JP2008088376A - Heat storage composition - Google Patents
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- JP2008088376A JP2008088376A JP2006273499A JP2006273499A JP2008088376A JP 2008088376 A JP2008088376 A JP 2008088376A JP 2006273499 A JP2006273499 A JP 2006273499A JP 2006273499 A JP2006273499 A JP 2006273499A JP 2008088376 A JP2008088376 A JP 2008088376A
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Abstract
Description
本発明は、例えば椅子、ソファー、クッション、マットレス、ベッド、食品用トレー、食品収納容器、食品梱包材、果物包装材、ＯＡ機器等の昇温防止材、自動車用ヘットレスト、シートクッション、自動車内装材、自動車天井材、車椅子用クッション、衝撃吸収用パッキン、内装用ウレタン、清掃用スポンジ、車両ワックス用スポンジ、台所用スポンジ、浴用スポンジ、水処理用微生物固定化担体、マウスパッド、ガラス目地材、土木用目地材、化粧用パフ材、ヘルメット内張り、建築用シーリング、衣料用パッド材、両面テープ基材、エアコン断熱材、保護梱包材、接着剤、粘着剤、コーティング剤、防振ゴムや防振ゲルなど、広範な用途に使用可能な蓄熱組成物に関する。 The present invention includes, for example, a chair, a sofa, a cushion, a mattress, a bed, a food tray, a food storage container, a food packaging material, a fruit packaging material, an OA device and the like, a heating rest material for an automobile, a seat cushion, and an automobile interior material. , Automotive ceiling materials, wheelchair cushions, shock absorbing packing, interior urethane, cleaning sponges, vehicle wax sponges, kitchen sponges, bath sponges, microbial immobilization carriers for water treatment, mouse pads, glass joint materials, civil engineering Joint materials, makeup puff materials, helmet lining, architectural sealing, clothing pad materials, double-sided tape base materials, air conditioner insulation materials, protective packaging materials, adhesives, adhesives, coating agents, anti-vibration rubber and anti-vibration gels The present invention relates to a heat storage composition that can be used for a wide range of applications.
従来より、メラミン樹脂などを用いてシェル壁を形成したシェル内に潜熱蓄熱剤を封入した蓄熱性マイクロカプセルが提案されている（特許文献１及び２参照）。 Conventionally, a heat storage microcapsule in which a latent heat storage agent is enclosed in a shell in which a shell wall is formed using melamine resin or the like has been proposed (see Patent Documents 1 and 2).
これらの蓄熱性マイクロカプセルを用いて所望形状の蓄熱成形体を製造する方法として、例えば蓄熱性マイクロカプセルを熱可塑性樹脂に混練し、この混練物を押し出し成形する方法がある。 As a method for producing a heat storage molded body having a desired shape using these heat storage microcapsules, for example, there is a method of kneading the heat storage microcapsules into a thermoplastic resin and extruding the kneaded product.
ところが、上記方法により成形体を製造する場合、成形時の熱によって蓄熱性マイクロカプセルが破壊されたり、破壊されないまでも、蓄熱剤を封入するシェルの熱膨張によりシェル壁と蓄熱剤との間に隙間が生じ、十分な蓄熱効果が得られないといった不具合があった。 However, when a molded body is produced by the above method, the heat-storing microcapsules are destroyed or not destroyed by the heat at the time of molding, so that the thermal expansion of the shell enclosing the heat storage agent causes the thermal expansion between the shell wall and the heat storage agent. There was a problem that a gap was generated and a sufficient heat storage effect could not be obtained.
本発明は、上述の技術的課題に鑑みなされたものであり、成形時の熱によって蓄熱性マイクロカプセルが破壊されたり、十分な蓄熱効果が得られないといった不具合が生じることがなく、優れた蓄熱効果を有する蓄熱組成物を提供することをその目的とするものである。 The present invention has been made in view of the above-described technical problems, and the heat storage microcapsules are not destroyed by heat at the time of molding, or a sufficient heat storage effect cannot be obtained, and excellent heat storage is achieved. The object is to provide a heat storage composition having an effect.
上記目的を達成するため、本発明は、成形温度が１００℃以下のポリマーマトリックス中にマイクロカプセル化された蓄熱性材料が含まれていることを特徴とする蓄熱組成物をその要旨とした。 In order to achieve the above object, the gist of the present invention is a heat storage composition characterized in that a heat storage material microencapsulated in a polymer matrix having a molding temperature of 100 ° C. or less is contained.
本発明の蓄熱組成物にあっては、成形温度が１００℃以下のポリマーマトリックス中にマイクロカプセル化された蓄熱性材料が含まれていることから、成形時の温度を低くすることができるため、成形時の熱によって、蓄熱性マイクロカプセルが破壊されたり、十分な蓄熱効果が得られないといった不具合が生じることがない。 In the heat storage composition of the present invention, since the heat storage material microencapsulated in a polymer matrix having a molding temperature of 100 ° C. or less is included, the temperature at the time of molding can be lowered. The heat at the time of molding does not break down the heat-storing microcapsules or fail to obtain a sufficient heat storage effect.
以下、本発明の蓄熱組成物を更に詳しく説明する。本発明の蓄熱組成物は、例えば椅子、ソファー、クッション、マットレス、ベッド、食品用トレー、食品収納容器、食品梱包材、果物包装材、ＯＡ機器等の昇温防止材、自動車用ヘットレスト、シートクッション、自動車内装材、自動車天井材、車椅子用クッション、衝撃吸収用パッキン、内装用ウレタン、清掃用スポンジ、車両ワックス用スポンジ、台所用スポンジ、浴用スポンジ、水処理用微生物固定化担体、マウスパッド、ガラス目地材、土木用目地材、化粧用パフ材、ヘルメット内張り、建築用シーリング、衣料用パッド材、両面テープ基材、エアコン断熱材、保護梱包材、接着剤、粘着剤、コーティング剤、防振ゴムや防振ゲルなど、広範な用途に使用可能である。 Hereinafter, the heat storage composition of the present invention will be described in more detail. The heat storage composition of the present invention includes, for example, a chair, a sofa, a cushion, a mattress, a bed, a food tray, a food storage container, a food packaging material, a fruit packaging material, an OA device and the like, a heat rest material for automobiles, and a seat cushion. , Automotive interior materials, automotive ceiling materials, wheelchair cushions, shock absorbing packing, interior urethane, cleaning sponges, vehicle wax sponges, kitchen sponges, bath sponges, microbial immobilization carriers for water treatment, mouse pads, glass Joint materials, joint materials for civil engineering, puff materials for makeup, helmet lining, sealing materials for buildings, pad materials for clothing, double-sided tape base materials, air conditioner insulation materials, protective packaging materials, adhesives, adhesives, coating agents, anti-vibration rubber It can be used for a wide range of applications such as anti-vibration gels.
本発明の蓄熱組成物は、成形温度が１００℃以下のポリマーマトリックス中にマイクロカプセル化された蓄熱性材料が含まれていることで特徴づけられたものである。 The heat storage composition of the present invention is characterized in that a heat storage material microencapsulated in a polymer matrix having a molding temperature of 100 ° C. or lower is included.
本発明の蓄熱組成物のマトリックスを構成するポリマーには、用途や使用状態に応じて、成形温度が１００℃以下の熱可塑性樹脂、熱可塑性エラストマー、熱硬化性樹脂、ゴム、ゲル、あるいは水系エマルジョン樹脂などを用いることができる。 The polymer constituting the matrix of the heat storage composition of the present invention includes a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, rubber, gel, or water-based emulsion having a molding temperature of 100 ° C. or less, depending on the application and usage conditions. Resins can be used.
熱可塑性樹脂としては、汎用プラスチック及びエンジニアリングプラスチックから選ばれる１種若しくは２種以上を挙げることができ、汎用プラスチックとしては、例えばポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリ塩化ビニル（ＰＶＣ）、ポリスチレン（ＰＳ）、アクリロニトリルブタジエンスチレン共重合体（ＡＢＳ）、アクリロニトリルスチレン共重合体（ＡＳ）、ポリメタクリル酸メチル（ＰＭＭＡ）、塩素化ポリエチレン（ＣＰＥ）、及びエチレン酢酸ビニル共重合体（ＥＶＡ）から選ばれる１種若しくは２種以上を挙げることができる。 Examples of the thermoplastic resin include one or more selected from general-purpose plastics and engineering plastics. Examples of the general-purpose plastics include polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), and polystyrene. (PS), acrylonitrile butadiene styrene copolymer (ABS), acrylonitrile styrene copolymer (AS), polymethyl methacrylate (PMMA), chlorinated polyethylene (CPE), and ethylene vinyl acetate copolymer (EVA) 1 type or 2 types or more which can be mentioned.
エンジニアリングプラスチックとしては、例えばポリアミド（ＰＡ）、ポリアセタール（ＰＯＭ）、ポリカーボネート（ＰＣ）、ポリフェニレンエーテル（ＰＰＥ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリメチルペンテン（ＴＰＸ）、シンジオタクチック・ポリスチレン（ＳＰＳ）、ポリサルフォン（ＰＳＦ）、ポリエーテルサルホン（ＰＥＳ）、ポリフタルアミド（ＰＰＡ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリシクロヘキシレンジメチレンテレフタレート（ＰＣＴ）、ポリアリレート（ＰＡＲ）、ポリエーテルイミド（ＰＥＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、熱可塑性ポリイミド
（ＰＩ）、液晶ポリマー（ＬＣＰ）、フッ素樹脂、ポリエーテルニトリル（ＰＥＮ）、ポリエチレンテレフタレート（ＰＥＴ）、変性ポリフェニレンエーテル（ｍＰＰＥ）、ポリサルホン（ＰＳＦ）、およびポリアミドイミド（ＰＡＩ）の群から選ばれる１種若しくは２種以上を挙げることができる。
Examples of engineering plastics include polyamide (PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether (PPE), polybutylene terephthalate (PBT), polymethylpentene (TPX), syndiotactic polystyrene (SPS), Polysulfone (PSF), polyethersulfone (PES), polyphthalamide (PPA), polyphenylene sulfide (PPS), polycyclohexylenedimethylene terephthalate (PCT), polyarylate (PAR), polyetherimide (PEI), poly Ether ether ketone (PEEK), thermoplastic polyimide (PI), liquid crystal polymer (LCP), fluororesin, polyether nitrile (PEN), polyethylene terephthalate (PE ), Modified polyphenylene ether (mPPE), mention may be made of one or more selected from the group of polysulfone (PSF), and polyamideimide (PAI).
熱可塑性エラストマーとしては、例えば熱可塑性スチレン（ＴＰＳ）、熱可塑性ポリオレフィン（ＴＰＯ）、熱可塑性ポリウレタン（ＴＰＵ）、熱可塑性ポリエステル系エラストマー（ＴＰＥＥ）、熱可塑性加硫エラストマー（ＴＰＶ）、熱可塑性塩化ビニル系エラストマー（ＴＰＶＣ）、熱可塑性ポリアミド系エラストマー（ＰＥＢＡＸ）から選ばれる１種若しくは２種以上を挙げることができる。 Examples of the thermoplastic elastomer include thermoplastic styrene (TPS), thermoplastic polyolefin (TPO), thermoplastic polyurethane (TPU), thermoplastic polyester elastomer (TPEE), thermoplastic vulcanized elastomer (TPV), and thermoplastic vinyl chloride. One type or two or more types selected from a thermoplastic elastomer (TPVC) and a thermoplastic polyamide elastomer (PEBAX) can be mentioned.
熱硬化性樹脂としては、例えばフェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、ウレタン樹脂、及びケイ素樹脂から選ばれる１種若しくは２種以上を挙げることができる。 Examples of the thermosetting resin include one or more selected from phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, urethane resin, and silicon resin.
ゴムとしては、ポリブタジエン（ＰＢ）、ニトリルゴム（ＮＢＲ）、天然ゴム（ＮＲ）、ブチルゴム（ＩＩＲ）、スチレンブタジエンゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、フッ素系ゴム、及びシリコンゴムから選ばれる１種若しくは２種以上を挙げることができる。 The rubber is selected from polybutadiene (PB), nitrile rubber (NBR), natural rubber (NR), butyl rubber (IIR), styrene butadiene rubber (SBR), chloroprene rubber (CR), fluorine-based rubber, and silicon rubber. A seed | species or 2 or more types can be mentioned.
ゲルとしては、ウレタン系ゲル及びシリコン系ゲルから選ばれる１種若しくは２種以上を挙げることができる。 As a gel, 1 type, or 2 or more types chosen from urethane type gel and silicon type gel can be mentioned.
水系エマルジョン樹脂としては、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリスチレン（ＰＳ）、エチレン酢酸ビニル共重合体（ＥＶＡ）及びポリウレタンから選ばれる１種若しくは２種以上を挙げることができる。 Examples of the aqueous emulsion resin include one or more selected from polymethyl methacrylate (PMMA), polystyrene (PS), ethylene vinyl acetate copolymer (EVA), and polyurethane.
尚、上記マトリックスを構成するポリマー成分の選択に際しては、後述するマイクロカプセルのシェル壁を構成する樹脂との相溶性のほか、当該蓄熱組成物の適用される材料
（用途）や使用形態、取り扱い性、成形性、入手容易性、温度性能（耐熱性や耐寒性）、耐候性、価格なども考慮するのが望ましい。
In addition, when selecting the polymer component constituting the matrix, in addition to the compatibility with the resin constituting the shell wall of the microcapsule described later, the material (use), usage form, and handleability to which the heat storage composition is applied. It is desirable to consider moldability, availability, temperature performance (heat resistance and cold resistance), weather resistance, price, and the like.
本発明の蓄熱組成物は、上記ポリマーマトリックス中にマイクロカプセル化された蓄熱性材料が含まれているのである。 The heat storage composition of the present invention includes a heat storage material microencapsulated in the polymer matrix.
本発明の蓄熱組成物に用いる蓄熱性材料には、使用目的に応じて目標温度に適合する相転移温度を有するものを適宜選択使用すればよく、パラフィン系炭化水素、天然ワックス、石油ワックス、ポリエチレングリコール、無機化合物の水和物などを用いることができる。特に住宅用の保温材、食品用トレーや容器として使用する場合、室温付近で固体−液体の相転移を起こす材料、即ち、５〜６０℃の融点を持つパラフィン系炭化水素を使用することが好ましく、具体例として、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン、ノナデカン、イコサン、ドコサン等が挙げられる。これらのパラフィン系炭化水素は、炭素数の増加と共に融点が上昇するため、目的に応じた融点を有する炭化水素を選択したり、２種以上の炭化水素を混合して使用することが可能である。上記材料には、マイクロカプセルの熱伝導性、比重を調節する目的で、カーボン、金属粉、アルコール等を添加しても良い。 The heat storage material used in the heat storage composition of the present invention may be appropriately selected and used as long as it has a phase transition temperature suitable for the target temperature according to the purpose of use. Paraffin hydrocarbons, natural wax, petroleum wax, polyethylene Glycols, hydrates of inorganic compounds, and the like can be used. In particular, when used as a heat insulating material for a house, a food tray or a container, it is preferable to use a material that causes a solid-liquid phase transition near room temperature, that is, a paraffinic hydrocarbon having a melting point of 5 to 60 ° C. Specific examples include pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, docosan and the like. These paraffinic hydrocarbons have melting points that increase as the number of carbon atoms increases, so it is possible to select hydrocarbons having a melting point according to the purpose or to use a mixture of two or more hydrocarbons. . Carbon, metal powder, alcohol or the like may be added to the above material for the purpose of adjusting the thermal conductivity and specific gravity of the microcapsules.
これらの蓄熱性材料を封入するマイクロカプセルのシェル材料としては、その耐熱温度が上記蓄熱性材料の融点に比べて十分に高いもの、例えば３０℃以上、好ましくは５０℃以上であって、該蓄熱組成物の用途に応じた強度を有する材質を適宜選択すればよく、具体的には、メラミン樹脂、アクリル樹脂、ウレタン樹脂等を好ましい例として挙げられる。 As the shell material of the microcapsule enclosing these heat storage materials, the heat-resistant temperature is sufficiently higher than the melting point of the heat storage material, for example, 30 ° C. or more, preferably 50 ° C. or more. What is necessary is just to select the material which has the intensity | strength according to the use of the composition suitably, Specifically, a melamine resin, an acrylic resin, a urethane resin etc. are mentioned as a preferable example.
マイクロカプセルの外径としては１〜５００μｍが好ましく、より好ましくは５〜１００μｍである。また、シェル内に封入される蓄熱性材料の量は、蓄熱効果の点からは多いほうが好ましいが、多過ぎると潜熱蓄熱剤の体積変化によりマイクロカプセルが破損する恐れがある。このため、マイクロカプセル全体の重量に対する蓄熱性材料の量は、２０〜８０重量％とすることが好ましく、４０〜６０重量％とすることがより好ましい。 The outer diameter of the microcapsule is preferably 1 to 500 μm, more preferably 5 to 100 μm. In addition, the amount of the heat storage material enclosed in the shell is preferably large from the viewpoint of the heat storage effect, but if it is too large, the microcapsule may be damaged due to the volume change of the latent heat storage agent. For this reason, the amount of the heat storage material relative to the total weight of the microcapsules is preferably 20 to 80% by weight, and more preferably 40 to 60% by weight.
マイクロカプセルの製造方法としては、界面重合法、ｉｎ−ｓｉｔｕ重合法、コアセルベート法等の従来の公知の製造方法から、潜熱蓄熱剤及びシェルの材質等に応じて適切な方法を選択すればよい。 As a method for producing the microcapsules, an appropriate method may be selected from conventionally known production methods such as an interfacial polymerization method, an in-situ polymerization method, a coacervate method and the like according to the latent heat storage agent and the material of the shell.
上記マイクロカプセルは、蓄熱組成物のポリマーマトリックスの１００重量部に対して１〜３００重量部の割合で含有されていることが好ましく、より好ましくは２０〜２００重量部であり、最適には５０〜１００重量部である。マイクロカプセルの含有量が１重量部未満では十分な蓄熱効果が得られず、マイクロカプセルの含有量が３００重量部を超えると、蓄熱組成物の成形性、接着性、強度、塗工性等が低下するため好ましくない。 The microcapsules are preferably contained in an amount of 1 to 300 parts by weight, more preferably 20 to 200 parts by weight, and most preferably 50 to 200 parts by weight with respect to 100 parts by weight of the polymer matrix of the heat storage composition. 100 parts by weight. If the content of the microcapsules is less than 1 part by weight, a sufficient heat storage effect cannot be obtained. If the content of the microcapsules exceeds 300 parts by weight, the heat storage composition has moldability, adhesiveness, strength, coatability, etc. Since it falls, it is not preferable.
尚、本発明の蓄熱組成物中には、上述の成分の他に、例えばマイカ鱗片、ガラス片、グラスファイバー、カーボンファイバー、炭酸カルシウム、バライト、沈降硫酸バリウム等の物質や、腐食防止剤、染料、酸化防止剤、制電剤、安定剤、湿潤剤などを必要に応じて適宜加えることができる。 In the heat storage composition of the present invention, in addition to the above components, for example, mica scale pieces, glass pieces, glass fibers, carbon fibers, calcium carbonate, barite, precipitated barium sulfate, corrosion inhibitors, dyes, etc. Antioxidants, antistatic agents, stabilizers, wetting agents and the like can be appropriately added as necessary.
本発明の蓄熱組成物は、シート状やフィルム状など固状の形態とする場合には、上記マトリックスを構成するポリマー成分に、マイクロカプセル化された蓄熱性材料を所定割合で配合し、これをバンバリーミキサーやロール等を用いて混練し、さらにカレンダー法や押し出し法などにより、用途、目的に応じた形状に成形する。 When the heat storage composition of the present invention is in a solid form such as a sheet or film, the polymer component constituting the matrix is blended with a predetermined ratio of the heat storage material microencapsulated. They are kneaded using a Banbury mixer, roll, etc., and further formed into a shape according to the application and purpose by a calendar method or an extrusion method.
ゲルまたはエマルジョンの形態とする場合には、上述のゲルや水性エマルジョンに、マイクロカプセル化された蓄熱性材料を所定割合で添加し、これを混合機で均一な分散状態となるまで混合する。 In the case of a gel or emulsion, a microencapsulated heat storage material is added to the above-described gel or aqueous emulsion at a predetermined ratio and mixed with a mixer until a uniform dispersion state is obtained.
尚、本発明は、下記実施例に限定されるものではなく、「特許請求の範囲」に記載された範囲で自由に変更して実施することができる。 In addition, this invention is not limited to the following Example, It can implement freely by changing in the range described in the "Claims".
以下、本発明の蓄熱組成物について、その温度保持効果（蓄熱性）を評価した。
熱硬化性ウレタンの主剤に最終配合で５０重量％となるように、３１℃で固体−液体相転移を起こすパラフィン系炭化水素を蓄熱性材料とし、この蓄熱性材料をシェル壁がメラミン樹脂により構成されたマイクロカプセル内に封入したマイクロカプセルを添加する。
次いで、硬化剤を加えて８０℃の温度で２時間加熱し、ウレタンを硬化させた。この後、硬化物を５０ｇの重量の円柱状に切り出し、サンプルとした。
Hereinafter, the temperature retention effect (heat storage property) of the heat storage composition of the present invention was evaluated.
A paraffinic hydrocarbon that causes a solid-liquid phase transition at 31 ° C is used as a heat storage material so that the final composition of the thermosetting urethane is 50% by weight, and the shell wall is composed of a melamine resin. The microcapsule encapsulated in the prepared microcapsule is added.
Next, a curing agent was added and heated at 80 ° C. for 2 hours to cure the urethane. Thereafter, the cured product was cut into a column having a weight of 50 g and used as a sample.
得られたサンプルの中心部に熱電対を差し込み、４０℃の恒温槽内に２時間静置し、その後、２５℃の室温に放置した状態で、サンプルの温度が下がっていく状態を１秒置きに測定した。尚、比較のため、マイクロカプセルの添加されいないウレタン硬化物のサンプルについても同様に試験し、その温度の降下状態を測定した。 Insert a thermocouple into the center of the obtained sample, leave it in a constant temperature bath at 40 ° C for 2 hours, and then leave it at room temperature of 25 ° C for 1 second. Measured. For comparison, a sample of a urethane cured product to which no microcapsule was added was also tested in the same manner, and the temperature drop state was measured.
図１から、実施例のサンプルと比較例のサンプルについて、測定開始時のサンプルの温度３４℃が、２７℃までに下がるのに要した時間を比べたとき、比較例のサンプルが約１７００秒であったのに対し、実施例のサンプルの場合、２倍の約３４００秒となり、マイクロカプセルを添加した実施例に係るサンプルが温度保持効果に優れることが確認された。 From FIG. 1, when comparing the time required for the sample temperature of 34 ° C. at the start of measurement to drop to 27 ° C. for the sample of the example and the sample of the comparative example, the sample of the comparative example was about 1700 seconds. On the other hand, in the case of the sample of the example, it was about 3400 seconds, which was twice as long, and it was confirmed that the sample according to the example to which the microcapsule was added was excellent in the temperature holding effect.
Claims (20)
（ＡＢＳ）、アクリロニトリルスチレン共重合体（ＡＳ）、ポリメタクリル酸メチル（ＰＭＭＡ）、塩素化ポリエチレン（ＣＰＥ）、及びエチレン酢酸ビニル共重合体（ＥＶＡ）から選ばれる１種若しくは２種以上であることを特徴とする請求項３記載の蓄熱組成物。 General-purpose plastics include polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile butadiene styrene copolymer (ABS), acrylonitrile styrene copolymer (AS), polymethyl methacrylate ( The heat storage composition according to claim 3, wherein the composition is one or more selected from PMMA), chlorinated polyethylene (CPE), and ethylene vinyl acetate copolymer (EVA).
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