JP2016216528A - Temperature sensitive coating and temperature detection body - Google Patents
Temperature sensitive coating and temperature detection body Download PDFInfo
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本発明は、示温塗料及び該示温塗料を用いて形成される硬化塗膜からなる温度検知体に関する。 TECHNICAL FIELD The present invention relates to a temperature indicating paint and a temperature detector comprising a cured coating film formed using the temperature indicating paint.
従来から、冷凍庫内の温度を目視で検知するために、温度の上昇及び下降により可逆的に変色する熱可逆変色性示温層を庫内に配置することが行なわれている。また、表面に熱可逆変色性示温層を設けることにより、例えば浴槽内の湯に浸漬することで、該示温層の変色による外観変化を視覚で楽しむように構成された玩具も市販されている。該示温層は、例えば、熱可逆変色性示温材料、バインダ樹脂及び溶剤を含有する示温塗料を被塗物表面に塗布し、得られた塗膜を乾燥及び硬化させることにより形成される。 Conventionally, in order to visually detect the temperature in the freezer, a thermoreversible color-changing temperature indicating layer that reversibly discolors as the temperature rises and falls has been placed in the refrigerator. In addition, a toy configured to provide a thermoreversible color-changing temperature indicating layer on the surface, for example, so that the appearance change due to the color change of the temperature indicating layer is visually enjoyed by being immersed in hot water in a bathtub is also commercially available. The temperature indicating layer is formed, for example, by applying a temperature indicating paint containing a thermoreversible color changing temperature indicating material, a binder resin and a solvent to the surface of an object to be coated, and drying and curing the obtained coating film.
従来の熱可逆変色性示温材料としては、例えば、四ヨウ化水銀（ＩＩ）酸銀錯体（特許文献１）、コバルト錯体化合物（特許文献２）、鉄トリアゾール錯化合物、ナフタレン、アントラセン、ピレン等の芳香族炭化水素と銅、マンガン、ロジウム等の遷移金属との錯体（特許文献３）等の金属錯体系や、電子供与性呈色性化合物と電子受容性化合物とを含有する有機系等が挙げられる。しかし、これらの示温材料は十分な耐熱性を有しておらず、２００℃を超えるような高温域では熱可逆変色性が損なわれ易い。 Conventional thermoreversible color-changing temperature indicating materials include, for example, silver tetraiodide (II) acid silver complex (Patent Document 1), cobalt complex compound (Patent Document 2), iron triazole complex compound, naphthalene, anthracene, pyrene, etc. Examples include metal complex systems such as complexes of aromatic hydrocarbons with transition metals such as copper, manganese, and rhodium (Patent Document 3), and organic systems containing an electron-donating color-forming compound and an electron-accepting compound. It is done. However, these temperature indicating materials do not have sufficient heat resistance, and thermoreversible discoloration tends to be impaired at a high temperature range exceeding 200 ° C.
特許文献４は、組成式：（Ｂｉ２Ｏ３）１−ｚ（ＭｘＯｙ）ｚ〔式中、ｚ＝０〜０．５であり、Ｍは重金属、アルカリ金属及びアルカリ土類金属よりなる群から選ばれる少なくとも１種の金属を示す。〕で表わされる熱可逆変色性顔料と、アルカリ金属のケイ酸塩又はアルカリ土類金属のケイ酸塩、ホウ酸塩及びリン酸塩よりなる群から選ばれる少なくとも１種のガラスフリットと、を含有し、調理用レンジ等の家庭用器具の温度表示に用いられる温度検知体を開示する。 Patent Document 4 has a composition formula: (Bi 2 O 3 ) 1-z (M x O y ) z [wherein z = 0 to 0.5, and M is a heavy metal, an alkali metal and an alkaline earth metal. At least one metal selected from the group consisting of: And at least one glass frit selected from the group consisting of alkali metal silicates or alkaline earth metal silicates, borates, and phosphates. And the temperature detection body used for the temperature display of household appliances, such as a cooking range, is disclosed.
特許文献４の実施例の温度検知体は変色温度領域がいずれも４００℃付近であり、火傷等が発症する８０〜１００℃の温度では変色しないため、該温度検知体を石油ストーブ等の暖房器具に取り付けた場合、動作中の暖房器具に誤って触れることによる火傷等を未然に防止できない。また、バインダとして使用するガラスフリットが高融点であるため、該温度検知体の形成には非常に高温での加熱が必要になり、適用範囲が制限される。また、ガラスフリットが鋼板等に対して十分な接着強度を有していないため、該温度検知体を凹凸形状を有する面に形成した場合には、該温度検知体が剥離し易い。 Since the temperature detection bodies of the examples of Patent Document 4 have a discoloration temperature range of around 400 ° C. and do not change color at temperatures of 80 to 100 ° C. at which burns or the like develop, the temperature detection bodies are used as heating appliances such as petroleum stoves. If it is attached to, it will not be possible to prevent burns or the like caused by accidentally touching the heating appliance in operation. Moreover, since the glass frit used as a binder has a high melting point, heating at a very high temperature is required to form the temperature detector, and the application range is limited. Further, since the glass frit does not have sufficient adhesive strength with respect to a steel plate or the like, when the temperature detection body is formed on a surface having an uneven shape, the temperature detection body is easily peeled off.
特許文献５では、調理や整髪の際の温度検知を目的として、スキレット、ソースパン、ソテーパン、バーベキューグリル等の調理器具やフラットアイロン、ヘアアイロン等の表面に温度検知体を取り付けている。該温度検知体は、熱変色性顔料組成物と熱安定性結合剤とを含む硬化塗膜からなり、熱変色性顔料組成物は、熱可逆変色性顔料を含む核と、該核の表面を被覆する透明被覆層と、からなる複合顔料粒、及び熱安定性顔料を含む。そして、熱可逆変色性顔料としてはバナジン酸ビスマス（ＢｉＶＯ４）や酸化ビスマス、透明性被覆層としてはシリカ被膜、熱安定性結合剤としてはシリコーン樹脂がそれぞれ例示されている（請求項１１、１６、１８等）。 In Patent Document 5, for the purpose of temperature detection during cooking and hair styling, a temperature detector is attached to the surface of cooking utensils such as skillet, saucepan, sotaperine, barbecue grill, flat iron, hair iron and the like. The temperature detector comprises a cured coating film containing a thermochromic pigment composition and a thermostable binder. The thermochromic pigment composition comprises a core containing a thermoreversible color changing pigment and a surface of the nucleus. A transparent coating layer to be coated, a composite pigment particle comprising, and a heat-stable pigment. Examples of the thermoreversible color-changing pigment include bismuth vanadate (BiVO 4 ) and bismuth oxide, a silica coating as the transparent coating layer, and a silicone resin as the heat-stable binder (claims 11 and 16). , 18 etc.).
すなわち、特許文献５は、バナジン酸ビスマスや酸化ビスマス等の熱可逆変色性顔料の耐熱性が不十分であり、高温に晒された場合にその熱可逆変色性が損なわれ易いことから（段落［００２４］）、熱可逆変色性顔料をシリカ等からなる透明性被覆層で覆った後に、シリコーン樹脂中に分散させて硬化塗膜（温度検知体）を形成する形態を開示している。この形態は、熱可逆変色性顔料を透明性被覆層で覆うことなくシリコーン樹脂中に単に分散させただけでは、高温に晒された場合に熱可逆変色性の低下を防止できないことを示している。なお、バナジン酸ビスマスの熱安定性が不十分であることは、例えば、特許文献６にも開示されている（第１カラム、２．関連技術の第２段落）。 That is, in Patent Document 5, the heat-reversible color-changing pigments such as bismuth vanadate and bismuth oxide have insufficient heat resistance, and the thermo-reversible color-changing property is easily impaired when exposed to high temperatures (paragraph [ )]), A thermoreversible color-changing pigment is covered with a transparent coating layer made of silica or the like and then dispersed in a silicone resin to form a cured coating film (temperature detector). This form shows that the thermoreversible color change pigment cannot be prevented from being lowered when exposed to high temperatures simply by dispersing the thermoreversible color change pigment in the silicone resin without covering with a transparent coating layer. . The fact that the thermal stability of bismuth vanadate is insufficient is also disclosed, for example, in Patent Document 6 (first column, 2. second paragraph of related technology).
本発明の目的は、所定の温度領域を境界にして、温度変化による可逆的かつ鮮明な変色を長期間にわたって安定的に繰り返す硬化塗膜を形成し得る示温塗料及び該硬化塗膜からなる温度検知体を提供することである。 An object of the present invention is to provide a temperature indicating coating that can form a cured coating film that repeats reversible and clear discoloration due to temperature change over a long period of time with a predetermined temperature region as a boundary, and temperature detection comprising the cured coating film. Is to provide a body.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、熱可逆変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤、及び溶剤を含む示温塗料を用いて形成された硬化塗膜中では、主に熱可逆変色性顔料、シリコーン樹脂及び薄片状無機充填材が協働的に作用し合い、２００〜３００℃又はそれを超えるような高温に晒されても、該顔料の熱可逆変色性の低下が顕著に抑制され、鮮明な変色が得られること、及び該硬化塗膜の変色温度領域を７０〜１００℃程度の範囲に調整することが可能であり、石油ストーブ等の暖房器具や蒸気配管等の火傷防止用温度検知体として有用であることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above problems, the present inventors have formed a thermoreversible color-changing pigment, a silicone resin, a flaky inorganic filler, an anti-settling agent, and a temperature indicating paint containing a solvent. In the cured coating film, the thermoreversible color-changing pigment, the silicone resin, and the flaky inorganic filler act cooperatively, and even when exposed to a high temperature of 200 to 300 ° C. or higher, Decrease in thermoreversible discoloration of the pigment is remarkably suppressed, clear discoloration is obtained, and the discoloration temperature region of the cured coating film can be adjusted to a range of about 70 to 100 ° C. The present invention has been found to be useful as a temperature detector for preventing burns such as heating appliances and steam pipes.
すなわち、本発明は、下記（１）〜（６）の示温塗料及び下記（７）の温度検知体を提供する。 That is, the present invention provides the following temperature indicating paints (1) to (6) and the temperature detector (7) below.
（１）熱可逆変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤、及び溶剤を含む示温塗料。
（２）熱可逆変色性顔料５〜５０重量％、シリコーン樹脂２０〜７０重量％、薄片状無機充填材１０〜６０重量％、沈降防止剤０．０５〜１０重量％、及び溶剤３〜５０重量％を含有する上記（１）の示温塗料。
（３）熱可逆変色性顔料が、バナジン酸ビスマス系顔料、及び酸化ビスマス系顔料よりなる群から選ばれる少なくとも１種である上記（１）又は（２）の示温塗料。
（４）シリコーン樹脂が、鎖状シリコーン樹脂及びアクリル変性鎖状シリコーン樹脂から選ばれる少なくとも１種である上記（１）〜（３）のいずれかの示温塗料。
（５）薄片状無機充填材が、鉱物系薄片状無機充填材である上記（１）〜（４）のいずれかの示温塗料。
（６）バナジン酸ビスマス系顔料、及び酸化ビスマス系顔料よりなる群から選ばれる少なくとも１種の熱可逆変色性顔料５〜５０重量％、鎖状シリコーン樹脂及びアクリル変性鎖状シリコーン樹脂から選ばれる少なくとも１種のシリコーン樹脂２０〜７０重量％、鉱物系薄片状無機充填材１０〜６０重量％、沈降防止剤０．０５〜１０重量％、及び溶剤３〜５０重量％を含有する示温塗料。
（７）上記（１）〜（６）のいずれかの示温塗料を用いて被塗体表面に形成された硬化塗膜からなり、所定の温度領域を境界にして温度変化により可逆的に変色する温度検知体。
(1) A temperature indicating paint containing a thermoreversible color-changing pigment, a silicone resin, a flaky inorganic filler, an anti-settling agent, and a solvent.
(2) Thermoreversible color-changing pigment 5 to 50% by weight, silicone resin 20 to 70% by weight, flaky inorganic filler 10 to 60% by weight, anti-settling agent 0.05 to 10% by weight, and solvent 3 to 50% by weight % (1) temperature indicating paint.
(3) The temperature indicating paint according to the above (1) or (2), wherein the thermoreversible color-changing pigment is at least one selected from the group consisting of bismuth vanadate pigments and bismuth oxide pigments.
(4) The temperature indicating paint according to any one of the above (1) to (3), wherein the silicone resin is at least one selected from a chain silicone resin and an acrylic-modified chain silicone resin.
(5) The temperature indicating paint according to any one of (1) to (4), wherein the flaky inorganic filler is a mineral-based flaky inorganic filler.
(6) At least one thermoreversible color-changing pigment selected from the group consisting of a bismuth vanadate pigment and a bismuth oxide pigment, at least selected from a chain silicone resin and an acrylic modified chain silicone resin A temperature indicating paint containing 20 to 70% by weight of one kind of silicone resin, 10 to 60% by weight of a mineral-based flaky inorganic filler, 0.05 to 10% by weight of an anti-settling agent, and 3 to 50% by weight of a solvent.
(7) It consists of a cured coating film formed on the surface of the object to be coated using the temperature indicating paint of any one of (1) to (6), and reversibly discolors due to a temperature change with a predetermined temperature region as a boundary. Temperature detector.
本発明の示温塗料によれば、所定の温度領域を境界にして、温度変化による可逆的かつ鮮明な変色を長期間にわたって安定的に繰り返す硬化塗膜から構成される温度検知体を提供することができる。 According to the temperature indicating paint of the present invention, it is possible to provide a temperature detector comprising a cured coating film that stably repeats reversible and clear discoloration due to a temperature change over a long period with a predetermined temperature region as a boundary. it can.
本発明の示温塗料は、熱可逆変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤、及び溶剤を含有することを特徴とする。熱可逆変色性顔料は耐熱性が十分ではなく、２００℃を超えるような高温に晒されるとその熱可逆変色性が低下するため、熱可逆変色性顔料をシリカ等からなる透明膜で被覆することが行なわれていた。これに対し、本発明では、主にシリコーン樹脂と薄片状無機充填材とを併用することによるものと考えられるが、本発明の示温塗料から形成された硬化塗膜中では、熱可逆変色性顔料が高温に晒されても、その熱可逆変色性の低下が顕著に抑制され、該硬化塗膜が所定の温度領域を境界にして温度変化（温度の上昇及び下降）による鮮明な変色を長期間にわたって安定的に繰り返し得ることが明らかになった。 The temperature indicating paint of the present invention is characterized by containing a thermoreversible color-changing pigment, a silicone resin, a flaky inorganic filler, an anti-settling agent, and a solvent. Thermoreversible color-changing pigments are not sufficiently heat resistant, and their thermoreversible color-changing properties decrease when exposed to high temperatures exceeding 200 ° C. Therefore, coat the thermoreversible color-changing pigments with a transparent film made of silica or the like. Was done. On the other hand, in the present invention, it is considered that it is mainly due to the combined use of silicone resin and flaky inorganic filler, but in the cured coating film formed from the temperature indicating paint of the present invention, a thermoreversible color-changing pigment. Even when exposed to a high temperature, the thermoreversible color change is remarkably suppressed, and the cured coating undergoes a clear color change due to a temperature change (temperature increase and decrease) for a long period of time at a predetermined temperature range. It has become clear that it can be repeated stably over time.
以下、本発明の示温塗料の必須成分である熱可逆変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤、及び溶剤について、順を追って詳しく説明する。 Hereinafter, the thermoreversible color-changing pigment, silicone resin, flaky inorganic filler, anti-settling agent, and solvent, which are essential components of the temperature indicating paint of the present invention, will be described in detail step by step.
本発明で使用する熱可逆変色性顔料（以下単に「変色性顔料」と称すことがある）は、所定の温度領域又は温度を境界にして温度変化（温度の上昇及び下降）に伴って可逆的に変色する無機化合物である。変色性顔料としては熱可逆変色性を有する無機化合物であれば特に限定されないが、暖房器具や蒸気配管等に誤って触れることによる火傷の発症等を防止する観点からは、例えば、バナジン酸ビスマス系顔料、酸化ビスマス系顔料等の７０〜１００℃の温度領域を境界にして変色する変色性顔料等が好ましい。また、温度検知体の用途に応じて、７０℃より低い温度領域又は１００℃よりも高い温度領域を境界にして変色する変色性顔料を用いることもできる。変色性顔料は１種を単独で又は２種以上を組み合わせて使用できる。 The thermoreversible color-changing pigment used in the present invention (hereinafter sometimes simply referred to as “color-changing pigment”) is reversible as the temperature changes (rising and rising) at a predetermined temperature range or temperature. It is an inorganic compound that changes color. The discoloration pigment is not particularly limited as long as it is an inorganic compound having thermoreversible discoloration, but from the viewpoint of preventing the occurrence of burns by accidentally touching a heater or steam pipe, for example, bismuth vanadate Color-changing pigments such as pigments and bismuth oxide pigments that change color at a temperature range of 70 to 100 ° C. are preferred. In addition, a color-changing pigment that changes color at a temperature range lower than 70 ° C. or a temperature range higher than 100 ° C. may be used depending on the application of the temperature detector. The discolorable pigments can be used alone or in combination of two or more.
バナジン酸ビスマス系顔料は、変色境界温度領域が７０〜８０℃であり、高温側では橙色に、低温側では黄色に呈色する特性を示し、火傷防止の観点からは特に有用である。バナジン酸ビスマス系顔料としては、バナジン酸ビスマス（ＢｉＶＯ４）及びバナジン酸ビスマス化合物から選ばれる少なくとも１種が挙げられる。バナジン酸ビスマス化合物とは、バナジン酸ビスマス中のＢｉ、Ｖ及びＯから選ばれる少なくとも１種の原子の一部が他の金属原子及び／又は非金属原子で置換され、熱可逆変色性を有する化合物である。 The bismuth vanadate pigment has a color change boundary temperature region of 70 to 80 ° C., and exhibits a characteristic of being colored orange on the high temperature side and yellow on the low temperature side, and is particularly useful from the viewpoint of preventing burns. Examples of the bismuth vanadate pigment include at least one selected from bismuth vanadate (BiVO 4 ) and bismuth vanadate compounds. The bismuth vanadate compound is a compound having a thermoreversible discoloration property in which a part of at least one atom selected from Bi, V and O in bismuth vanadate is substituted with another metal atom and / or a nonmetal atom. It is.
バナジン酸ビスマス系顔料は、入手し易さ等の観点から、バナジン酸ビスマス及び／又はバナジン酸ビスマス化合物と共に、他の無機化合物を微量成分として含むものでもよい。他の無機化合物としては、リン酸アルミニウム〔Ａｌ（ＰＯ３）３〕、酸化アルミニウム（Ａｌ２Ｏ３）等のアルミニウム化合物、モリブデン酸カルシウム（ＣａＭｏＯ４）等のモリブデン酸塩等が挙げられる。微量成分として他の無機化合物を含む場合、バナジン酸ビスマス及び／又はバナジン酸ビスマス化合物の含有量は、好ましくは全量の９０重量％以上、より好ましくは全量の９０〜９９．５重量％、さらに好ましくは全量の９３〜９８重量％である。 The bismuth vanadate pigment may contain other inorganic compounds as a minor component together with bismuth vanadate and / or a bismuth vanadate compound from the viewpoint of availability. Examples of other inorganic compounds include aluminum compounds such as aluminum phosphate [Al (PO 3 ) 3 ] and aluminum oxide (Al 2 O 3 ), and molybdates such as calcium molybdate (CaMoO 4 ). When other inorganic compounds are contained as a minor component, the content of bismuth vanadate and / or bismuth vanadate compound is preferably 90% by weight or more of the total amount, more preferably 90 to 99.5% by weight of the total amount, and further preferably Is 93 to 98% by weight of the total amount.
バナジン酸ビスマス系顔料の平均粒径は、シリコーン樹脂や薄片状無機充填材によるバナジン酸ビスマス系顔料の耐熱性の向上及び熱可逆変色性の保持を図る観点から、好ましくは０．１〜５０μｍ、より好ましくは０．５〜３０μｍ、更に好ましくは１〜２０μｍである。 The average particle diameter of the bismuth vanadate pigment is preferably 0.1 to 50 μm from the viewpoint of improving the heat resistance of the bismuth vanadate pigment by the silicone resin or the flaky inorganic filler and maintaining the thermoreversible discoloration. More preferably, it is 0.5-30 micrometers, More preferably, it is 1-20 micrometers.
バナジン酸ビスマス系顔料としては市販品を用いてもよく、該市販品としては、例えば、リソパックイエロー６６０１Ｂ、リソパックイエロー６６１５Ｂ、リソパックジョンブリアン６６１３Ｐ（いずれも商品名、ＣＡＰＰＥＬＬＥ ＰＩＧＭＥＮＴＳ ＮＶ社製）、ＤＣＣイエロー２０９４（商品名、ドミニオンカラー・コーポレイション社製）、Ｓｉｃｏｐａｌ Ｙｅｌｌｏｗ Ｋ１１６０ＦＧ（商品名、ＢＡＳＦ社製）、Ｖａｎａｄｕｒ Ｐｌｕｓ ９０１０（商品名、ＨＥＵＢＡＣＨ社製）等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて使用できる。 Commercially available products may be used as the bismuth vanadate pigments. Examples of the commercially available products include lithopack yellow 6601B, lithopack yellow 6615B, and lithopack John Brian 6613P (all trade names, manufactured by CAPPELLE PIMMENTS NV) DCC Yellow 2094 (trade name, manufactured by Dominion Color Corporation), Sicopal Yellow K1160FG (trade name, manufactured by BASF), Vanadur Plus 9010 (trade name, manufactured by HEUBACH), and the like. These can be used individually by 1 type or in combination of 2 or more types.
酸化ビスマス系顔料は、変色境界温度領域が７０℃以上であり、高温側では黄色又は黄橙色に、低温側では薄黄色に呈色する特性を示す。酸化ビスマス系顔料としては、例えば、酸化ビスマス（ＩＩＩ）、酸化ビスマス（ＩＩＩ）化合物等が挙げられる。酸化ビスマス（ＩＩＩ）化合物とは、酸化ビスマス（ＩＩＩ）中のＢｉ、及びＯから選ばれる少なくとも１種の原子の一部が他の金属原子及び／又は非金属原子で置換され、熱可逆変色性を有する化合物である。酸化ビスマス（ＩＩＩ）は微量成分としてＡｇ、Ｃｕ、Ｐｂ等の金属やＦｅ２Ｏ３等の金属酸化物を含むものでもよい。また、酸化ビスマス（ＩＩＩ）の平均粒径は特に限定されないが、好ましくは１．５〜４μｍである。なお、酸化ビスマス系顔料も、市販品を特に限定なく使用できる。 The bismuth oxide pigment has a color change boundary temperature region of 70 ° C. or higher, and exhibits a characteristic of yellow or yellow-orange on the high temperature side and light yellow on the low temperature side. Examples of bismuth oxide pigments include bismuth oxide (III) and bismuth oxide (III) compounds. The bismuth (III) oxide compound is a thermoreversible color-changing property in which at least one atom selected from Bi and O in bismuth (III) oxide is substituted with another metal atom and / or a nonmetal atom. It is a compound which has this. Bismuth oxide (III) may contain a metal such as Ag, Cu or Pb or a metal oxide such as Fe 2 O 3 as a trace component. The average particle diameter of bismuth oxide (III) is not particularly limited, but is preferably 1.5 to 4 μm. In addition, a commercial item can also be used for bismuth oxide pigment without particular limitation.
本発明の示温塗料における熱可逆変色性顔料の含有量は特に限定されないが、好ましくは該塗料全量の５〜５０重量％、より好ましくは該塗料全量の１０〜３０重量％、さらに好ましくは該塗料全量の１５〜２５重量％である。熱可逆変色性顔料の含有量が前記範囲内にあることによって、示温塗料から形成される硬化塗膜が高温に晒されても、該顔料の熱可逆変色性の低下が顕著に抑制され、該硬化塗膜の温度変化による可逆的な変色が鮮明になり、視認し易くなる。 The content of the thermoreversible color-changing pigment in the temperature indicating paint of the present invention is not particularly limited, but is preferably 5 to 50% by weight of the total amount of the paint, more preferably 10 to 30% by weight of the total amount of the paint, and further preferably the paint. It is 15 to 25% by weight of the total amount. When the content of the thermoreversible color-changing pigment is within the above range, even when the cured coating film formed from the temperature indicating paint is exposed to a high temperature, a decrease in the thermoreversible color-changing property of the pigment is remarkably suppressed, Reversible discoloration due to temperature change of the cured coating film becomes clear and easy to visually recognize.
本発明の示温塗料では、熱可逆変色性顔料と、熱可逆変色性を示さない一般的な顔料とを組み合わせて用いることもできる。この組み合わせにより、硬化塗膜の変色の色を変更することが可能になるので、被塗体の構造や色彩等に応じて、変色をより視認し易くすることもできる。 In the temperature indicating paint of the present invention, a thermoreversible color change pigment and a general pigment that does not exhibit thermoreversible color change can also be used in combination. This combination makes it possible to change the discoloration color of the cured coating film, so that the discoloration can be made easier to see according to the structure and color of the object to be coated.
シリコーン樹脂は、例えば、他成分を硬化塗膜中に保持するマトリックス樹脂になると共に、主に薄片状無機充填材との協働により、変色性顔料を高温から保護し、硬化塗膜が２００〜３００℃又はそれを超えるような高温に晒されても、その熱可逆変色性を保持するものと考えられる。これにより、硬化塗膜を安定的にかつ長期にわたって可逆的かつ鮮明に視認性良く変色させることができる。なお、シリコーン樹脂単独では、変色性顔料の熱可逆変色性の低下を十分に抑制できず、長期的に可逆的に変色する硬化塗膜が得られない傾向がある。 The silicone resin becomes, for example, a matrix resin that holds other components in the cured coating film, and mainly protects the discolorable pigment from high temperature by cooperating with the flaky inorganic filler. Even when exposed to a high temperature of 300 ° C. or higher, it is considered that the thermoreversible discoloration is maintained. Thereby, the cured coating film can be discolored stably and reversibly over a long period of time with high visibility. In addition, the silicone resin alone cannot sufficiently suppress a decrease in thermoreversible discoloration of the discolorable pigment, and there is a tendency that a cured coating film that reversibly discolors in the long term cannot be obtained.
シリコーン樹脂としては特に限定されないが、鎖状シリコーン樹脂、鎖状シリコーン樹脂の側鎖及び／又は末端に有機基が導入された変性鎖状シリコーン樹脂、鎖状シリコーン樹脂中の珪素原子の一部が二価基により架橋された架橋シリコーン樹脂、環状ポリシロキサン等が挙げられる。これらの中でも、変色性顔料の熱可逆変色性の低下を抑制又は防止する観点から、鎖状シリコーン樹脂、変性鎖状シリコーン樹脂等が好ましい。鎖状シリコーン樹脂としては、例えば、メチルシリコーン、メチルフェニルシリコーン等が挙げられる。変性鎖状シリコーン樹脂としては、例えば、アクリル変性シリコーン樹脂、ポリエステル変性シリコーン樹脂、エポキシ変性シリコーン樹脂等が挙げられる。変性鎖状シリコーン樹脂の中では、アクリル変性シリコーン樹脂が好ましい。シリコーン樹脂は１種を単独で又は２種以上を組み合わせて使用できる。 The silicone resin is not particularly limited, but a chain silicone resin, a modified chain silicone resin in which an organic group is introduced into the side chain and / or terminal of the chain silicone resin, a part of silicon atoms in the chain silicone resin Examples thereof include a crosslinked silicone resin crosslinked with a divalent group and a cyclic polysiloxane. Among these, a chain silicone resin, a modified chain silicone resin, and the like are preferable from the viewpoint of suppressing or preventing a decrease in thermoreversible color change of the color change pigment. Examples of the chain silicone resin include methyl silicone and methylphenyl silicone. Examples of the modified chain silicone resin include acrylic modified silicone resin, polyester modified silicone resin, and epoxy modified silicone resin. Among the modified chain silicone resins, acrylic modified silicone resins are preferable. A silicone resin can be used individually by 1 type or in combination of 2 or more types.
シリコーン樹脂としては市販品を用いてもよく、該市販品としては、例えば、ＫＲ−１１２、ＫＲ−２１１、ＫＲ−２１２、ＫＲ−２５５、ＫＲ−２７１、ＫＲ−２７２、ＫＲ−２８２、ＫＲ−３００、ＫＲ−３１１、ＫＲ−２６２１−１、Ｘ−４０−２６６７Ａ、ＫＲ−４８０、ＫＲ−２２０Ｌ、ＫＲ−２２０ＬＰ、ＫＲ−２４２Ａ、ＫＲ−２５１（いずれも商品名、信越化学工業（株）製）、ＴＳＲ１１６、ＴＳＲ１１７、ＴＳＲ１４４、ＴＳＲ１４５、ＴＳＲ１４５２、ＴＳＲ１６５、ＴＳＲ１８０、ＴＳＲ１９４、ＸＲ３２−９０１、ＸＲ−３２−９０１、ＸＲ３２−Ａ１６１２、ＸＲ３３０３、ＹＲ４７、ＹＲ３３７０（いずれも商品名、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）、８０４ＲＥＳＩＮ、８０５ＲＥＳＩＮ、８０６ＡＲＥＳＩＮ、８４０ＲＥＳＩＮ、ＳＲ２４００（いずれも商品名、東レ・ダウコーニング（株）製）等が挙げられる。 Commercially available products may be used as the silicone resin. Examples of the commercially available products include KR-112, KR-211, KR-212, KR-255, KR-271, KR-272, KR-282, KR- 300, KR-311, KR-2621-1, X-40-2667A, KR-480, KR-220L, KR-220LP, KR-242A, KR-251 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) ), TSR116, TSR117, TSR144, TSR145, TSR1452, TSR165, TSR180, TSR194, XR32-901, XR-32-901, XR32-A1612, XR3303, YR47, YR3370 (all trade names, Momentive Performance Materials Japan GK), 804 RESIN 805RESIN, 806ARESIN, 840RESIN, SR2400 (all trade names, manufactured by Dow Corning Toray Co., Ltd.), and the like.
本発明の示温塗料におけるシリコーン樹脂の含有量は特に限定されないが、好ましくは該塗料全量の２０〜７０重量％、より好ましくは該塗料全量の３０〜５０重量％、さらに好ましくは該塗料全量の３５〜４５重量％である。シリコーン樹脂の含有量が前記範囲内にあることによって、硬化塗膜が高温に晒されても変色性顔料の熱可逆変色性が十分に保持され、温度変化による硬化塗膜の可逆的な変色を長期にわたって繰返しかつ鮮明に視認できる。また、硬化塗膜が十分な機械特性や耐熱性を有し、硬化塗膜に亀裂や割れが発生したり、硬化塗膜の被塗体からの部分的な剥離等が発生したりするのを防止できる。 The content of the silicone resin in the temperature indicating paint of the present invention is not particularly limited, but is preferably 20 to 70% by weight of the total amount of the paint, more preferably 30 to 50% by weight of the total amount of the paint, and further preferably 35 of the total amount of the paint. ~ 45 wt%. When the content of the silicone resin is within the above range, the thermoreversible discoloration of the discolorable pigment is sufficiently maintained even when the cured coating is exposed to a high temperature, and reversible discoloration of the cured coating due to a temperature change is achieved. Visible clearly and repeatedly over a long period of time. In addition, the cured coating film has sufficient mechanical properties and heat resistance, so that the cured coating film may be cracked or cracked, or the cured coating film may be partially peeled off from the substrate. Can be prevented.
本発明の示温塗料では、シリコーン樹脂の他に適量のバインダを含むことができる。バインダとしては、例えば、アルコキシオリゴマー（例えば、商品名：ＫＲ５００、ＫＲ４００等、いずれも信越化学工業（株）製）、エチルシリケート等が挙げられる。これらのバインダを添加することにより、例えば、湿気硬化により常温でも硬化させることができ、尚且つ耐熱性や熱可逆変色性も同様に維持することができる。 The temperature indicating paint of the present invention may contain an appropriate amount of a binder in addition to the silicone resin. Examples of the binder include alkoxy oligomers (for example, trade names: KR500, KR400, etc., both manufactured by Shin-Etsu Chemical Co., Ltd.), ethyl silicate, and the like. By adding these binders, for example, moisture curing can be performed at room temperature, and heat resistance and thermoreversible discoloration can be maintained in the same manner.
薄片状無機充填材は、例えば、主にシリコーン樹脂と協働して、硬化塗膜の機械特性や耐熱性を高め、硬化塗膜の伸び縮み等による亀裂や割れの発生を防止すると共に、硬化塗膜が２００〜３００℃又はそれを超えるような高温に晒された場合でも、変色性顔料の熱可逆変色性の低下を防止するものと考えられ、これにより、硬化塗膜を安定的にかつ長期にわたって鮮明に視認性良く変色させることができる。薄片状無機充填材が変色性顔料の熱可逆変色性の低下を防止する効果を示す理由は現状では明らかではないが、その厚み方向の表面が硬化塗膜中にて硬化塗膜の厚み方向表面を臨むように配向することがその一因になっていると推測される。 The flaky inorganic filler, for example, mainly in cooperation with silicone resin, improves the mechanical properties and heat resistance of the cured coating, prevents cracking and cracking due to expansion and contraction of the cured coating, and cures Even when the coating film is exposed to a high temperature of 200 to 300 ° C. or higher, it is considered to prevent the thermoreversible discoloration of the discolorable pigment from being deteriorated. It can be discolored vividly over a long period of time with good visibility. The reason why the flaky inorganic filler exhibits the effect of preventing the thermoreversible discoloration of the discolorable pigment from being deteriorated is not clear at present, but the surface in the thickness direction is the surface of the cured coating in the thickness direction. It is presumed that this is caused by the orientation to face the surface.
薄片状無機充填材としては、その外観形状が薄片状又は鱗片状又は板状の無機化合物であれば特に限定されないが、例えば、ガラスフレーク；金マイカ、白マイカ、セリサイト等の天然マイカやフッ素金マイカ、カリウム四ケイ素マイカ、ナトリウム四ケイ素マイカ、ナトリウムテニオライト、リチウムテニオライト等の合成マイカ等のマイカ、モンモリロナイト等の天然スメクタイト、ナトリウムヘクトライト、リチウムヘクトライト、サポナイト等の合成スメクタイト，タルク、クレー（カオリン）、焼成カオリンクレー、水酸化アルミニウム、アルミナ、ケイ酸カルシウム、シリカ、セリサイト、モンモリロナイト、窒化硼素、二硫化モリブデン等が挙げられる。なお、アルミナ、シリカ等は沈降防止剤としても機能する。薄片状無機充填材は１種を単独で又は２種以上を組み合わせて使用できる。薄片状無機充填材としては各種市販品を用いてもよい。 The flaky inorganic filler is not particularly limited as long as its external shape is a flaky, scaly, or plate-like inorganic compound. For example, glass flakes; natural mica such as gold mica, white mica, sericite, and fluorine Mica such as gold mica, potassium tetrasilicon mica, sodium tetrasilicon mica, sodium teniolite and lithium teniolite, mica such as montmorillonite, natural smectite such as montmorillonite, synthetic smectite such as sodium hectorite, lithium hectorite and saponite, talc, Examples include clay (kaolin), calcined kaolin clay, aluminum hydroxide, alumina, calcium silicate, silica, sericite, montmorillonite, boron nitride, and molybdenum disulfide. Alumina, silica, etc. also function as an anti-settling agent. The flaky inorganic filler can be used alone or in combination of two or more. Various commercially available products may be used as the flaky inorganic filler.
上記で例示した薄片状無機充填材の中でも、硬化塗膜の温度変化による可逆的な変色を長期にわたって維持する観点、硬化塗膜の鮮明な変色を得る観点等から、マイカ、タルク、クレー（カオリン）等の鉱物系薄片状無機充填材が好ましく、マイカやタルク等の体質顔料（白色顔料）としても用いられる鉱物系薄片状無機充填材がより好ましく、マイカとタルクとの併用がさらに好ましい。 Among the flaky inorganic fillers exemplified above, mica, talc, clay (kaolin) from the viewpoint of maintaining reversible discoloration due to temperature change of the cured coating film over a long period of time, and obtaining a clear discoloration of the cured coating film. Mineral-based flaky inorganic fillers such as mica and talc are preferred, mineral-based flaky inorganic fillers used as extender pigments (white pigments) such as mica and talc are more preferred, and a combination of mica and talc is more preferred.
薄片状無機充填材の寸法は特に限定されず、それ以外の各成分の種類や含有量等に応じて適宜選択されるが、粒径が好ましくは０．１〜１００μｍ程度、より好ましくは１〜５０μｍ程度、更に好ましくは３〜２０μｍ程度であり、厚さが好ましくは０．００１〜１０μｍ程度、より好ましくは０．０１〜５μｍ程度、さらに好ましくは０．０５〜３μｍ程度であり、アスペクト比（粒径／厚さ）が好ましくは１以上、より好ましくは２〜１０００、さらに好ましくは２〜１００である。また、薄片状無機充填材は、シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤、脂肪族金属塩等で表面処理を施したものでもよい。 The size of the flaky inorganic filler is not particularly limited and is appropriately selected according to the type and content of each of the other components, but the particle size is preferably about 0.1 to 100 μm, more preferably 1 to 1. The thickness is preferably about 50 μm, more preferably about 3 to 20 μm, and the thickness is preferably about 0.001 to 10 μm, more preferably about 0.01 to 5 μm, still more preferably about 0.05 to 3 μm, and the aspect ratio ( (Particle diameter / thickness) is preferably 1 or more, more preferably 2 to 1000, and still more preferably 2 to 100. Further, the flaky inorganic filler may be subjected to a surface treatment with a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, an aliphatic metal salt or the like.
本発明の示温塗料における薄片状無機充填材の含有量は特に限定されないが、好ましくは該塗料全量の１０〜６０重量％、より好ましくは該塗料全量の１５〜５５重量％、さらに好ましくは該塗料全量の１８〜５０重量％、特に好ましくは該塗料全量の２０〜４０重量％である。薄片状無機充填材の含有量が前記範囲内にあることによって、硬化塗膜の機械特性や耐熱性、耐久性等を高め、硬化塗膜における割れ、欠け、剥離等の発生を抑制し、硬化塗膜中の変色性顔料の熱可逆変色性を安定的にかつ長期的に保持し、硬化塗膜の温度変化による変色を視認し易い鮮明なものとすることができる。 The content of the flaky inorganic filler in the temperature indicating paint of the present invention is not particularly limited, but is preferably 10 to 60% by weight of the total amount of the paint, more preferably 15 to 55% by weight of the total amount of the paint, and still more preferably the paint It is 18 to 50% by weight of the total amount, particularly preferably 20 to 40% by weight of the total amount of the coating material. The content of the flaky inorganic filler is within the above range, thereby improving the mechanical properties, heat resistance, durability, etc. of the cured coating, suppressing the occurrence of cracking, chipping, peeling, etc. in the cured coating and curing. The thermoreversible discoloration of the discolorable pigment in the coating film can be maintained stably and for a long period of time, and the discoloration due to the temperature change of the cured coating film can be clearly seen.
沈降防止剤は、例えば、各種塗料における沈降防止剤と同様に、変色性顔料、シリコーン樹脂、及び薄片状無機充填材を溶剤に溶解及び／又は分散させて塗料形態に調製した本発明の示温塗料の保存安定性を高め、また、本発明の示温塗料を被塗体表面に塗布した際の液垂れを防止するために用いられる。 The anti-settling agent is, for example, the temperature indicating paint of the present invention prepared in a paint form by dissolving and / or dispersing a discolorable pigment, a silicone resin, and a flaky inorganic filler in a solvent, like the anti-settling agent in various paints. It is used to improve the storage stability of the liquid and to prevent dripping when the temperature indicating paint of the present invention is applied to the surface of the substrate.
沈降防止剤としては、主に非水系塗料に用いられる沈降防止剤を特に限定なく使用でき、例えば、有機粘土系化合物（Ａｌ、Ｃａ、Ｚｎのアミン塩、ステアレート塩、レシチン塩、アルキルスルホン酸塩等）、有機系ワックス類（ポリエチレンワックス、酸化ポリエチレンワックス、ポリエチレンアマイドワックス、脂肪酸アマイドワックス、水添ヒマシ油ワックス等）等が挙げられる。沈降防止剤は１種を単独で又は２種以上を組み合わせて使用できる。また、これらの沈降防止剤はいずれも市販されている。 As the anti-settling agent, an anti-settling agent mainly used in non-aqueous paints can be used without any particular limitation. For example, organoclay compounds (Al, Ca, Zn amine salts, stearate salts, lecithin salts, alkylsulfonic acids) Salt), organic waxes (polyethylene wax, oxidized polyethylene wax, polyethylene amide wax, fatty acid amide wax, hydrogenated castor oil wax, etc.). One type of anti-settling agent can be used alone, or two or more types can be used in combination. These anti-settling agents are all commercially available.
沈降防止剤の中でも、例えば、変色性顔料や薄片状無機充填材の塗料中での均一分散性等の観点から、有機系ワックス類が好ましく、脂肪酸アマイドワックスがさらに好ましい。脂肪酸アマイドワックスは、一般式（１）：Ｒ１−Ｃ（＝Ｏ）−ＮＨ−Ｒ２〔式中、Ｒ１及びＲ２は、それぞれ独立に炭素数１２〜２２の飽和または不飽和の脂肪族基を示す。〕で表わされる脂肪酸アマイド（以下、「脂肪酸アマイド（１）」と称すことがある。）と、アルキルシクロヘキサン、エタノール、イソプロパノールその他の、脂肪酸アマイド（１）を溶解可能な溶剤と、を含有する。前記一般式（１）において、Ｒ１及びＲ２で示される炭素数１２〜２２の脂肪族基としては、前記炭素数の脂肪族基であれば特に限定されず、直鎖状、分岐鎖状又は環状のいずれでもよく、飽和脂肪族基又は不飽和脂肪族基のいずれでもよい。 Among the anti-settling agents, for example, organic waxes are preferable, and fatty acid amide waxes are more preferable from the viewpoint of uniform dispersibility of the discolorable pigment and the flaky inorganic filler in the coating material. The fatty acid amide wax has the general formula (1): R 1 —C (═O) —NH—R 2 [wherein R 1 and R 2 are each independently a saturated or unsaturated fat having 12 to 22 carbon atoms. Indicates a group. And a solvent capable of dissolving fatty acid amide (1), such as alkylcyclohexane, ethanol, isopropanol, and the like. In the general formula (1), the aliphatic group having 12 to 22 carbon atoms represented by R 1 and R 2 is not particularly limited as long as the aliphatic group has the above carbon number, and is linear or branched. Or any of cyclic | annular form may be sufficient and either a saturated aliphatic group or an unsaturated aliphatic group may be sufficient.
脂肪酸アマイド（１）の具体例としては、例えば、ラウリン酸アマイド、ミリスチン酸アマイド、パルミチン酸アマイド、ステアリン酸アマイド、ベヘニン酸アマイド等の飽和脂肪酸アマイド、オレイン酸アマイド、エルカ酸アマイドなどの不飽和脂肪酸アマイド、メチレンビスステアリン酸アマイド、エチレンビスステアリン酸アマイド等のアルキレンビス脂肪酸アマイド等が挙げられる。脂肪酸アマイド（１）又は脂肪酸アマイド（１）を含有する脂肪酸アマイドワックスの市販品としては、例えば、脂肪酸アマイドＴ（商品名、花王（株）製）、ディスパロン（登録商標）ＰＦＡ−１３１（商品名、楠本化成(株)製）等が挙げられる。 Specific examples of the fatty acid amide (1) include, for example, saturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, and erucic acid amide. Examples thereof include alkylene bis fatty acid amides such as amide, methylene bis stearic acid amide and ethylene bis stearic acid amide. Examples of commercially available fatty acid amide (1) or fatty acid amide wax containing fatty acid amide (1) include fatty acid amide T (trade name, manufactured by Kao Corporation), Dispalon (registered trademark) PFA-131 (trade name). , Enomoto Kasei Co., Ltd.).
本発明の示温塗料における沈降防止剤の含有量は特に限定されないが、好ましくは該塗料全量の０．０５〜１０重量％、より好ましくは該塗料全量の０．１〜５重量％、さらに好ましくは該塗料全量の１〜３重量％である。沈降防止剤の含有量が前記範囲内にあることによって、主目的である各成分の沈降防止や液垂れ防止が十分に達成され、良好な塗工性を有する塗料とすることができると共に、変色性顔料や薄片状無機充填材の塗料中での分散性を高めることにより、間接的に変色性顔料の熱可逆変色性の低下を抑制し、熱可逆変色性の長寿命化に寄与するものと考えられる。 The content of the anti-settling agent in the temperature indicating paint of the present invention is not particularly limited, but is preferably 0.05 to 10% by weight of the total amount of the paint, more preferably 0.1 to 5% by weight of the total amount of the paint, and further preferably It is 1 to 3% by weight of the total amount of the paint. When the content of the anti-settling agent is within the above range, the main purpose of preventing the settling and dripping prevention of each component is sufficiently achieved, and it is possible to obtain a paint having good coating properties and discoloration. Of dispersible pigments and flaky inorganic fillers in paints, which indirectly suppresses the decrease in thermoreversible discoloration of discolorable pigments and contributes to extending the life of thermoreversible discoloration Conceivable.
溶剤としては、変色性顔料、シリコーン樹脂、及び薄片状無機充填材をほぼ均一に溶解及び／又は分散できるものであれば特に限定されず、従来から塗料用途に用いられる溶剤をいずれも使用できるが、例えば、トルエン、キシレン、エチルベンゼン、ソルベントナフサ等の芳香族炭化水素類、ヘキサン、ヘブタン等の鎖状炭化水素類、シクロへキサン、メチルシクロへキサン等の環状炭化水素類、酢酸エチル、酢酸ｉｓｏ−プロピル、酢酸ブチル、酢酸ｉｓｏ−ブチル、酢酸アミル、蟻酸エチル、プロピオン酸ブチル、メチルセロソルブアセテート、セロソルブアセテート等のエステル類、メチルイソブチルケトン、メチルエチルケトン、ジイソブチルケトン、アセトン等のケトン類、メタノール、エタノール、プロパノール、ｉｓｏ−プロパノール、ブタノール、ｉｓｏ−ブタノール、ｔｅｒｔ−ブタノール等の低級アルコール類、テトラヒドロフラン、ジオキサン等の環状エーテル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール等のグリコール類、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等のグリコールエーテル類、メチルセロソルブアセテート、メトキシプロピルアセテート等のアセテート類等が挙げられる。これらの溶剤は１種を単独で又は必要に応じて２種以上を組み合わせて使用できる。溶剤は、変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤等の各成分の種類及び含有量、最終的に得られる硬化塗膜の用途等に応じて適宜選択される。 The solvent is not particularly limited as long as it can dissolve and / or disperse the color-changing pigment, silicone resin, and flaky inorganic filler almost uniformly, and any solvent conventionally used for paints can be used. For example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene and solvent naphtha, chain hydrocarbons such as hexane and hebutane, cyclic hydrocarbons such as cyclohexane and methylcyclohexane, ethyl acetate, iso-acetate Esters such as propyl, butyl acetate, iso-butyl acetate, amyl acetate, ethyl formate, butyl propionate, methyl cellosolve acetate, cellosolve acetate, ketones such as methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, acetone, methanol, ethanol, Propanol, iso-propyl Lower alcohols such as panol, butanol, iso-butanol and tert-butanol, cyclic ethers such as tetrahydrofuran and dioxane, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, ethylene glycol, diethylene glycol, tri Examples include glycols such as ethylene glycol and propylene glycol, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, and acetates such as methyl cellosolve acetate and methoxypropyl acetate. These solvent can be used individually by 1 type or in combination of 2 or more type as needed. A solvent is suitably selected according to the kind and content of each component, such as a color-change pigment, a silicone resin, a flaky inorganic filler, and an anti-settling agent, and the use of the finally obtained cured coating film.
本発明の示温塗料における溶剤の含有量は特に限定されないが、好ましくは該塗料全量の３〜５０重量％、より好ましくは該塗料全量の３〜２０重量％、さらに好ましく該塗料全量の５〜１５重量％である。溶剤の含有量を前記範囲内とすることによって、各成分の該塗料中での分散性を高め、所望の熱可逆変色性、機械特性及び耐熱性を有する硬化塗膜が得られると共に、該塗料に十分な塗工性を付与することができる。 The solvent content in the temperature indicating paint of the present invention is not particularly limited, but is preferably 3 to 50% by weight of the total amount of the paint, more preferably 3 to 20% by weight of the total amount of the paint, and further preferably 5 to 15% of the total amount of the paint. % By weight. By setting the content of the solvent within the above range, the dispersibility of each component in the paint can be improved, and a cured coating film having desired thermoreversible discoloration, mechanical properties, and heat resistance can be obtained. Sufficient coatability can be imparted.
本発明の示温塗料は、硬化塗膜の熱可逆変色性や耐久性を損なわない範囲で、必要に応じて、上記した各成分の他に、塗料に配合される一般的な添加剤を含むことができる。該添加剤としては、例えば、シリコーン樹脂の硬化触媒や硬化促進剤、二酸化チタン繊維、チタン酸カリウム繊維、ワラストナイト等の繊維状無機充填材、各種粒状無機充填材、消泡剤、レベリング剤、塗面調整剤、紫外線吸収剤、光安定剤、増粘剤、密着改良剤、つや消し剤等が挙げられる。添加剤は１種を単独で又は２種以上を組み合わせて使用できる。 The temperature indicating paint of the present invention contains general additives to be blended in the paint in addition to the above-described components as necessary within the range not impairing the thermoreversible discoloration and durability of the cured coating film. Can do. Examples of the additive include silicone resin curing catalysts and curing accelerators, fibrous inorganic fillers such as titanium dioxide fibers, potassium titanate fibers, and wollastonite, various granular inorganic fillers, antifoaming agents, and leveling agents. , Coating surface conditioners, ultraviolet absorbers, light stabilizers, thickeners, adhesion improvers, matting agents and the like. An additive can be used individually by 1 type or in combination of 2 or more types.
本発明の示温塗料は、例えば、変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤、及び必要に応じて配合される上記添加剤の少なくとも１種を溶剤と混合し、各成分を溶剤に溶解及び／又は分散させることにより調製できる。各成分と溶剤との混合には、塗料調製用の一般的な混合装置を使用でき、該混合装置の具体例としては、例えば、ペイントシェーカー、ビーズミル、ニーダー、ボールミル、ダイノーミル、ペブルミル、ロールミル、サンドグラインドミル、ディスパー等が挙げられる。 The temperature indicating paint of the present invention comprises, for example, a color-changing pigment, a silicone resin, a flaky inorganic filler, an anti-settling agent, and at least one of the above-mentioned additives blended as necessary, mixed with a solvent, and each component is mixed. It can be prepared by dissolving and / or dispersing in a solvent. For mixing the components and the solvent, a general mixing apparatus for preparing a paint can be used. Specific examples of the mixing apparatus include, for example, paint shaker, bead mill, kneader, ball mill, dyno mill, pebble mill, roll mill, sand A grind mill, a disper, etc. are mentioned.
本発明の示温塗料を被塗体の表面に塗布し、得られた塗膜を加熱し、該塗膜中のシリコーン樹脂等を硬化させ、かつ溶剤を除去することにより、温度検知体として用いられる硬化塗膜を形成できる。また、前述のバインダ（アルコキシオリゴマー、エチルシリケート等）を添加することにより、湿気硬化により硬化塗膜を得ることもできる。 It is used as a temperature detector by applying the temperature indicating paint of the present invention to the surface of an object to be coated, heating the obtained coating film, curing the silicone resin in the coating film, and removing the solvent. A cured coating film can be formed. Further, by adding the above-mentioned binder (alkoxy oligomer, ethyl silicate, etc.), a cured coating film can be obtained by moisture curing.
被塗体を構成する素材としては特に限定されないが、例えば、金属、プラスチック、ガラス、ガラス以外のセラミックス等が挙げられる。金属としては、例えば、鉄、アルミニウム、アルミめっき鋼板、チンフリー鋼板（ＴＦＳ）、ステンレス鋼板、リン酸亜鉛処理鋼板、亜鉛・亜鉛合金めっき鋼板、冷間圧延鋼板、熱間圧延鋼板等が挙げられる。プラスチックとしては、例えば、ポリカーボネート、ポリエチレン、ポリプロピレン、ポリエステル、ＡＢＳ樹脂、繊維強化プラスチック（ＦＲＰ）等が挙げられる。これらの中でも、被塗体の素材としては、金属やプラスチックが好ましく、金属がより好ましい。被塗体は２種以上の素材から構成されるものでもよいが、示温塗料を塗布する箇所は金属及び／又はプラスチックで構成されることが好ましい。 Although it does not specifically limit as a raw material which comprises a to-be-coated body, For example, ceramics other than a metal, a plastics, glass, glass, etc. are mentioned. Examples of the metal include iron, aluminum, aluminum-plated steel plate, chin-free steel plate (TFS), stainless steel plate, zinc phosphate-treated steel plate, zinc / zinc alloy-plated steel plate, cold rolled steel plate, hot rolled steel plate and the like. . Examples of the plastic include polycarbonate, polyethylene, polypropylene, polyester, ABS resin, and fiber reinforced plastic (FRP). Among these, as a raw material of a to-be-coated body, a metal and a plastic are preferable and a metal is more preferable. The object to be coated may be composed of two or more kinds of materials, but the portion to which the temperature indicating paint is applied is preferably composed of metal and / or plastic.
被塗体は、具体的には、表面が８０℃を超える高温になることがある被塗体が好ましい。該被塗体の具体例としては、例えば、ストーブ、ヒータ等の加熱暖房器具、鍋、フライパン、スキレット、ソースパン、ソテーパン、グリル、調理用ヒータ、やかん、ケトル等の加熱調理器具、湯沸かし器、湯呑、カップ、どんぷり、お椀等の食器類、高温の流動物を貯留するタンク、高温の流動物や水蒸気を流動させる工業用パイプ、ボイラー等の工業用設備等が挙げられる。このような被塗体の表面に本発明の示温塗料から形成される硬化塗膜（温度検知体）を設けることにより、被塗体表面の温度を硬化塗膜の変色により容易に視認できる。したがって、高温状態の該被塗体に誤って触れることによる火傷の発症等を未然に防止できる。 Specifically, the target object whose surface may become a high temperature exceeding 80 ° C. is preferable. Specific examples of the object to be coated include, for example, heating and heating appliances such as a stove and a heater, pans, frying pans, skillets, saucepans, taper, grills, cooking heaters, kettles, kettles and other heating cooking appliances, water heaters, and hot water baths. And tableware such as cups, dumplings, rice cakes, tanks for storing high-temperature fluids, industrial pipes for flowing high-temperature fluids and steam, and industrial equipment such as boilers. By providing a cured coating film (temperature detection body) formed from the temperature indicating paint of the present invention on the surface of such an object to be coated, the temperature of the surface of the object to be coated can be easily visually recognized by discoloration of the cured film. Accordingly, it is possible to prevent the occurrence of burns and the like due to accidental contact with the object to be coated in a high temperature state.
本発明の示温塗料の被塗体表面への塗布方法としては特に限定されず、公知の塗布方法をいずれも採用でき、例えば、フローコート法、ロールコート法、吹き付け法、エアレススプレー法、エアスプレー法、刷毛塗り法、コテ塗り法、浸漬法、引き上げ法、ノズル法、巻き取り法、流し法、盛り付け法、パッチング法、静電塗装法、バーコーダ法、カーテンコータ法、カーテンフローコート法、エアナイフ法、グラビア法、スクリーン印刷法等が挙げられる。また、本発明の示温塗料の塗布量（塗工量）は特に限定されないが、好ましくは８０〜３００ｇ／ｍ２程度、より好ましくは１００〜２００ｇ／ｍ２程度である。 The application method of the temperature indicating paint of the present invention to the surface of the substrate is not particularly limited, and any known application method can be employed, for example, a flow coating method, a roll coating method, a spraying method, an airless spray method, an air spray. Method, brush coating method, trowel coating method, dipping method, pulling method, nozzle method, winding method, sink method, laying method, patching method, electrostatic coating method, bar coder method, curtain coater method, curtain flow coating method, air knife Method, gravure method, screen printing method and the like. The coating amount of the temperature indicating paint of the present invention (coating amount) is not particularly limited, preferably 80~300g / m 2, more preferably about 100 to 200 g / m 2 approximately.
こうして被塗体表面に塗布された示温塗料の塗膜を加熱し、シリコーン樹脂の硬化及び溶剤の乾燥除去等を行なうことにより、所定の温度領域を境界にして、温度変化により可逆的に変色する硬化塗膜からなる本発明の温度検知体が形成される。変色境界温度領域は、主に硬化塗膜中の変色性顔料の種類によって決まる。ここで硬化前の塗膜の加熱温度は、シリコーン樹脂の種類や被塗体への塗布量等に応じて適宜選択されるが、好ましくは１５０〜２５０℃程度、より好ましくは２００〜２５０℃程度である。前記のような温度範囲で加熱しても、変色性顔料の熱可逆変色性は十分に保持される。 The coating of the temperature indicating paint applied to the surface of the object is heated, and the silicone resin is cured and the solvent is removed by drying, so that the color changes reversibly with a temperature change at a predetermined temperature range. The temperature detector of the present invention comprising a cured coating film is formed. The color change boundary temperature region is mainly determined by the type of the color changing pigment in the cured coating film. Although the heating temperature of the coating film before hardening here is suitably selected according to the kind of silicone resin, the application quantity to a to-be-coated body, etc., Preferably it is about 150-250 degreeC, More preferably, it is about 200-250 degreeC. It is. Even when heated in the above temperature range, the thermoreversible discoloration of the discolorable pigment is sufficiently maintained.
本発明の温度検知体を構成する硬化塗膜は、マトリックス樹脂であるシリコーン樹脂の硬化物中に、変色性顔料や薄片状無機充填材等がほぼ均一に分散したものであり、また、薄片状無機充填材は主にその表面が該硬化塗膜の厚み方向表面を臨むように配向しているものと考えられる。該硬化塗膜は、前記のような構造的特徴を有することにより、機械特性や耐熱性、耐用性に優れると共に、可逆的かつ鮮明な変色を長期間にわたって繰り返すことができるものと考えられる。 The cured coating film constituting the temperature detector of the present invention is a cured product of a silicone resin that is a matrix resin, in which a discolorable pigment, a flaky inorganic filler, and the like are dispersed almost uniformly. It is considered that the inorganic filler is oriented so that its surface mainly faces the surface in the thickness direction of the cured coating film. The cured coating film is considered to be excellent in mechanical properties, heat resistance and durability due to having the structural characteristics as described above, and capable of repeating reversible and clear discoloration over a long period of time.
本発明の温度検知体を構成する硬化塗膜の厚さは特に限定されないが、硬化塗膜の耐久性や耐熱性等の点からは、好ましくは１０〜１００μｍ、より好ましくは２０〜６０μｍである。また、本発明では、硬化塗膜の厚さが前記範囲になるように、示温塗料の塗布量を適宜調整することが好ましい。 Although the thickness of the cured coating film which comprises the temperature detection body of this invention is not specifically limited, From points, such as durability of a cured coating film, and heat resistance, Preferably it is 10-100 micrometers, More preferably, it is 20-60 micrometers. . Moreover, in this invention, it is preferable to adjust the application quantity of a temperature indicating paint suitably so that the thickness of a cured coating film may become the said range.
本発明では、硬化塗膜の被塗体に対する接着性や密着性を更に向上させるために、被塗体と硬化塗膜との間にプライマー塗膜を設けても良い。該プライマー塗膜は、プライマー塗料を被塗体表面に塗布し、得られたプライマー塗膜を加熱等の硬化方法で硬化させることにより形成される。また、被塗体表面にプライマー塗膜を形成し、該プライマー塗膜の表面に本発明の示温塗料からなる塗膜を形成した後、これらの塗膜を一体的に硬化させることもできる。ここで、プライマー塗料としては特に限定されないが、シリコーン樹脂をマトリックスとする塗膜に用いられ、かつ耐熱性を有するプライマー塗料が好ましい。該プライマー塗料としては、例えば、ヒートップＳ、ヒートップＳＬ、ヒートップＳＬＺ（いずれも商品名、熱研化学工業（株）製）、無機ジンクリッチプライマー等が挙げられる。さらに、本発明の温度検知体を構成する硬化塗膜の表面に、クリアー塗料等の上塗り塗料を塗装してもよい。 In this invention, in order to further improve the adhesiveness and adhesiveness with respect to the to-be-coated body of a cured coating film, you may provide a primer coating film between a to-be-coated body and a cured coating film. The primer coating film is formed by applying a primer coating to the surface of an object to be coated and curing the obtained primer coating film by a curing method such as heating. Moreover, after forming a primer coating film on the surface of a to-be-coated body, and forming the coating film which consists of the temperature indicating paints of this invention on the surface of this primer coating film, these coating films can also be hardened | cured integrally. Here, the primer coating is not particularly limited, but a primer coating that is used for a coating film having a silicone resin as a matrix and has heat resistance is preferable. Examples of the primer paint include Hetop S, Hetop SL, and Hetop SLZ (all trade names, manufactured by Thermoken Chemical Industry Co., Ltd.), inorganic zinc rich primers, and the like. Furthermore, an overcoating material such as a clear coating material may be applied to the surface of the cured coating film constituting the temperature detector of the present invention.
以下に実施例及び比較例を挙げ、本発明を具体的に説明する。以下において、「部」及び「％」は、特に断らない限り、それぞれ「重量部」及び「重量％」を意味するものとする。また、下記の材料を用いた。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified. The following materials were used.
［熱可逆変色性顔料］
＜バナジン酸ビスマス系顔料＞
商品名：リソパックイエロー６６０１Ｂ、ＣＡＰＰＥＬＬＥ ＰＩＧＭＥＮＴＳ ＮＶ社製、比重：６．６ｇ／ｃｍ３、平均粒径：５μｍ、吸油量：２４ｇ／１００ｇ、バナジウム含有量：１４．９％、組成：バナジン酸ビスマス（ＢｉＶＯ４）９５％、リン酸アルミニウム（Ａｌ（ＰＯ３）３）３％、モリブデン酸カルシウム（ＣａＭｏＯ４）１％、酸化アルミニウム（Ａｌ２Ｏ３）１％、温度上昇に伴って黄色から黄橙色を経て橙色に変色
[Thermal reversible color-changing pigment]
<Bismuate vanadate pigment>
Product name: Risopack Yellow 6601B, manufactured by CAPPELLE PIGMENTS NV, specific gravity: 6.6 g / cm 3 , average particle size: 5 μm, oil absorption: 24 g / 100 g, vanadium content: 14.9%, composition: bismuth vanadate (BiVO 4 ) 95%, aluminum phosphate (Al (PO 3 ) 3 ) 3%, calcium molybdate (CaMoO 4 ) 1%, aluminum oxide (Al 2 O 3 ) 1%, yellow to yellow with increasing temperature Turns orange through orange
＜酸化ビスマス系顔料＞
酸化ビスマス（ＩＩＩ）、安田薬品（株）製、平均粒径：２．４１μｍ、温度上昇に伴って薄黄色から黄色を経て黄橙色に変色
<Bismuth oxide pigment>
Bismuth (III) oxide, manufactured by Yasuda Pharmaceutical Co., Ltd., average particle size: 2.41 μm, changes from light yellow to yellow-orange as the temperature rises
［シリコーン樹脂］
商品名：ＴＳＲ−１１７、メチルフェニルシリコーン樹脂、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製
［薄片状無機充填材］
＜タルク＞
商品名：タルクＭＳ４１２、富士タルク(株)製
＜マイカ＞
商品名：マイカＭ１０１、白石カルシウム(株)製
［沈降防止剤］
商品名：ディスバロンＰＦＡ−１３１、脂肪酸アマイドワックス、楠本化成(株)製
［溶剤（Ｅ）］
キシレン
[Silicone resin]
Product name: TSR-117, methylphenyl silicone resin, manufactured by Momentive Performance Materials Japan LLC [Flame-like inorganic filler]
<Talc>
Product name: Talc MS412, manufactured by Fuji Talc Co., Ltd. <Mica>
Product name: Mica M101, manufactured by Shiraishi Calcium Co., Ltd. [Anti-settling agent]
Product name: Disvalon PFA-131, fatty acid amide wax, manufactured by Enomoto Kasei Co., Ltd. [Solvent (E)]
Xylene
（実施例１）
シリコーン樹脂４０部、及び沈降防止剤（ディスバロンＰＦＡ−１３１）２部をディスパーにて１０〜２０分撹拌した後、それを撹拌しながらバナジン酸ビスマス系顔料２０部、タルク（薄片状無機充填材、タルクＭＳ４１２）１５部、マイカ（薄片状無機充填材、マイカＭ１０１）１５部、及びキシレン８部を投入し、さらに１５〜２０分撹拌した後、横型分散機（ダイノーミル）にて粒ゲージで５０μｍ以下になるまで分散し、本発明の示温塗料を調製した。
Example 1
40 parts of a silicone resin and 2 parts of an anti-settling agent (Disvalon PFA-131) were stirred with a disper for 10 to 20 minutes, and while stirring them, 20 parts of a bismuth vanadate pigment and talc (flaky inorganic filler) , 15 parts of talc MS412), 15 parts of mica (flaky inorganic filler, mica M101) and 8 parts of xylene, and further stirred for 15 to 20 minutes, and then 50 μm with a horizontal gauge (Dynomill) with a particle gauge. Dispersion was carried out until the temperature was as follows to prepare the temperature indicating paint of the present invention.
［評価用試料の作製］
冷間圧延鋼板の表面に、上記で得られた示温塗料を２回スプレー塗布して厚さ３０〜６０μｍの塗膜を形成し、２３０℃で３０分間焼き付け、硬化塗膜からなる温度検知体を設け、評価用試料とした。この評価用試料を用いて、以下に示す、熱可逆変色性の有無、耐久性及び耐熱性を評価した。結果を表１に示す。
[Preparation of sample for evaluation]
On the surface of the cold-rolled steel sheet, the temperature-indicating paint obtained above is sprayed twice to form a coating film having a thickness of 30 to 60 μm, baked at 230 ° C. for 30 minutes, and a temperature detector comprising a cured coating film is formed. A sample for evaluation was provided. Using this evaluation sample, the presence / absence, durability and heat resistance of thermoreversible discoloration shown below were evaluated. The results are shown in Table 1.
［熱可逆変色性の有無］
上記で得られた評価用試料をホットプレートに載せて徐々に加熱し、該試料の表面温度を測定しながら、所定の変色温度を境にして変色するか否かを目視で確認し、かつその変色が可逆的なものであるか否かを目視で確認し、下記の評価基準に従って評価した。
◎：表面温度が変色温度を超えると鮮やかに変色し、変色温度を下回ると直ぐに元の色に戻る。
○：表面温度が変色温度を超えると比較的容易に視認できる程度に変色し、変色温度を下回ると元の色に戻る。
×：表面温度が変色温度を超えると変色するものの、変色の度合いが小さく、注意して視認しないと変色が判りづらい。
[Existence of thermoreversible discoloration]
The evaluation sample obtained above is placed on a hot plate and gradually heated, and while measuring the surface temperature of the sample, it is visually confirmed whether or not the color changes at a predetermined color change temperature. Whether or not the discoloration was reversible was visually confirmed and evaluated according to the following evaluation criteria.
A: When the surface temperature exceeds the color change temperature, the color changes vividly. When the surface temperature falls below the color change temperature, the original color is restored immediately.
◯: When the surface temperature exceeds the color change temperature, the color changes to such an extent that it can be visually recognized relatively easily. When the surface temperature falls below the color change temperature, the original color is restored.
X: Although the color changes when the surface temperature exceeds the color change temperature, the degree of color change is small, and the color change is difficult to understand unless carefully viewed.
［熱可逆変色性の耐久性（熱可逆変色の繰返し性）］
上記熱可逆変色性の確認試験を１０００サイクル実施し、熱可逆変色性及び塗膜外観に異常がないか目視により確認し、下記の基準に基づいて評価した。
◎：１０００サイクルを経過しても、表面温度が変色温度を超えると鮮やかに変色し、変色温度を下回ると直ぐに元の色に戻り、塗膜外観にも異常がない。
○：１０００サイクルを経過しても、表面温度が変色温度を超えると比較的容易に視認できる程度に変色し、変色温度を下回ると元の色に戻り、塗膜外観にも異常がない。
×：１０００サイクルを経過すると、変色が不鮮明になり、注視した状態でも判別しにくい。
[Durability of thermoreversible discoloration (repeatability of thermoreversible discoloration)]
The test for confirming the thermoreversible discoloration was conducted 1000 cycles, and it was visually confirmed whether there was any abnormality in the thermoreversible discoloration and the appearance of the coating film, and evaluated based on the following criteria.
A: Even after 1000 cycles, when the surface temperature exceeds the color change temperature, the color changes vividly. When the surface temperature falls below the color change temperature, the original color is restored immediately, and there is no abnormality in the appearance of the coating film.
○: Even after 1000 cycles, when the surface temperature exceeds the color change temperature, the color changes to such a degree that it can be visually recognized relatively easily.
X: After 1000 cycles, the discoloration becomes unclear, and it is difficult to discriminate even with a gaze.
［熱可逆変色性の耐熱性］
上記で得られた評価用試料を４００℃、５００℃又は６００℃で１時間加熱し（この時点では変色している）、室温放置する（この時点では元の温度に戻る）サイクルを、４００℃で１００サイクル、５００℃で５０サイクル又は６００℃で３０サイクル実施し、熱可逆変色性及び塗膜外観を以下の基準で評価した。
[Thermal reversible color change heat resistance]
The evaluation sample obtained above was heated at 400 ° C., 500 ° C. or 600 ° C. for 1 hour (discolored at this time) and left at room temperature (returned to the original temperature at this time). 100 cycles, 50 cycles at 500 ° C. or 30 cycles at 600 ° C., and thermoreversible discoloration and coating appearance were evaluated according to the following criteria.
◎：熱可逆変色性の低下がなく、鮮明な変色及び速やかな元の色への戻りが得られ、塗膜外観にも異常がない。
○：元の色に戻った時に、加熱時の色が若干残るものの大きな変化はなく、塗膜外観にも異常がない。
△：元の色に戻った時に加熱時の色が残り、徐々に熱可逆変色性がなくなるか、または塗膜に割れ、剥がれなどの異常が見られる。
×：加熱時の色になったまま元の色には戻らなくなり、熱可逆変色性を示さないか、または、加熱による割れ、剥がれなどの塗膜異常が生じる。
(Double-circle): There is no fall of thermoreversible discoloration, a clear discoloration and quick return to the original color are obtained, and there is no abnormality in the appearance of the coating film.
○: When returning to the original color, although the color remains slightly during heating, there is no significant change, and there is no abnormality in the appearance of the coating film.
(Triangle | delta): The color at the time of a heating will remain when it returns to the original color, and thermoreversible discoloration will lose | disappear gradually, or abnormalities, such as a crack and peeling, are seen in a coating film.
X: The original color is not restored while maintaining the color at the time of heating, and thermoreversible discoloration is not exhibited, or coating film abnormality such as cracking and peeling due to heating occurs.
（実施例２〜５）
下記表１に示す配合割合（部）で、熱可逆変色性顔料、シリコーン樹脂、薄片状無機充填材、沈降防止剤、及び溶剤を使用する以外は、実施例１と同様にして、実施例２〜５の示温塗料を調製し、これらを用いて硬化塗膜（温度検知体）を作製し、その熱可逆変色性及びその耐久性、耐熱性を実施例１と同様にして評価した。結果を表１に示す。
(Examples 2 to 5)
Example 2 in the same manner as in Example 1 except that the thermoreversible color-changing pigment, silicone resin, flaky inorganic filler, anti-settling agent, and solvent are used in the blending ratio (parts) shown in Table 1 below. The temperature indicating paints of 5 to 5 were prepared, and cured coating films (temperature detectors) were prepared using them. The thermoreversible discoloration, durability, and heat resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.
表１より、本発明による硬化塗膜（温度検知体）の熱可逆変色性は、耐久性及び４００℃での耐熱性に優れ、長期間にわたって安定的に変色することが判る。特に、熱可逆変色性顔料としてバナジン酸ビスマス系顔料を用いた場合には、６００℃という高温に晒されても、鮮明な変色を伴う熱可逆変色性が非常に長期にわたって維持されることが判る。
From Table 1, it can be seen that the thermoreversible discoloration of the cured coating film (temperature detector) according to the present invention is excellent in durability and heat resistance at 400 ° C., and stably discolors over a long period of time. In particular, when a bismuth vanadate pigment is used as the thermoreversible color-changing pigment, it can be seen that the thermoreversible color-changing property with vivid color change is maintained for a very long time even when exposed to a high temperature of 600 ° C. .
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| CN109233409A (en) * | 2017-05-18 | 2019-01-18 | 东北林业大学 | Temperature causes preparation and the technique for applying of Reversible Color-Changing Coating |
| CN110359315A (en) * | 2019-07-25 | 2019-10-22 | 广州美术学院 | A kind of production method of furniture fabric |
| WO2021234285A1 (en) * | 2020-05-19 | 2021-11-25 | Seb S.A. | Sol-gel coating comprising a temperature indicator |
| WO2021234284A1 (en) * | 2020-05-19 | 2021-11-25 | Seb S.A. | Fluoropolymer-based coating with temperature indicator |
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| CN106947371A (en) * | 2017-04-13 | 2017-07-14 | 江苏大使同丰涂料有限公司 | A kind of high temperature color multivariable reversible thermopaint and preparation method thereof |
| CN109233409A (en) * | 2017-05-18 | 2019-01-18 | 东北林业大学 | Temperature causes preparation and the technique for applying of Reversible Color-Changing Coating |
| KR101863272B1 (en) * | 2018-01-31 | 2018-06-29 | 주식회사 이피이 | Connecting joint coated with high elongation elastic paint with temperature sensitive color change |
| CN110359315A (en) * | 2019-07-25 | 2019-10-22 | 广州美术学院 | A kind of production method of furniture fabric |
| WO2021234285A1 (en) * | 2020-05-19 | 2021-11-25 | Seb S.A. | Sol-gel coating comprising a temperature indicator |
| WO2021234284A1 (en) * | 2020-05-19 | 2021-11-25 | Seb S.A. | Fluoropolymer-based coating with temperature indicator |
| FR3110590A1 (en) * | 2020-05-19 | 2021-11-26 | Seb S.A. | Sol-gel coating including a temperature indicator |
| FR3110588A1 (en) * | 2020-05-19 | 2021-11-26 | Seb S.A. | Fluoropolymer based coating including temperature indicator |
| CN113737542A (en) * | 2021-09-18 | 2021-12-03 | 江苏聚杰微纤科技集团股份有限公司 | High-thermal-conductivity quick-response type thermochromic fabric and preparation method thereof |
| KR200496388Y1 (en) * | 2022-03-04 | 2023-01-18 | 윤용철 | bread mold |
| CN115232568A (en) * | 2022-07-29 | 2022-10-25 | 无锡市太湖防腐材料有限公司 | Irreversible temperature indicating paster for high temperature warning |
| CN115232568B (en) * | 2022-07-29 | 2023-12-08 | 无锡市太湖防腐材料有限公司 | Irreversible temperature indicating patch for high-temperature warning |
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