of the first aspect to the ninth aspect. According to a tenth aspect, a heat storage layer comprising a heat storage material, a finely divided cellulose fiber, and a heat storage layer of a water-soluble polymer, wherein the heat storage layer has a thickness of 0.1 to 5,000 μm, The heat storage material is formed by capturing the cellulose fibers and the water-soluble polymer with each other to form a film shape. According to a twelfth aspect, in the heat exchanger, the heat storage layer according to the tenth aspect or the eleventh aspect is formed on the surface of the thermally conductive substrate. The heat exchanger according to the twelfth aspect, wherein the heat conductive substrate is a partition wall of a flow path through which the heat medium flows, and the heat storage layer is formed on a surface opposite to a heat medium flow side of the partition wall. A heat exchanger according to the thirteenth aspect, wherein the heat medium is cooling water of a prime mover. According to a fifteenth aspect, the heat exchanger according to the thirteenth aspect or the fourteenth aspect, wherein the heat exchanger is mounted on a vehicle. [Effects of the Invention]
本發明之蓄熱層形成用組成物係藉由塗佈此且使其乾燥，可得到不產生孔或破裂等之龜裂而均勻的膜狀之蓄熱層，又，可得到與基材之密著性優異，已固定化於基材的蓄熱層。The composition for forming a heat storage layer of the present invention is coated and dried to obtain a film-like heat storage layer which is free from cracks such as pores or cracks, and can be obtained in close contact with the substrate. Excellent in properties, it has been immobilized on the heat storage layer of the substrate.
本發明者等係研討當形成膜狀之蓄熱層，有助於層構造之形狀之保持，且，不阻礙蓄熱性能的材料之採用。 具體而言係關於，在可吸收、緩和因蓄熱層形成時、或蓄熱材料之相轉移或化學反應而產生的形態變化及體積變化的材料，又，可提昇蓄熱材料彼此、或蓄熱材料與基材之結著性的材料，還有利用水蒸氣等之作動流體與蓄熱材料之接觸所致的化學反應熱的化學蓄熱材料中，不阻礙該作動流體之向化學蓄熱材料之到達的材料，進行研討。 然後，本發明者等係注目於若由已微細化的纖維素纖維之水分散液除去水，則纖維素纖維形成不織布狀或網目狀之構造體之情事，研討藉由此構造體，是否可達成上述之體積變化之抑制、或蓄熱材料彼此之結著性之提昇，然後該構造體是否不阻礙作動流體與蓄熱材料之接觸，以致完成本發明。 以下，關於本發明進而加以詳細敘述。The inventors of the present invention have studied the use of a material that does not inhibit the heat storage performance when forming a film-like heat storage layer to contribute to maintaining the shape of the layer structure. Specifically, the material which can absorb and alleviate the morphological change and the volume change caused by the phase transfer or chemical reaction of the heat storage material, and the heat storage material or the heat storage material and the base can be improved. In the chemical heat storage material which utilizes the chemical reaction heat caused by the contact between the actuating fluid such as water vapor and the heat storage material, the material which does not hinder the arrival of the chemical fluid to the chemical heat storage material is performed. Discussion. Then, the inventors of the present invention pay attention to the fact that when the water is removed from the aqueous dispersion of the finely divided cellulose fibers, the cellulose fibers form a structure having a non-woven fabric or a mesh shape, and whether or not the structure can be used The suppression of the volume change described above or the improvement of the adhesion of the heat storage materials to each other is achieved, and then the structure does not hinder the contact of the actuation fluid with the heat storage material, so that the present invention is completed. Hereinafter, the present invention will be described in detail.
[(A) 蓄熱材料] 作為可使用於本發明的蓄熱材料係無特別限定，可舉出作為上述的顯熱蓄熱材料、潛熱蓄熱材料及化學蓄熱材料可使用的各種之蓄熱材料。[(A) Heat storage material] The heat storage material which can be used in the present invention is not particularly limited, and various heat storage materials which can be used as the above-described sensible heat storage material, latent heat storage material, and chemical heat storage material are exemplified.
作為前述顯熱蓄熱材料係例如可舉出土壤、砂、岩石、混凝土板、磚等之非金屬系材料；鋼、鎂、熔鹽、陶瓷磚等之金屬系材料等。在本發明係因為作為蓄熱層而固定化使用，所以前述顯熱蓄熱材料係成為粉末之形態者為較佳。Examples of the sensible heat storage material include non-metallic materials such as soil, sand, rock, concrete slab, and brick; and metal materials such as steel, magnesium, molten salt, and ceramic tile. In the present invention, since the heat storage layer is used as a heat storage layer, it is preferable that the sensible heat storage material is in the form of a powder.
作為前述潛熱蓄熱材料，如為可伴隨相變化而進行發熱、吸熱的化合物則無特別限制，例如，可舉出無機鹽水合物、烴(石蠟)、脂肪酸、脂肪酸酯、脂肪族酮、脂肪族醇、脂肪族醚、包接水合物及強關聯電子系統(Strongly correlated electronic systems)物質等。 其中，從作為蓄熱層之使用容易度，此等化合物之藉由示差掃描熱量測定法(DSC法)而測定的融點係在10~250℃之範圍為較佳，在20~200℃之範圍為更佳。The latent heat storage material is not particularly limited as long as it can generate heat and absorb heat with a phase change, and examples thereof include an inorganic salt hydrate, a hydrocarbon (paraffin), a fatty acid, a fatty acid ester, an aliphatic ketone, and a fat. Alkaloids, aliphatic ethers, inclusion hydrates, and strongly associated electronic systems. Among them, from the ease of use as a heat storage layer, the melting point of these compounds measured by differential scanning calorimetry (DSC method) is preferably in the range of 10 to 250 ° C, and in the range of 20 to 200 ° C. For better.
作為上述無機鹽水合物之具體例係可舉出碳酸鈉10水合物、碳酸鉀6水合物、硝酸鋰3水合物、硝酸鎳6水合物、硝酸鎂6水合物、硝酸鋁9水合物、硝酸鐵6水合物、硫酸鈉10水合物、硫酸鋁10水合物、硫代硫酸鈉5水合物、四硼酸鈉10水合物、醋酸鈉3水合物、氯化鎂6水合物、氫氧化鍶8水合物、氫氧化鋇8水合物等。Specific examples of the inorganic salt hydrate include sodium carbonate 10 hydrate, potassium carbonate hexahydrate, lithium nitrate trihydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, aluminum nitrate hexahydrate, and nitric acid. Iron 6 hydrate, sodium sulfate 10 hydrate, aluminum sulfate 10 hydrate, sodium thiosulfate 5 hydrate, sodium tetraborate 10 hydrate, sodium acetate trihydrate, magnesium chloride 6 hydrate, cesium hydroxide 8 hydrate, Barium hydroxide 8 hydrate, and the like.
作為上述烴係可使用碳原子數8~60之烴，作為具體例係可舉出十四烷、十五烷、十六烷、十七烷、十八烷、十九烷、二十烷、二十一烷、二十二烷、二十三烷、二十四烷、二十五烷、二十六烷、二十七烷、二十八烷、二十九烷、三十烷、三十一烷、三十二烷、三十三烷等。As the hydrocarbon system, a hydrocarbon having 8 to 60 carbon atoms can be used, and specific examples thereof include tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and eicosane. T-dodecane, docosane, heptacosane, tetracosane, dipentadecane, hexadecane, heptacosane, octacosane, octadecane, triacontane, three Undecane, tridodecane, triacontane, and the like.
作為上述脂肪酸之具體例係可舉出辛酸、壬酸、癸酸(羊脂酸)、十二烷酸(月桂酸)、十四烷酸(肉荳蔻酸)、十六烷酸(棕櫚酸)、十八烷酸(硬脂酸)、二十烷酸、二十二烷酸，二十四烷酸，二十六烷酸，二十八烷酸，三十烷酸等。在此等之中，由取得性之觀點，碳原子數10~18之直鏈飽和脂肪酸為較佳。Specific examples of the above fatty acid include caprylic acid, capric acid, capric acid (mastic acid), dodecanoic acid (lauric acid), myristic acid (myristic acid), and palmitic acid (palmitic acid). , octadecanoic acid (stearic acid), eicosanoic acid, behenic acid, tetracosanoic acid, hexadecanoic acid, octacosanoic acid, triacontanic acid and the like. Among these, from the viewpoint of availability, a linear saturated fatty acid having 10 to 18 carbon atoms is preferred.
作為上述脂肪酸酯係可使用碳原子數8~30之長鏈脂肪酸酯，作為具體例係可舉出棕櫚酸丙酯、棕櫚酸異丙酯、硬脂酸乙烯酯、硬脂酸異丙酯、硬脂酸丁酯、癸二酸二甲酯等。又，由取得性之觀點，碳原子數10~18之直鏈飽和脂肪酸之甲酯、乙酯、丙酯、丁酯可較佳使用。As the fatty acid ester, a long-chain fatty acid ester having 8 to 30 carbon atoms can be used, and specific examples thereof include propyl palmitate, isopropyl palmitate, vinyl stearate, and isopropyl stearate. Ester, butyl stearate, dimethyl sebacate, and the like. Further, from the viewpoint of availability, a methyl ester, an ethyl ester, a propyl ester or a butyl ester of a linear saturated fatty acid having 10 to 18 carbon atoms can be preferably used.
作為上述脂肪酸酮係可使用碳原子數8~30之脂肪酸酮，作為具體例係可舉出2-壬酮，十三醛，2-十五烷酮，8-十五烷酮，3-十六烷酮，4,4-雙環己酮等。在此等之中，由具有適於產業上之利用的潛熱量，合成亦容易的觀點，氧原子數1之脂肪酸酮可較佳使用。As the fatty acid ketone, a fatty acid ketone having 8 to 30 carbon atoms can be used, and specific examples thereof include 2-nonanone, tridecanal, 2-pentadecanone, 8-pentadecanone, and 3-de. Hexadecanone, 4,4-dicyclohexanone, and the like. Among these, a fatty acid ketone having an oxygen atom number of 1 can be preferably used from the viewpoint of having a latent heat suitable for industrial use and easy synthesis.
作為上述脂肪族醇係可使用碳原子數4~60之脂肪族醇，可為於1分子中具有1個之羥基的單醇，亦可為於1分子中具有2個以上之羥基的多元醇。又，於同一分子中，亦可具有除了羧基、磺酸基、羧酸酐基、烷氧基羰基、鹵代甲醯基、胺甲醯基、氰基、甲醯基、巰基、胺基、亞胺基等之醇性羥基以外之官能基。An aliphatic alcohol having 4 to 60 carbon atoms may be used as the aliphatic alcohol, and a monool having one hydroxyl group in one molecule may be used, or a polyol having two or more hydroxyl groups in one molecule may be used. . Further, in the same molecule, it may have a carboxyl group, a sulfonic acid group, a carboxylic acid anhydride group, an alkoxycarbonyl group, a halogenated methyl group, an amine carbenyl group, a cyano group, a decyl group, a fluorenyl group, an amine group, or a sub A functional group other than an alcoholic hydroxyl group such as an amine group.
作為上述脂肪族醇之具體例係可舉出2-十二烷醇、1-十四烷醇、7-十四烷醇、1-十八烷醇、1-二十烷醇、1,10-癸二醇、新戊二醇、三羥甲基乙烷、季戊四醇等。又，表示固相-固相轉移，可舉出1,1,1-三羥甲基-2-胺基乙烷等。Specific examples of the above aliphatic alcohol include 2-dodecanol, 1-tetradecanol, 7-tetradecanol, 1-octadecyl alcohol, 1-eicosyl alcohol, and 1,10. - decanediol, neopentyl glycol, trimethylolethane, pentaerythritol, and the like. Further, examples of the solid phase-solid phase transfer include 1,1,1-trishydroxymethyl-2-aminoethane and the like.
又，具有烴直鏈構造，且每1個碳原子具有1個羥基而一般上以式[1]所示的化合物係具有高潛熱(亦即融解熱)，由提高作為蓄熱材料之性能的觀點，亦可使用此等之多元醇。 式[1]：H-(CH(OH))n -H(式中，n為4~10。) 作為如此的多元醇之具體例係可舉出赤蘚糖醇、蘇糖醇、核糖醇、***糖醇、木糖醇、糖醇(lyxitol)、阿洛糖醇(allitol)、塔羅糖醇、阿卓糖醇(altritol) 、葡萄糖醇(glucitol)、甘露醇、艾杜糖醇、半乳糖醇、D-山梨醇(gulitol)等之醛醣醇(alditol)等。Further, it has a hydrocarbon linear structure and has one hydroxyl group per one carbon atom, and generally the compound represented by the formula [1] has high latent heat (that is, heat of fusion), and the viewpoint of improving the performance as a heat storage material is obtained. It is also possible to use such polyols. Formula [1]: H-(CH(OH)) n -H (wherein n is 4 to 10.) Specific examples of such a polyol include erythritol, threitol, and ribitol. , arabitol, xylitol, lyxitol, allitol, talitol, altitol, glucitol, mannitol, iditol, Alditol such as galactitol or D-sorbitol.
在此等之中，由具有適於產業上之利用的潛熱量的觀點，至少1個羥基存在於分子末端的醇(1級醇)可較佳使用。Among these, an alcohol (a primary alcohol) having at least one hydroxyl group present at the molecular end is preferably used from the viewpoint of having a latent heat suitable for industrial use.
作為上述脂肪族醚係可使用碳原子數14~60之脂肪族醚，作為具體例係可舉出庚醚、辛醚、十四烷基醚、十六烷基醚等。在此等之中，由具有高潛熱量，合成亦容易的觀點，氧原子數1之具有對稱構造的醚(對稱醚)可較佳使用。An aliphatic ether having 14 to 60 carbon atoms can be used as the aliphatic ether, and specific examples thereof include heptyl ether, octyl ether, tetradecyl ether, and cetyl ether. Among these, an ether (symmetric ether) having a symmetrical structure having an oxygen atom number of 1 can be preferably used from the viewpoint of having high latent heat and being easy to synthesize.
作為上述包接水合物之具體例係可舉出氟化四丁基銨水合物、溴化四丁基銨水合物、三羥甲基乙烷水合物、環戊烷水合物、HCHC-141b水合物、HFC-134a水合物、二氧化碳水合物等。Specific examples of the above-mentioned inclusion hydrate include tetrabutylammonium fluoride hydrate, tetrabutylammonium bromide hydrate, trimethylolethane hydrate, cyclopentane hydrate, and HCHC-141b hydrate. , HFC-134a hydrate, carbon dioxide hydrate, and the like.
作為上述強關聯電子系統物質之具體例係可舉出V(1-X) WX O2 (0≦X≦0.0650)、V(1-X) TaX O2 (0≦X≦0.117)、 V(1-X) NbX O2 (0≦X≦0.115)、V(1-X) RuX O2 (0≦X≦0.150)、 V(1-X) MoX O2 (0≦X≦0.161)、V(1-X) ReX O2 (0≦X≦0.0964)、LiMn2 O4 、LiVS2 、LiVO2 、NaNiO2 、LiRh2 O4 、V2 O3 、V4 O7 、V6 O11 、Ti4 O7 、SmBaFe2 O5 、EuBaFe2 O5 、GdBaFe2 O5 、TbBaFe2 O5 、DyBaFe2 O5 、HoBaFe2 O5 、YBaFe2 O5 、PrBaCo2 O5.5 、DyBaCo2 O5.54 、HoBaCo2 O5.48 、YBaCo2 O5.49 等之過渡金屬氧化物等。此等係任一均表示金屬-絕緣體相轉移。Specific examples of the strongly correlated electronic system substance include V (1-X) W X O 2 (0≦X≦0.0650) and V (1-X) Ta X O 2 (0≦X≦0.117). V (1-X) Nb X O 2 (0≦X≦0.115), V (1-X) Ru X O 2 (0≦X≦0.150), V (1-X) Mo X O 2 (0≦X ≦0.161), V (1-X) Re X O 2 (0≦X≦0.0964), LiMn 2 O 4 , LiVS 2 , LiVO 2 , NaNiO 2 , LiRh 2 O 4 , V 2 O 3 , V 4 O 7 , V 6 O 11 , Ti 4 O 7 , SmBaFe 2 O 5 , EuBaFe 2 O 5 , GdBaFe 2 O 5 , TbBaFe 2 O 5 , DyBaFe 2 O 5 , HoBaFe 2 O 5 , YBaFe 2 O 5 , PrBaCo 2 O 5.5 a transition metal oxide such as DyBaCo 2 O 5.54 , HoBaCo 2 O 5.48 or YBaCo 2 O 5.49 . Any of these lines represents a metal-insulator phase transfer.
作為前述化學蓄熱材料係如為可伴隨可逆的化學反應而進行發熱、吸熱的化合物則無特別限制，例如可舉出藉由水蒸氣(水)、氨、氫、二氧化碳等之氣體之吸收(吸藏)或放出，表示發熱或吸熱的金屬鹽化合物。The chemical heat storage material is not particularly limited as long as it can generate heat and absorb heat in response to a reversible chemical reaction, and examples thereof include absorption by a gas such as water vapor (water), ammonia, hydrogen, or carbon dioxide. A metal salt compound that expresses heat or absorbs heat.
作為在上述金屬鹽化合物的金屬係可舉出第一族元素、第二族元素及過渡元素的金屬以及鋁等，具體而言可舉出由鋰、鈉、鉀、鎂、鈣、鋇、錳、鐵、鈷、鎳、銅、鋅、銀、錫及鋁所構成的群中選擇至少一種的金屬。 作為上述金屬鹽化合物係可舉出上述的金屬之碳酸鹽、硝酸鹽、硫酸鹽、矽酸鹽、膦酸鹽、羧酸鹽、鹵化物、氧化物及氫氧化物、金屬複合氧化物、添加金屬鹽之金屬氧化物以及此等之水合物。Examples of the metal of the metal salt compound include a metal of a first group element, a second group element, and a transition element, and aluminum, and specific examples thereof include lithium, sodium, potassium, magnesium, calcium, barium, and manganese. At least one metal selected from the group consisting of iron, cobalt, nickel, copper, zinc, silver, tin, and aluminum. Examples of the metal salt compound include a metal carbonate, a nitrate, a sulfate, a citrate, a phosphonate, a carboxylate, a halide, an oxide and a hydroxide, a metal composite oxide, and the like. Metal oxides of metal salts and hydrates thereof.
作為如此的金屬鹽化合物之具體例係可舉出氫氧化鎂(氧化鎂)、硫酸鈣(水合物)、氯化鈣(水合物)、氫氧化鈣(氧化鈣)、鋁矽酸鹽(沸石)等。 又，例如，可舉出日本特開2015-215155號公報所開示的蓄熱材料，亦即，苯基膦酸鎂、苯基膦酸錳等之苯基膦酸化合物之金屬鹽；2,5-二羥基對苯二甲酸鎂、對苯二甲酸錳等之芳香族羧酸化合物之金屬鹽等。 在此等之中，鋁矽酸鹽、苯基膦酸化合物之金屬鹽、芳香族羧酸化合物之金屬鹽可較佳使用。Specific examples of such a metal salt compound include magnesium hydroxide (magnesium oxide), calcium sulfate (hydrate), calcium chloride (hydrate), calcium hydroxide (calcium oxide), and aluminosilicate (zeolite). )Wait. Further, for example, a heat storage material disclosed in Japanese Laid-Open Patent Publication No. 2015-215155, that is, a metal salt of a phenylphosphonic acid compound such as phenylphosphonic acid or manganese phenylphosphonate; 2,5- A metal salt of an aromatic carboxylic acid compound such as magnesium dihydroxyterephthalate or manganese terephthalate. Among these, aluminosilicate, a metal salt of a phenylphosphonic acid compound, and a metal salt of an aromatic carboxylic acid compound can be preferably used.
在較佳的態樣中，在本發明係作為上述蓄熱材料，使用成為具有10nm～100μm之平均粒徑的粉體之形態的化合物為最佳。 尚，所謂在本發明使用的蓄熱材料的平均粒徑係藉由基於Mie理論的雷射繞射‧散射法而測定而得的50%體積直徑(中位徑)。 又，此等蓄熱材料係可單獨一種、或是亦可組合二種以上而使用。In a preferred embodiment, in the present invention, a compound which is in the form of a powder having an average particle diameter of 10 nm to 100 μm is preferably used as the heat storage material. Further, the average particle diameter of the heat storage material used in the present invention is a 50% by volume diameter (median diameter) measured by a laser diffraction ‧ scattering method based on the Mie theory. Further, these heat storage materials may be used singly or in combination of two or more.
[(B)已微細化的纖維素纖維] 本發明之蓄熱層形成用組成物，其特徵為含有(B) 已微細化的纖維素纖維。 已微細化的纖維素纖維係實際上以後述的纖維素纖維分散液之形態使用。在蓄熱層之形成，由該分散液除去水，則纖維素纖維係相互重疊或是互相纏繞等，然後與後述的(C)水溶性高分子一起捕捉蓄熱材料彼此譬如說使其結著，有助於包含蓄熱材料的膜(亦即層構造)之形成。又，在形成蓄熱層於基材上的情況，亦可承擔作為用以使蓄熱層結著於該基材上之有用的黏合劑之角色。[(B) Cellulose fiber which has been refined] The composition for forming a heat storage layer of the present invention is characterized by containing (B) a cellulose fiber which has been refined. The cellulose fiber which has been refined is actually used in the form of a cellulose fiber dispersion described later. In the formation of the heat storage layer, the water is removed from the dispersion, and the cellulose fibers are overlapped with each other or entangled with each other, and then the heat storage material is captured together with the (C) water-soluble polymer described later, for example, to be adhered thereto. It facilitates the formation of a film (ie, a layer structure) containing a heat storage material. Further, in the case where the heat storage layer is formed on the substrate, it is also possible to assume the role of a useful binder for adhering the heat storage layer to the substrate.
作為成為在本發明使用的已微細化的纖維素纖維之原料的纖維素係可廣泛地運用使用於以往之纖維素纖維之製造的原料。可將例如木材、竹、麻、黃麻、洋麻、農作物/食物殘渣等來自植物之纖維素、或是細菌纖維素、海鞘纖維素等微生物或是動物產生之纖維素作為原料而使用。此等纖維素係可單獨一種、或是亦可組合二種以上而使用。 其中，將來自植物之纖維素或細菌纖維素作為原料而使用為較佳。As the cellulose which is a raw material of the finely divided cellulose fibers used in the present invention, a raw material used for the production of the conventional cellulose fibers can be widely used. For example, cellulose derived from plants such as wood, bamboo, hemp, jute, kenaf, crops/food residue, or microorganisms such as bacterial cellulose or sea squirt cellulose or cellulose produced by animals can be used as a raw material. These celluloses may be used singly or in combination of two or more. Among them, cellulose derived from plants or bacterial cellulose is preferably used as a raw material.
上述纖維素之粉碎方法係不限定，但於微細化至合於本發明之目的的纖維之大小(長度)係高壓均質機、研磨機(石臼式磨碎機)、或是粒研磨機等之媒體攪拌磨機之可得到強的剪切應力的方法為較佳。又，在此等之中使用高壓均質機而微細化為較佳，例如日本特開2005-270891號公報所開示的濕式粉碎法，亦即，藉由將已分散纖維素的水分散液，由一對之噴嘴以高壓各自噴射而使其衝撞，粉碎纖維素者，例如藉由使用Star Burst system (Sugino Machine公司製之濕式微粒化裝置)而可實施。The pulverization method of the cellulose is not limited, but the size (length) of the fiber which is refined to the object of the present invention is a high pressure homogenizer, a grinder (stone grinder), or a grain grinder. A method of obtaining a strong shear stress by a media agitating mill is preferred. In addition, it is preferable to use a high-pressure homogenizer to refine it, for example, the wet pulverization method disclosed in Japanese Laid-Open Patent Publication No. 2005-270891, that is, by dispersing an aqueous dispersion of cellulose. The nozzles are jetted by a pair of nozzles at high pressure, and the cellulose is pulverized, for example, by using a Star Burst system (a wet micronization apparatus manufactured by Sugino Machine Co., Ltd.).
在使用前述之高壓均質機而微細化纖維素纖維時，微細化或均質化之程度係成為相依於向高壓均質機之超高壓室壓送的壓力、和通過超高壓室的次數(處理次數)、以及水分散液中之纖維素濃度。 壓送壓力(處理壓力)係通常為50~250MPa，較佳為100 ~245MPa。在壓送壓力為未達50MPa之情況係纖維素纖維之微細化變為不充分，不能得到藉由微細化而期待的效果。 又，微細化處理時之水分散液中之纖維素濃度為0.1~ 30質量%，較佳為1~10質量%。水分散液中之纖維素濃度若未達0.1質量%則生產性顯著低下，若為高於30質量%的濃度則粉碎效率低下，不能得到所期望之已微細化的纖維素纖維。 微細化之處理次數係亦依據前述水分散液中之纖維素濃度，在纖維素濃度為0.1~1質量%之情況係處理次數為10~50道次左右被充分地微細化，但在1~10質量%係成為需要50~200道次左右。又，在超過30質量%的高濃度的情況係成為需要數百次以上之處理次數，由工業上的觀點視之為不切實際。When the cellulose fiber is refined by using the above-described high-pressure homogenizer, the degree of refinement or homogenization becomes the pressure depending on the pressure of the ultrahigh pressure chamber of the high-pressure homogenizer, and the number of times of passing the ultra-high pressure chamber (the number of times of treatment) And the concentration of cellulose in the aqueous dispersion. The pressure feed pressure (treatment pressure) is usually 50 to 250 MPa, preferably 100 to 245 MPa. When the pressure feed pressure is less than 50 MPa, the refinement of the cellulose fibers is insufficient, and the effect expected by miniaturization cannot be obtained. Further, the cellulose concentration in the aqueous dispersion at the time of the refining treatment is 0.1 to 30% by mass, preferably 1 to 10% by mass. When the cellulose concentration in the aqueous dispersion is less than 0.1% by mass, the productivity is remarkably lowered. When the concentration is more than 30% by mass, the pulverization efficiency is lowered, and the desired finely divided cellulose fibers cannot be obtained. The number of times of micronization is also based on the cellulose concentration in the aqueous dispersion. When the cellulose concentration is 0.1 to 1% by mass, the number of treatments is sufficiently miniaturized from 10 to 50 passes, but in 1~ 10% by mass is required to be about 50 to 200 times. Moreover, in the case of a high concentration of more than 30% by mass, the number of times of processing required for hundreds of times or more is considered to be impractical from an industrial viewpoint.
使用於本發明的已微細化的纖維素纖維(C)係例如藉由使用雷射繞射‧散射式粒度分布計，可評估微細化之程度。 在本發明係在測定藉由前述之濕式粉碎法等而得到的纖維素纖維之水分散液之體積粒度分布時，使用表示纖維中位尺寸的在體積累計50%的粒徑(中位徑)為0.01～40 μm，特佳為0.05～10μm的纖維素纖維為較佳。 作為粒徑而測定的纖維中位尺寸，若未達0.01μm，則纖維素纖維過度地短纖維化而無法得到添加效果，亦即，即使接著打算由所得到的蓄熱層形成用組成物形成蓄熱層，膜之均勻性亦變得不充分而產生孔或破裂於膜等之成膜性為差，又，有無法充分地得到該膜之向基材之結著性的情況。又，若纖維中位尺寸大於40μm，則成為纖維素纖維之微細化不充分者，在此情況，亦因為打算形成的蓄熱層之膜之均勻性變得不充分所以無法得到所期待的效果(成膜性、向基材之結著性)，進而亦有使向蓄熱材料之流體(氣體)之接觸降低，大幅地損及蓄熱材料之性能的疑慮。又，藉由設為上述範圍，在形成的蓄熱層上纖維素纖維形成濾網狀之網目構造，可緩和蓄熱材料之伴隨相變化或化學反應的體積變化。The finely divided cellulose fibers (C) used in the present invention can be evaluated for the degree of miniaturization, for example, by using a laser diffraction ‧ scattering type particle size distribution meter. In the present invention, when measuring the volume particle size distribution of the aqueous dispersion of the cellulose fibers obtained by the above-described wet pulverization method or the like, a particle diameter (median diameter) representing a median size of the fiber of 50% is used. A cellulose fiber of 0.01 to 40 μm, particularly preferably 0.05 to 10 μm, is preferred. When the median size of the fiber measured as the particle diameter is less than 0.01 μm, the cellulose fibers are excessively fibrillated and the addition effect cannot be obtained, that is, even if it is intended to form a heat storage material from the obtained composition for forming a heat storage layer. In the layer, the uniformity of the film is also insufficient, and the film formation property such as generation of pores or cracks in the film is poor, and the film may not sufficiently exhibit the adhesion to the substrate. In addition, when the median size of the fiber is more than 40 μm, the cellulose fiber is insufficiently refined. In this case, the uniformity of the film of the heat storage layer to be formed is insufficient, so that the desired effect cannot be obtained ( The film-forming property and the adhesion to the substrate) may further reduce the contact between the fluid (gas) of the heat storage material and greatly impair the performance of the heat storage material. Further, by setting it as the above range, the cellulose fibers on the formed heat storage layer form a mesh-like mesh structure, and the volume change accompanying the phase change or the chemical reaction of the heat storage material can be alleviated.
尚，被使用於本發明的已微細化的纖維素纖維係關於纖維直徑無特別限制，但例如0.001～10μm，較佳為0.01～1μm者。 又，關於長寬比(L/D)亦無特別限制，例如10～100,000，較佳為100～10,000。In addition, the fine cellulose fiber to be used in the present invention is not particularly limited in terms of fiber diameter, but is, for example, 0.001 to 10 μm, preferably 0.01 to 1 μm. Further, the aspect ratio (L/D) is also not particularly limited, and is, for example, 10 to 100,000, preferably 100 to 10,000.
又，被使用於本發明的已微細化的纖維素纖維係以藉由前述之濕式粉碎法而得到的纖維素纖維之水分散液之形態，可使用於蓄熱層形成用組成物之調製。In addition, the finely divided cellulose fibers used in the present invention can be used for the preparation of the heat storage layer-forming composition in the form of an aqueous dispersion of the cellulose fibers obtained by the wet pulverization method described above.
在本發明之蓄熱層形成用組成物，(B) 已微細化的纖維素纖維之調配量係相對於前述(A) 蓄熱材料100質量份為0.01～100質量份，較佳為0.01～10質量份，更佳為0.1～5質量份。 若將已微細化的纖維素纖維之調配量，設為超過上述數值範圍者，則使朝向蓄熱材料之流體(氣體)之接觸降低，有損及蓄熱材料之蓄熱性能的疑慮，又若將該調配量設為未達上述數值範圍，則有無法充分地得到所期望之成膜性或向基材之結著性的情況。In the composition for forming a heat storage layer of the present invention, the blending amount of the (B) finely divided cellulose fibers is 0.01 to 100 parts by mass, preferably 0.01 to 10 parts by mass based on 100 parts by mass of the (A) heat storage material. More preferably, it is 0.1 to 5 mass parts. When the amount of the finely divided cellulose fibers is more than the above numerical range, the contact with the fluid (gas) toward the heat storage material is lowered to impair the heat storage performance of the heat storage material, and if When the blending amount is less than the above numerical range, the desired film formability or the adhesion to the substrate may not be sufficiently obtained.
[(C)水溶性高分子] 本發明之蓄熱層形成用組成物，以使成膜性提昇的目的作為黏合劑成分包含水溶性高分子。水溶性高分子係可與前述之(B) 已微細化的纖維素纖維一起有助於蓄熱材料彼此或蓄熱材料與基材之結著。 作為該水溶性高分子係無特別限定，例如由聚乙烯醇、改質聚乙烯醇、聚乙烯吡咯啶酮、聚乙二醇、聚丙烯酸鹽之部分中和物、陽離子化纖維素、甲基纖維素、乙基纖維素、羧甲基纖維素、(羧甲基)(乙基)纖維素、羥乙基纖維素、(羥乙基)(甲基)纖維素、(乙基)(羥乙基)纖維素、羥丙基纖維素、(羥丙基)(甲基)纖維素、陽離子化澱粉所構成的群中選擇至少一種。在此等之中，聚乙烯醇可較佳使用。 該水溶性高分子之由GPC所得的以聚苯乙烯換算而測定的重量平均分子量Mw係無特別限定，但例如10,000～1,000,000、較佳為50,000～500,000，更佳為100,000～300,000。[(C) Water-Soluble Polymer] The composition for forming a heat storage layer of the present invention contains a water-soluble polymer as a binder component for the purpose of improving film formability. The water-soluble polymer can contribute to the accumulation of the heat storage materials or the heat storage material and the substrate together with the cellulose fibers which have been micronized as described above (B). The water-soluble polymer is not particularly limited, and is, for example, a polyvinyl alcohol, a modified polyvinyl alcohol, a polyvinylpyrrolidone, a polyethylene glycol, a partial neutralizer of a polyacrylate, a cationized cellulose, and a methyl group. Cellulose, ethyl cellulose, carboxymethyl cellulose, (carboxymethyl) (ethyl) cellulose, hydroxyethyl cellulose, (hydroxyethyl) (methyl) cellulose, (ethyl) (hydroxyl At least one selected from the group consisting of ethyl cellulose, hydroxypropyl cellulose, (hydroxypropyl) (methyl) cellulose, and cationized starch. Among these, polyvinyl alcohol can be preferably used. The weight average molecular weight Mw measured by GPC of the water-soluble polymer in terms of polystyrene is not particularly limited, but is, for example, 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 300,000.
在本發明之蓄熱層形成用組成物，(C) 水溶性高分子之調配量係相對於前述(A) 蓄熱材料100質量份為0.01～100質量份，較佳為0.01～10質量份，更佳為0.1～5質量份，特佳為0.5~1質量份。 若將水溶性高分子之調配量設為超過上述數值範圍者，則使朝向蓄熱材料之流體(氣體)之接觸降低，有損及蓄熱材料之蓄熱性能的疑慮，又無法緩和伴隨蓄熱材料之相變化或化學反應的體積變化，有已形成的蓄熱層破損的疑慮。若將該調配量設為未達上述數值範圍，則有無法充分地得到所期望之成膜性或向基材之結著性的情況。In the composition for forming a heat storage layer of the present invention, the amount of the (C) water-soluble polymer is 0.01 to 100 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the (A) heat storage material. It is preferably 0.1 to 5 parts by mass, particularly preferably 0.5 to 1 part by mass. When the amount of the water-soluble polymer is more than the above numerical range, the contact with the fluid (gas) toward the heat storage material is lowered, and the heat storage performance of the heat storage material is impaired, and the phase accompanying the heat storage material cannot be alleviated. The volume change of the change or chemical reaction has the doubt that the formed heat storage layer is broken. When the blending amount is less than the above numerical range, the desired film formability or the adhesion to the substrate may not be sufficiently obtained.
[其他添加劑] 本發明之蓄熱層形成用組成物係只要不損及本發明之效果，亦可按照必要含有其他成分。 作為其他成分係可含有有機黏合劑、矽烷偶合劑等之接著輔助劑、增黏劑、溶劑、分散劑、整平劑、流變調整劑、流動性改良劑、消泡劑等之添加劑。[Other Additives] The composition for forming a heat storage layer of the present invention may contain other components as necessary, as long as the effects of the present invention are not impaired. The other component may contain an additive such as an organic binder or a decane coupling agent, an adhesion promoter, a solvent, a dispersant, a leveling agent, a rheology modifier, a fluidity improver, and an antifoaming agent.
[蓄熱層形成用組成物之調製方法] 本發明之蓄熱層形成用組成物係處於(A) 蓄熱材料、(B) 已微細化的纖維素纖維、(C) 水溶性高分子、以及依期望之其他添加劑為已均勻地分散、溶解於該組成物中的狀態為較佳。該調製方法係無特別限定，但例如可舉出將(A)成分、(B)成分及(C)成分以特定之比例混合，依期望而更添加其他添加劑而混合，設為均勻的溶液的方法、在此等各成分之中，例如混合(A)成分及(B)成分之一部分而設為均勻的溶液後，加入剩下的(C)成分，藉由期望而更添加其他添加劑而混合，設為均勻的溶液的方法，或是除了此等之成分進而使用慣用之溶媒(水等)的方法等。 又，可舉出藉由前述之濕式粉碎法而以水分散液之形態調製(B) 已微細化的纖維素纖維，於已得到的水分散液混合(A)成分及(C)成分(以及依期望而其他添加劑)的方法。[Preparation method of the composition for forming a heat storage layer] The composition for forming a heat storage layer of the present invention is (A) a heat storage material, (B) a cellulose fiber which has been refined, (C) a water-soluble polymer, and a desired The other additives are preferably uniformly dispersed and dissolved in the composition. The preparation method is not particularly limited, and examples thereof include mixing the component (A), the component (B), and the component (C) in a specific ratio, and mixing them with other additives as desired, and forming a uniform solution. In the above-mentioned components, for example, a part of the components (A) and (B) are mixed to form a uniform solution, and then the remaining component (C) is added, and further additives are added as desired. A method of setting a uniform solution or a method of using a conventional solvent (water or the like) in addition to the components. Further, by the wet pulverization method described above, (B) the cellulose fibers which have been refined in the form of an aqueous dispersion are mixed, and the components (A) and (C) are mixed in the obtained aqueous dispersion ( And other additives as desired).
在使用水等之溶媒的情況，蓄熱層形成用組成物的固形分之比例係只要各成分均勻地分散、溶解於溶媒就無特別限定，但例如為1~50質量%、或1~30質量%、或1~25質量%。在此所謂固形分係由蓄熱層形成用組成物之全成分除去溶媒成分(水等)者。When a solvent such as water is used, the ratio of the solid content of the composition for forming a heat storage layer is not particularly limited as long as the components are uniformly dispersed and dissolved in the solvent, but it is, for example, 1 to 50% by mass or 1 to 30% by mass. %, or 1 to 25% by mass. Here, the solid fraction is obtained by removing the solvent component (water or the like) from the entire component of the heat storage layer forming composition.
[蓄熱層] 本發明係亦將蓄熱層設為對象，其係含有蓄熱材料、已微細化的纖維素纖維及水溶性高分子，在此前述蓄熱材料係該等為相互藉由前述纖維素纖維及前述水溶性高分子而捕捉，形成膜形狀而成。 例如，可藉由於適當的基材上塗佈本發明之蓄熱層形成用組成物，使已得到的塗膜乾燥的方法，由本發明之蓄熱層形成用組成物製作蓄熱層，如此地進行而藉由本發明之蓄熱層形成用組成物而製作的蓄熱層亦為本發明之對象。 前述基材係可按照該蓄熱層所適用的用途而適宜地選擇，例如可舉出鋁、銅、鋼材、不鏽鋼等之金屬材料；玻璃、氧化鋁等之陶瓷等。 前述蓄熱層形成用組成物之向基材上之塗佈方法係無特別限定，但例如可採用噴霧塗佈、旋轉塗佈、流動塗佈、輥塗佈、狹縫塗佈、在狹縫後旋轉塗佈、噴墨塗佈、澆鑄塗佈、印刷等之一般使用的手法。 在塗佈後，使形成於基材之表面的塗膜乾燥的手段係無特別限制，例如可採用加熱乾燥、送風乾燥、減壓乾燥等，以往一般周知之技術。 塗膜之乾燥條件(乾燥時間、乾燥溫度等)係按照上述蓄熱層形成用組成物之塗佈量及由蓄熱層形成用組成物之水分揮發速度，例如在以40~100℃進行1~24小時之範圍適宜地選擇。 以如此的方式進行而得到的蓄熱層之厚度係一般而言，為0.1～5,000μm，較佳為1～2,000μm。[The heat storage layer] The present invention also relates to a heat storage layer, which comprises a heat storage material, a finely divided cellulose fiber, and a water-soluble polymer, wherein the heat storage material is the cellulose fiber by the foregoing And the water-soluble polymer is captured and formed into a film shape. For example, a method of drying the obtained coating film by applying the composition for forming a heat storage layer of the present invention to a suitable substrate, and forming a heat storage layer from the composition for forming a heat storage layer of the present invention, can be carried out in this manner. The heat storage layer produced by the composition for forming a heat storage layer of the present invention is also an object of the present invention. The substrate may be appropriately selected depending on the application to which the heat storage layer is applied, and examples thereof include metal materials such as aluminum, copper, steel, and stainless steel; and ceramics such as glass and alumina. The coating method on the substrate for forming the heat storage layer is not particularly limited, and for example, spray coating, spin coating, flow coating, roll coating, slit coating, or slit may be employed. A general method of spin coating, inkjet coating, casting coating, printing, and the like. The means for drying the coating film formed on the surface of the substrate after the application is not particularly limited, and for example, heat drying, air drying, vacuum drying, or the like can be employed. The drying conditions (drying time, drying temperature, and the like) of the coating film are in accordance with the coating amount of the composition for forming a heat storage layer and the water evaporation rate of the composition for forming a heat storage layer, for example, 1 to 24 at 40 to 100 ° C. The range of hours is suitably selected. The thickness of the heat storage layer obtained in this manner is generally 0.1 to 5,000 μm, preferably 1 to 2,000 μm.
[熱交換器] 本發明亦將設置有前述蓄熱層的熱交換器，具體而言，係於熱傳導性基材之表面形成前述蓄熱層的熱交換器設為對象。 前述熱傳導性基材係構成熱媒體流通的流路(熱媒體流路)之隔壁而形成，然後藉由於與該隔壁之熱媒體流通側相反側之面形成前述蓄熱層，促進蓄熱層與熱媒體之間之熱傳導。 前述熱媒體係例如可設為原動機之冷卻水。 本發明設為對象物的熱交換器係例如可作為裝載於車輛的熱交換器而使用。 [實施例][Heat exchanger] The present invention also provides a heat exchanger provided with the above-described heat storage layer, and specifically, a heat exchanger that forms the heat storage layer on the surface of the heat conductive substrate. The heat conductive substrate is formed by forming a partition wall of a flow path (heat medium flow path) through which the heat medium flows, and then the heat storage layer is formed on the surface opposite to the heat medium flow side of the partition wall to promote the heat storage layer and the heat medium. Heat transfer between. The heat medium can be, for example, a cooling water of a prime mover. The heat exchanger which is an object of the present invention can be used, for example, as a heat exchanger mounted on a vehicle. [Examples]
以下，舉出實施例而更具體地說明本發明，但本發明係不被限定於下述之實施例。 尚，在實施例，使用於試料之調製及物性之分析的裝置及條件係如以下所述。Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples described below. Further, in the examples, the apparatus and conditions for the analysis of the preparation and physical properties of the sample are as follows.
(1) 雷射繞射‧散射式粒度分布計 裝置：Malvern Instruments公司製Mastersizer(登錄商標)2000 (2) TG-DTA 裝置：Rigaku公司製 Thermo plus EVO II TG8120 氣體流量調整器：Rigaku公司製 Thermo plus EVO II用MASS FLOW UNIT (3) 起泡器 裝置：AS ONE公司製PFA氣體洗淨瓶(球過濾器孔徑：20～30μm)(1) Laser diffraction ‧ scattering type particle size distribution device: Mastersizer (registered trademark) 2000 manufactured by Malvern Instruments Inc. (2) TG-DTA device: Thermo plus EVO II TG8120 manufactured by Rigaku Co., Ltd. Gas flow regulator: Thermo by Rigaku Co., Ltd. MASS FLOW UNIT for plus EVO II (3) Bubbler unit: PFA gas cleaning bottle made by AS ONE (ball filter aperture: 20 to 30 μm)
又，使用於試料之調製的成分之詳細係如以下所述。 ‧ 聚乙烯醇(PVA)：JAPAN VAM & POVAL公司製，製品名 AT-17 ‧ 沸石：三菱樹脂公司製，製品名 AQSOA(登錄商標) Z02Further, the details of the components used for the preparation of the sample are as follows. ‧ Polyvinyl alcohol (PVA): manufactured by JAPAN VAM & POVAL, product name AT-17 ‧ Zeolite: manufactured by Mitsubishi Plastics Co., Ltd., product name AQSOA (registered trademark) Z02
[製造例1：已微細化的纖維素纖維水分散液之調製] 使市售纖維素粉末[Celite公司製，Fibra-Cell BH-100] 5質量份分散於純水495質量份，進行微細化處理(Sugino Machine公司製，Star Burst system) (200MPa、50Pass)，得到已微細化的纖維素纖維水分散液。將已得到的纖維素纖維水分散液量取於培養皿中，以110℃進行5小時乾燥，除去水分而測定殘渣之量，測定濃度。該結果，水中之已微細化的纖維素纖維濃度(固形分濃度)為0.74質量%。 將已得到的纖維素纖維使用雷射繞射‧散射式粒度分布計，表示將水作為分散媒而測定的纖維中位尺寸的在體積累計50%之粒徑為0.6μm。[Production Example 1: Preparation of a finely divided cellulose fiber aqueous dispersion] 5 parts by mass of a commercially available cellulose powder [Fila-Cell BH-100, manufactured by Celite Co., Ltd.] was dispersed in 495 parts by mass of pure water to be miniaturized. Treatment (Sibero Machine Co., Ltd., Star Burst system) (200 MPa, 50 Pass) was carried out to obtain a finely divided aqueous cellulose fiber dispersion. The obtained cellulose fiber aqueous dispersion was weighed in a Petri dish, and dried at 110 ° C for 5 hours to remove water, and the amount of the residue was measured, and the concentration was measured. As a result, the concentration of the cellulose fibers (solid content concentration) which had been refined in water was 0.74% by mass. The obtained cellulose fiber was subjected to a laser diffraction/scattering particle size distribution meter, and the particle diameter of the median size of the fiber measured by using water as a dispersion medium was 50%, and the particle diameter was 0.6 μm.
[實施例1] 於藉由製造例1而得到的已微細化的纖維素纖維水分散液1.35g(固形分0.01g)，加入事先調製的2質量%聚乙烯醇水溶液0.50g(固形分0.01g)及水2.15g。進而添加沸石1.00g，攪拌大約15分鐘，藉此得到蓄熱層形成用組成物(固形分：20質量%)。[Example 1] 1.35 g of a finely divided aqueous cellulose fiber dispersion obtained by Production Example 1 (solid content: 0.01 g), and 0.50 g of a 2% by mass aqueous solution of polyvinyl alcohol prepared in advance (solid content: 0.01) g) and water 2.15g. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer (solid content: 20% by mass).
[實施例2] 於微細纖維素水分散液0.10g[中越紙漿工業公司製，商品名 BB-CNF-A-10，紙漿原料：竹漂白紙漿、固形分濃度：10質量%、依上述測定所得的粒徑(纖維中位尺寸)：18μm] (固形分0.01g)，加入事先調製的2質量%聚乙烯醇水溶液0.50g(固形分0.01g)及水3.40g。進而添加沸石1.00g，攪拌大約15分鐘，藉此得到蓄熱層形成用組成物(固形分：20質量%)。[Example 2] 0.10 g of a fine cellulose aqueous dispersion [manufactured by Nakagawa Pulp Co., Ltd., trade name: BB-CNF-A-10, pulp raw material: bamboo bleached pulp, solid content concentration: 10% by mass, according to the above measurement Particle size (median size of fiber): 18 μm] (solid content: 0.01 g), and 0.50 g (solid content: 0.01 g) of a 2% by mass aqueous polyvinyl alcohol solution prepared in advance and 3.40 g of water were added. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer (solid content: 20% by mass).
[比較例1] 將沸石1.00g添加至水4.00g，攪拌大約15分鐘，藉此得到比較例之蓄熱層形成用組成物(固形分：20質量%)。[Comparative Example 1] 1.00 g of zeolite was added to 4.00 g of water, and the mixture was stirred for about 15 minutes to obtain a composition for forming a heat storage layer of a comparative example (solid content: 20% by mass).
[比較例2] 於事先調製的2質量%聚乙烯醇水溶液0.50g(固形分0.01g)加入水3.50g而稀釋。進而添加沸石1.00g，攪拌大約15分鐘，藉此得到比較例之蓄熱層形成用組成物(固形分：20質量%)。[Comparative Example 2] 0.50 g of a 2% by mass aqueous polyvinyl alcohol solution prepared in advance (solid content: 0.01 g) was added to 3.50 g of water to be diluted. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer of a comparative example (solid content: 20% by mass).
[比較例3] 於事先調製的2質量%聚乙烯醇水溶液2.50g(固形分0.05g)加入水1.50g而稀釋。進而添加沸石1.00g，攪拌大約15分鐘，藉此得到比較例之蓄熱層形成用組成物(固形分：21質量%)。[Comparative Example 3] 2.50 g of a 2% by mass aqueous polyvinyl alcohol solution prepared in advance (solid content: 0.05 g) was added to 1.50 g of water to be diluted. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer of a comparative example (solid content: 21% by mass).
[比較例4] 於藉由製造例1而得到的已微細化的纖維素纖維1.35g(固形分0.01g)，加入水2.65g。進而添加沸石1.00g，攪拌大約15分鐘，藉此得到比較例之蓄熱層形成用組成物(固形分：20質量%)。[Comparative Example 4] 1.35 g (solid content: 0.01 g) of the finely obtained cellulose fibers obtained in Production Example 1 was added, and 2.65 g of water was added. Further, 1.00 g of zeolite was added and stirred for about 15 minutes to obtain a composition for forming a heat storage layer of a comparative example (solid content: 20% by mass).
於表1表示實施例及比較例之蓄熱層形成用組成物之調配。尚，表1中，「份」係表示「質量份」。 Table 1 shows the blending of the heat storage layer-forming compositions of the examples and the comparative examples. In addition, in Table 1, "parts" means "parts by mass".
[成膜性之評估] 將在實施例1及實施例2以及比較例1至比較例4調製的蓄熱層形成用組成物1.5mL，藉由溶液澆鑄法塗佈於25mm平方之玻璃基板上，形成塗膜。將該塗膜以110℃乾燥，形成厚度約1mm之蓄熱層。 將乾燥後之塗膜(蓄熱層)以目視觀察，評估龜裂之有無。又，將該已形成蓄熱層的玻璃基板相對於該基板之水平面傾斜至垂直，此時，以目視確認由基板之蓄熱層(膜)之浮起或脫落之有無，評估向基板之密著性。尚，評估係各自根據以下之基準而評估。將所得到的結果合併表示於表3。 ＜＜龜裂有無評估基準＞＞ A：無龜裂 C：有龜裂 ＜＜密著性評估基準＞＞ A：蓄熱層密著於基板，無浮起或脫落 C：蓄熱層未密著於基板[Evaluation of Film Formation Property] 1.5 mL of the composition for forming a heat storage layer prepared in Example 1 and Example 2 and Comparative Example 1 to Comparative Example 4 was applied onto a 25 mm square glass substrate by a solution casting method. A coating film is formed. The coating film was dried at 110 ° C to form a heat storage layer having a thickness of about 1 mm. The dried coating film (heat storage layer) was visually observed to evaluate the presence or absence of cracks. In addition, the glass substrate on which the heat storage layer was formed was inclined to be perpendicular to the horizontal plane of the substrate. In this case, the presence or absence of floating or falling off of the heat storage layer (film) of the substrate was visually observed, and the adhesion to the substrate was evaluated. . The assessments are each evaluated against the following benchmarks. The results obtained are combined and shown in Table 3. <<Criteria for evaluation of cracks>> A: No cracks C: Cracks <<Adhesion evaluation criteria>> A: The heat storage layer is adhered to the substrate, and there is no floating or falling off C: The heat storage layer is not tightly attached to Substrate
如表3所示，在實施例1及實施例2調製的蓄熱層形成用組成物係於玻璃基板上形成無龜裂的均勻的膜狀之含沸石之蓄熱層，且，在將該已形成蓄熱層的玻璃基板相對於該基板之水平面傾斜至垂直的情況，亦未觀察到該蓄熱層由玻璃基板之浮起或脫落，確認密著且固定化於玻璃基板上。 另一方面，在僅包含沸石的組成物(比較例1)、僅包含沸石和水溶性高分子或纖維素纖維的組成物(比較例2、比較例4)係於乾燥後之塗膜(蓄熱層)可看到龜裂，又，在傾斜玻璃基板的情況，在蓄熱層觀察到由玻璃基板之浮起或脫落。 尚，在僅包含沸石和水溶性高分子的組成物，和在增加水溶性高分子之調配量的情況(比較例3)係與實施例之組成物相同，形成無龜裂的均勻的膜狀，然後密著且固定化於玻璃基板的蓄熱層。As shown in Table 3, the heat storage layer-forming composition prepared in the first embodiment and the second embodiment is formed on the glass substrate to form a uniform film-like zeolite-containing heat storage layer having no cracks, and the formed layer is formed. When the glass substrate of the heat storage layer was inclined to be perpendicular to the horizontal plane of the substrate, the heat storage layer was not observed to float or fall off from the glass substrate, and it was confirmed that the heat storage layer was adhered to the glass substrate. On the other hand, the composition containing only zeolite (Comparative Example 1) and the composition containing only zeolite and water-soluble polymer or cellulose fiber (Comparative Example 2, Comparative Example 4) were coated on a dried film (heat storage) The layer can be seen to be cracked, and in the case of tilting the glass substrate, floating or falling off of the glass substrate is observed in the heat storage layer. Further, in the case of a composition containing only zeolite and a water-soluble polymer, and a case where the amount of the water-soluble polymer was increased (Comparative Example 3), the composition was the same as that of the example, and a uniform film-like form without cracks was formed. Then, it is adhered and fixed to the heat storage layer of the glass substrate.
＜水蒸氣吸附性之評估＞ 根據前述之成膜性之評估之結果，使用實施例1及實施例2以及比較例3之蓄熱層形成用組成物，進行以下所示的水蒸氣吸附性之評估。又，將僅使用沸石粉末的例作為比較例1採用，同樣地進行水蒸氣吸附性之評估。 尚，本實施例係藉由對於蓄熱層(沸石)的水蒸氣之吸附、脫水行為，評估作為蓄熱層之蓄熱性能者。<Evaluation of Water Vapor Adsorption> The heat storage layer-forming compositions of Examples 1 and 2 and Comparative Example 3 were used to evaluate the water vapor adsorption properties shown below based on the results of the evaluation of the film formation properties described above. . Further, an example in which only the zeolite powder was used was used as Comparative Example 1, and the evaluation of the water vapor adsorption property was carried out in the same manner. Further, in the present embodiment, the heat storage performance as the heat storage layer was evaluated by the adsorption and dehydration behavior of the water vapor of the heat storage layer (zeolite).
＜＜試驗順序＞＞ 於TG-DTA用鋁盤(f5mm)，以固形分成為10mg之方式，將在實施例1、實施例2、或比較例3調製的蓄熱層形成用組成物分取約50μL。 將此在110℃之加熱板上乾燥，於鋁盤中形成蓄熱層而作為試料。又，另外於鋁盤量取沸石粉末10mg，將此作為比較例1之試料。 於TG-DTA裝置本體與氣體流量調整器之間設置起泡器(23℃)，設為可將高濕度之空氣(含水蒸氣之空氣：Air/H2 O)向裝置本體導入。尚，藉由將Air/H2 O流路保持在23℃以上，防止氣體流路中之凝結。 使用下述表2所示的溫度/氣體程式，於TG-DTA裝置本體導入Air/H2 O，追蹤各試料(蓄熱層、沸石粉末)之質量變化及發熱、吸熱行為。將藉由各試料而得到的TG及TG/DTA圖表，各自表示於第1圖(實施例1)、第2圖(實施例2)、第3圖(比較例1)及第4圖(比較例3)。<<Testing procedure>> The composition for forming a heat storage layer prepared in Example 1, Example 2, or Comparative Example 3 was dispensed in an aluminum disk (f5 mm) for TG-DTA, and the solid content was 10 mg. 50 μL. This was dried on a hot plate at 110 ° C to form a heat storage layer in an aluminum pan as a sample. Further, 10 mg of zeolite powder was weighed in an aluminum pan, and this was used as a sample of Comparative Example 1. A bubbler (23 ° C) is provided between the main body of the TG-DTA device and the gas flow rate adjuster, so that high-humidity air (air containing water vapor: Air/H 2 O) can be introduced into the apparatus body. Further, by keeping the Air/H 2 O flow path at 23 ° C or higher, condensation in the gas flow path is prevented. Air/H 2 O was introduced into the TG-DTA apparatus using the temperature/gas program shown in Table 2 below, and the mass change, heat generation, and heat absorption behavior of each sample (heat storage layer, zeolite powder) were followed. The TG and TG/DTA charts obtained by each sample are shown in Fig. 1 (Example 1), Fig. 2 (Example 2), Fig. 3 (Comparative Example 1), and Fig. 4 (Comparative Example 3).
尚，表2所示的程式中，在TG-DTA裝置流動Air/H2 O的期間(No.3、No.7)係對應於向蓄熱層(沸石)之水蒸氣之吸附步驟，裝置中之氣體(Air/H2 O、N2 )之流量為零之期間(No.4、No.8(、No.10))係對應於蓄熱層(沸石)之脫水步驟。又，流動N2 氣體的期間(No.1-2、No.5-6、No.9)係對應於除去系統內之水蒸氣的步驟。In the program shown in Table 2, during the period in which the TG-DTA device flows Air/H 2 O (No. 3, No. 7), the adsorption step corresponding to the water vapor to the heat storage layer (zeolite) is performed in the apparatus. The period (No. 4, No. 8 (No. 10)) in which the flow rate of the gas (Air/H 2 O, N 2 ) is zero corresponds to the dehydration step of the heat storage layer (zeolite). Moreover, the period (No. 1-2, No. 5-6, No. 9) in which the N 2 gas flows is a step corresponding to the removal of water vapor in the system.
根據由各試料而得到的TG/DTA結果，將Air/H2 O氣體流入30分鐘後之試料之質量增加率設為水蒸氣之吸附率[%]，又將Air/H2 O氣體流入所致的試料之質量增加初期之增加速度設為初期之水蒸氣之吸附速度[%/分鐘]，評估在各試料的水蒸氣之吸附行為。 尚，將在表2的No.2～No.5、No.6～No.9各自作為1週期算出各值，以合計2週期之平均值進行評估。將所得到的結果合併表示於表3。 ‧ 蓄熱層乾燥質量[mg] =向鋁盤之試料之投入質量[mg]×(100+TG(質量變化)之最小值[%])/100 ‧ 蓄熱層質量變化量[mg] =｛向鋁盤之試料之投入質量[mg]×(100+TG(質量變化)之值[%])/100｝-蓄熱層乾燥質量[mg] ‧ 蓄熱層質量變化率[%] =[蓄熱層質量變化量[mg]/蓄熱層乾燥質量[mg]]×100 ‧ Air/H2 O氣體流入30分鐘後之吸附率 =流入Air/H2 O氣體30分鐘後(表2中之程式No.3、No.7結束之後)之蓄熱層質量變化率[%] ‧ 初期之水蒸氣之吸附速度[%/分鐘] =(在質量增加開始時間t的蓄熱層質量變化率[%]-由質量增加開始時間t開始1分鐘後之蓄熱層質量變化率[%])/[質量增加開始時間t[分鐘]-(質量增加開始時間t+1)[分鐘]]According to the TG/DTA results obtained from the respective samples, the mass increase rate of the sample after the Air/H 2 O gas flowed for 30 minutes was set as the adsorption rate [%] of the water vapor, and the Air/H 2 O gas was introduced into the place. The increase rate at the initial stage of the mass increase of the sample was set as the initial adsorption rate of water vapor [%/min], and the adsorption behavior of water vapor in each sample was evaluated. In addition, each of No. 2 - No. 5 and No. 6 - No. 9 of Table 2 was calculated as one cycle, and the average value of two cycles was evaluated. The results obtained are combined and shown in Table 3. ‧ Heat storage layer drying quality [mg] = input mass to the aluminum plate sample [mg] × (100 + TG (minus of mass change) [%]) / 100 ‧ Heat storage layer mass change amount [mg] = {向Input quality of sample of aluminum plate [mg] × (value of 100 + TG (mass change) [%]) / 100} - dry heat of regenerator layer [mg] ‧ mass change rate of heat storage layer [%] = [heat storage layer quality Change amount [mg] / heat storage layer dry mass [mg]] × 100 ‧ Air/H 2 O gas adsorption rate after 30 minutes of inflow = 30 minutes after flowing into Air/H 2 O gas (program No. 3 in Table 2) The rate of change of the mass of the heat storage layer after the end of No. 7 [%] ‧ The adsorption rate of water vapor at the beginning [%/min] = (the rate of change of the mass of the heat storage layer at the start time t of the mass increase [%] - increased by mass The heat storage layer mass change rate [%] after 1 minute from the start time t / [mass increase start time t [minute] - (mass increase start time t+1) [minutes]]
又根據由各試料而得到的TG/DTA結果，得到DTA曲線之波峰溫度[℃]及DTA面積[μV・sec/mg]，作為在各試料的水蒸氣之脫水行為而評估。尚，與吸附行為相同，將在表2的No.2～No.5、No.6～No.9各自作為1週期算出各值，以合計2週期之平均值進行評估。將所得到的結果合併表示於表3。Further, based on the TG/DTA results obtained from the respective samples, the peak temperature [°C] of the DTA curve and the DTA area [μV·sec/mg] were obtained and evaluated as the dehydration behavior of the water vapor in each sample. In the same manner as in the adsorption behavior, each of No. 2 to No. 5 and No. 6 to No. 9 in Table 2 was calculated as one cycle, and the average value of two cycles was evaluated. The results obtained are combined and shown in Table 3.
如表3所示，確認由在實施例1及實施例2調製的蓄熱層形成用組成物而得到的試料係表示與蓄熱材料本身(沸石、比較例1)同等之水蒸氣吸附行為及脫水行為，亦即形成維持蓄熱性能的良好的層而成。 另一方面，確認由在比較例3調製的蓄熱層形成用組成物而得到的試料係相較於蓄熱材料(沸石、比較例1)，水蒸氣之吸附率、質量增加速度較大幅地變差，又，於DTA看不到波峰，幾乎未進行水蒸氣之吸附、脫水，亦即層雖然形成但成為蓄熱性能大幅地劣化的層。As shown in Table 3, the sample obtained by the composition for forming a heat storage layer prepared in the first embodiment and the second embodiment showed the same water vapor adsorption behavior and dehydration behavior as the heat storage material itself (zeolite, comparative example 1). That is, a good layer that maintains heat storage performance is formed. On the other hand, it was confirmed that the sample system obtained by the composition for forming a heat storage layer prepared in Comparative Example 3 was more deteriorated in the rate of increase in the adsorption rate and the mass of the water than the heat storage material (zeolite, Comparative Example 1). Further, no peak was observed in DTA, and almost no adsorption or dehydration of water vapor was performed, that is, a layer which was formed to have a large deterioration in heat storage performance.
[第1圖]第1圖係表示由實施例1之蓄熱層形成用組成物得到的試料之TG-DTA圖表的圖。 [第2圖]第2圖係表示由實施例2之蓄熱層形成用組成物得到的試料之TG-DTA圖表的圖。 [第3圖]第3圖係表示由比較例1之蓄熱層形成用組成物得到的試料之TG-DTA圖表的圖。 [第4圖]第4圖係表示由比較例3之蓄熱層形成用組成物得到的試料之TG-DTA圖表的圖。[Fig. 1] Fig. 1 is a view showing a TG-DTA chart of a sample obtained from the composition for forming a heat storage layer of Example 1. [Fig. 2] Fig. 2 is a view showing a TG-DTA chart of a sample obtained from the composition for forming a heat storage layer of Example 2. [Fig. 3] Fig. 3 is a view showing a TG-DTA chart of a sample obtained from the composition for forming a heat storage layer of Comparative Example 1. [Fig. 4] Fig. 4 is a view showing a TG-DTA chart of a sample obtained from the composition for forming a heat storage layer of Comparative Example 3.
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