JPH0435514B2 - - Google Patents
Info
- Publication number
- JPH0435514B2 JPH0435514B2 JP11959987A JP11959987A JPH0435514B2 JP H0435514 B2 JPH0435514 B2 JP H0435514B2 JP 11959987 A JP11959987 A JP 11959987A JP 11959987 A JP11959987 A JP 11959987A JP H0435514 B2 JPH0435514 B2 JP H0435514B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- cro
- color
- chromic acid
- reversible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 29
- 230000002441 reversible effect Effects 0.000 claims description 19
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 15
- -1 chromic acid compound Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000005562 fading Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 235000019646 color tone Nutrition 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Glass Compositions (AREA)
Description
(イ)産業上の利用分野
本発明は、温度により色調が変わる物質の性質
を利用する温度管理材の一種である可逆性温材に
関するものである。
(ロ) 従来の技術
従来、可逆性示温材は、温度変化に対して急激
な変色を示すといつた温度表示能力に重点をおい
て開発されてきた。したがつて、可逆性示温材と
して提案され、商品化されてきたものは、相転移
による変色をする金属ヨウ化物、分子配向の変化
によ変色をする液晶、電子授受による変色を示す
有機化合物等、いれもある特定の温度で劇的な色
調の変化を示す材料であ。また、これらの可逆性
示温材は、応用面でも広範囲な分野での適用が行
われ始め、従来からある示温塗料、ラベル、クレ
ヨンといつた半製品から、温度計、玩具、衣料品
といつたものへの適用まで、活発な商品開発が行
われている。
(ハ) 発明が解決しようとする問題点
しかし、これらの材料及び商品群の使用状況を
見ると、一時的な使用を主とした、使い捨てに近
い用途や、せいぜい100℃程度までの比較的穏や
かな条件での使用といつた用途に限られている。
これは、従来品の耐熱限界温度が低く、200℃前
後の温度範囲で分解してしまうためである。
この従来の材料の耐熱限界温度の低さは、使用
環境の限定のみならず、加工法、適用商品の面で
も制約を与えている。加工法に関しては、例え
ば、塗装法として広く使われている焼付付け塗装
などでは、とくに焼付け温度の低い方法以外はま
つたく使用できない。また、窯業などで用いられ
ている釉薬によるガラス化も不可能である。ま
た、適用商品に関しては、耐熱限界温度以上に温
度上昇する可能性のあるものは無論適用外である
が、その他にも、耐久消費財に代表される使用年
限の極めて長い商品には、示温性材料の耐熱性、
耐久性が低く、褪色によりその商品価値を著しく
下げてしまうう危険性があり、適用が困難であつ
た。
にもかかわらず、示温材料の適用が望まれる商
品は非常に多い。しかし、上記のごとく従来材料
のもつ使用環境、加工法、適用商品の限界を破る
ためには、耐熱温度を高める必要があり、広範な
用途に適用することを考えると、最低でも500℃
の耐熱温度が望まれる。しかし、これは従来材料
の単なる改良では不可能であつた。
本発明は、かかる状況下においてなされたもの
であり、広範な用途を可能とする少なくとも50℃
の耐熱温度を有する可逆性示温材を提供しようと
するものである。
(ニ) 問題点を解決するための手段及び作用
上記点に鑑み鋭意研究を行つた結果、本発明者
らはある一群の無機系クロム酸化合物が、良好な
耐熱性を有すると共に可逆的な示温特性を発現す
る事実を見出した。
かくして本発明によれば下式：
MCrO4
（式中、ＭはNa2，K2，Rb2，Cs2，Sr，Tl2，
１／３（Tl2Mg2），１／２（Tl2Sr），１／２
（Tl2Ba）又はPbを示す）
で表わされるクロム酸化合物又はこれらの混合物
からなる可逆性示温材が提供される。
この発明におけるクロム酸化合物は、
Na2CrO4，K2CrO4，Rb2CrO4，Cs2CrO4，
SrCrO4，Tl2CrO4，Tl2Mg2（CrO4）3，Tl2Sr
（CrO4）2，Tl2Ba（CrO4）2及びPbCrO4の群の中か
ら選択される。これらのうち、市販されているも
のはそのまま用いることができ、Tl2CrO4は例え
ばTlNO3とK2CrO4とから沈澱反応により簡便に
得ることができ、Tl2Mg2（CrO4）3，Tl2Sr
（CrO4）2，Tl2Br（CrO4）2などは、例えば市販品の
MgCrO4，SrCrO4やBaCrO4と上記Tl2CrO4とを
所定比で焼結させることにより簡便に得ることが
できる。
上記クロム酸化合物は単独又は２種以上の混合
物の形でそのまま可逆性示温材として機能する。
混合物として用いる場合の各比率は任意に決定で
きる。これらのクロム酸化合物からなる可逆性示
温材は通常、粉末の形態そのままあるいは適当な
無機バインダーや有機バインダーと混合して塗布
したり、場合によつては透明基板間に狭持したり
所望の形状に成形して温度管理や表示を意図する
各種用途に適用することができる。
なお本発明の可逆性示温材には色調調製のため
に、他の耐熱性顔料を混入することも可能であ
る。例えば、室温で明るい黄色、150℃で明るい
黄赤に変色するTl2CrO4に、コバルトグリーン系
顔料を少量混入することで、室温での色調を黄緑
色に、150℃の色調を茶色に変えることができる。
(ホ) 実施例
以下、本発明に係る可逆性示温材を実施例によ
り詳細に説明する。
Na2CrO4，K2CrO4，Rb2CrO4，Cs2CrO4，
SrCrO4，Tl2rO4，Tl2Mg（CrO4）3，Tl2Sr
（CrO4）2，Tl2Ba（CrO4）2及びPbCrO4の各クロム
酸化合物の熱変色特性及び耐熱特性について調べ
た。ここで、Na2CrO4，K2CrO4，Rb2CrO4，
Cs2CrO4，SrCrO4，PbCrO4は、市販試薬を用い
た。Tl2CrO4は、TlNO3及びK2CrO4を水溶液中
で沈澱反応を行なうことで得たものを用いた。
Tl2Mg（CrO4）3，及びTl2Sr（CrO4）2，Tl2Ba
（CrO4）2は、市販のMgCrO4及びSrCrO4BaCrO4
を先に合成したTl2CrO4と焼成することで得た。
合成した各クロム酸化合物は、Ｘ線解析により各
化合物であると確認された。
熱変色特性を示すデータを得るために各クロム
酸化合物粉体の、室温，100℃，200℃，300℃に
おける拡散反射スペクトルの測定を行つた。結果
を第１図〜第１０図に示す。また、ここぇ得られ
た各スペクトルから、ハンター色度座標値を求
め、プロツトしたものを第１１図〜第２０図に示
す。この色度座標値から各温度の色を求め表１に
まとめた。
(a) Industrial Application Field The present invention relates to a reversible heating material, which is a type of temperature control material that utilizes the property of a substance that changes color tone depending on temperature. (B) Prior Art Conventionally, reversible temperature indicating materials have been developed with emphasis on temperature indicating ability, such as rapid color change in response to temperature changes. Therefore, materials that have been proposed and commercialized as reversible temperature indicating materials include metal iodides that change color due to phase transition, liquid crystals that change color due to changes in molecular orientation, and organic compounds that change color due to electron transfer. , are materials that exhibit dramatic color changes at certain temperatures. In addition, these reversible temperature-indicating materials have begun to be applied in a wide range of fields, ranging from semi-finished products such as conventional temperature-indicating paints, labels, and crayons to thermometers, toys, and clothing. Active product development is underway, including application to products. (c) Problems to be solved by the invention However, when looking at the usage status of these materials and product groups, it is found that they are mainly used for temporary use, almost disposable, and for relatively mild temperatures up to around 100℃ at most. It is limited to use under certain conditions.
This is because conventional products have a low heat resistance limit and decompose in the temperature range of around 200°C. This low heat resistance limit temperature of conventional materials not only limits the environment in which they can be used, but also imposes restrictions on processing methods and applicable products. As for processing methods, for example, baking coating, which is widely used as a coating method, cannot be used unless the baking temperature is particularly low. Furthermore, it is impossible to vitrify it using glazes used in the ceramic industry. Regarding applicable products, it is of course not applicable to those whose temperature may rise above the heat-resistant limit temperature, but there are other products with extremely long useful life, such as durable consumer goods, that have temperature indicators. heat resistance of the material,
It was difficult to apply because it had low durability and there was a risk that its commercial value would be significantly lowered due to fading. Nevertheless, there are a large number of products for which temperature indicating materials are desired to be applied. However, as mentioned above, in order to break the limits of the usage environment, processing method, and applicable products of conventional materials, it is necessary to increase the heat resistance temperature.
A heat-resistant temperature of However, this has not been possible by simply improving conventional materials. The present invention was made under such circumstances, and enables a wide range of applications.
The object of the present invention is to provide a reversible temperature indicating material having a heat resistance temperature of . (d) Means and action for solving the problems As a result of intensive research in view of the above points, the present inventors have discovered that a certain group of inorganic chromic acid compounds have good heat resistance and a reversible temperature indicator. We have discovered the fact that this characteristic is expressed. Thus, according to the invention, the following formula: MCrO 4 (wherein M is Na 2 , K 2 , Rb 2 , Cs 2 , Sr, Tl 2 ,
1/3 (Tl 2 Mg 2 ), 1/2 (Tl 2 Sr), 1/2
A reversible temperature indicating material made of a chromic acid compound represented by (Tl 2 Ba) or Pb) or a mixture thereof is provided. The chromic acid compound in this invention is
Na 2 CrO 4 , K 2 CrO 4 , Rb 2 CrO 4 , Cs 2 CrO 4 ,
SrCrO 4 , Tl 2 CrO 4 , Tl 2 Mg 2 (CrO 4 ) 3 , Tl 2 Sr
(CrO 4 ) 2 , Tl 2 Ba(CrO 4 ) 2 and PbCrO 4 . Among these, commercially available ones can be used as they are, and Tl 2 CrO 4 can be easily obtained, for example, from TlNO 3 and K 2 CrO 4 by a precipitation reaction, and Tl 2 Mg 2 (CrO 4 ) 3 , Tl 2 Sr
(CrO 4 ) 2 , Tl 2 Br (CrO 4 ) 2 , etc. are commercially available products.
It can be easily obtained by sintering MgCrO 4 , SrCrO 4 or BaCrO 4 and the above-mentioned Tl 2 CrO 4 at a predetermined ratio. The above-mentioned chromic acid compounds function as a reversible temperature indicating material either alone or in the form of a mixture of two or more.
When used as a mixture, each ratio can be arbitrarily determined. These reversible temperature indicating materials made of chromic acid compounds are usually applied in powder form or mixed with a suitable inorganic or organic binder, or in some cases, they are sandwiched between transparent substrates or shaped into a desired shape. It can be molded into a shape and used for various purposes such as temperature control and display. Note that it is also possible to mix other heat-resistant pigments into the reversible temperature indicating material of the present invention in order to adjust the color tone. For example, by mixing a small amount of cobalt green pigment into Tl 2 CrO 4 , which changes color to bright yellow at room temperature and bright yellow-red at 150°C, the color changes to yellow-green at room temperature and brown at 150°C. be able to. (E) Examples Hereinafter, the reversible temperature indicating material according to the present invention will be explained in detail with reference to Examples. Na 2 CrO 4 , K 2 CrO 4 , Rb 2 CrO 4 , Cs 2 CrO 4 ,
SrCrO 4 , Tl 2 rO 4 , Tl 2 Mg(CrO 4 ) 3 , Tl 2 Sr
The thermochromic properties and heat resistance properties of each chromic acid compound (CrO 4 ) 2 , Tl 2 Ba(CrO 4 ) 2 and PbCrO 4 were investigated. Here, Na 2 CrO 4 , K 2 CrO 4 , Rb 2 CrO 4 ,
Commercially available reagents were used for Cs 2 CrO 4 , SrCrO 4 , and PbCrO 4 . Tl 2 CrO 4 was obtained by performing a precipitation reaction of TlNO 3 and K 2 CrO 4 in an aqueous solution.
Tl 2 Mg(CrO 4 ) 3 , and Tl 2 Sr(CrO 4 ) 2 , Tl 2 Ba
(CrO 4 ) 2 is commercially available MgCrO 4 and SrCrO 4 BaCrO 4
was obtained by calcination with previously synthesized Tl 2 CrO 4 .
Each synthesized chromic acid compound was confirmed to be each compound by X-ray analysis. In order to obtain data showing thermochromic properties, the diffuse reflection spectra of each chromic acid compound powder were measured at room temperature, 100°C, 200°C, and 300°C. The results are shown in FIGS. 1 to 10. Furthermore, Hunter chromaticity coordinate values were obtained from each of the obtained spectra and plotted as shown in FIGS. 11 to 20. The color at each temperature was determined from these chromaticity coordinate values and summarized in Table 1.
【表】
拡散反射スペクトル図（第１図〜第１０図）か
ら、温度上昇にしたがい、上記した全てのクロム
酸化合物の反射スペクトル端が長波長側へシフト
していることが分かる。この温度により可逆的に
反射スペクトル端がシフトするという特性から、
これらの化合物を可逆性示温材として用いること
ができることが分かる。そして表示色調は、ハン
ター色度座標値をプロツトした図（第１１図〜第
２０図）や表１からも分かるように、温度により
概ね黄色系の色（低温域）から赤色系の色（高温
域）けと変色する。また、これらの化合物を混合
して用いた場合には、各温度において、それぞれ
の化合物の示す色の中間色を呈する。また、温度
により色を変えない耐熱性顔料を混合することに
より、各クロム酸化合物の各温度における色と、
該耐熱性顔料の色の中間色を呈するようにもでき
る。
次に、クロム酸化合物の耐熱試験として、釉薬
による塗布試験を行なつた。これは、従来の技術
の項で述べたように、可逆性示温材を広範な用途
に供するため、特にその加工法の面での適合性を
示すためのものである。使用した釉薬は、酸化
鉛、酸化ホウ素を含有した比較的低融点のもの
で、内融点は580℃である。各クロム酸化合物１
部に対して、釉薬１部を乳鉢にとり、良く混合し
てインク化した後、結晶化ガラスの上にスクリー
ン印刷を行つた。塗布面を乾燥した後、580℃10
分間の条件で、焼付けを行つた。また従来品との
比較のため、金属ヨウ化物についても同様の加工
を試みた。使用したヨウ化物は、示温特性を有す
ることが良く知られている、ヨウ化鉛、ヨウ化銀
及びHgAgxCu(2-x)I4である。
その結果、各クロム酸化合物を塗布した試料は
ほぼ粉体のときと同様な色調を呈し、熱変色性も
良好であつた。一方ヨウ化物を塗布した試料は、
熱分解し、すべて灰褐色あるいは黒色へ褪色して
しまい、熱変色特性は失われていた。このことか
ら、本発明で示したクロム酸化合物からなる示温
材は、従来材料では不可能であつた580℃の焼付
けに対して充分な耐性を持つたものであると言え
る。また、先ず挙げた釉薬以外にも比較的低融点
の釉薬や熱硬化性樹脂などを用いた塗布法に対し
て充分な耐久性を示すことが期待できる。
さらに、Tl2CrO4に関しては、耐久性の確認の
意味で、紫外線照射と、加熱エージングによる褪
色の有無を確認する試験も行つた。
紫外線照射試験は、太陽光や蛍光燈の光による
顔料の褪色（日焼け）が生じないことを確認する
ための試験である。試験は、以下の方法で行つ
た。粉体のTl2CrO4及び釉薬で結晶化ガラス上に
塗布した顔料に対して、波長365nm強度7mWの
紫外光を連続240時間照射した。紫外線照射試料
に対して、拡散反射光スペクトルを測定し、照射
前の状態と比較した。
測定した結果、紫外線照射前とほとんど変わら
ないスペクトルが得られた。強力な紫外線照射に
よつてもほとんど褪色を示さなかつたことから、
実際に使用する際には、日焼けによる褪色は、問
題にならないほど小さいものと考えられる。
また、加熱エージングによる試験を行つた。こ
の試験は比較的高温の状態が続いた場合に、熱分
会や酸化によつて褪色が生じないことを確認する
ための試験である。試験は、結晶化化ガラス上に
前述の方法でスクリーン印刷した試料を240時間、
400℃に保持し、その前後での色の変化を調べた。
結果として、加熱エージングの前後では、ほと
んど変化がなく、示温特性も変わらなかつた。し
たがつて、比較的高温の状態が長く続くような用
途にあつてもこの可逆性示温材は、その示温特性
を保持し続けることが期待できる。
(ヘ) 発明の効果
本発明の可逆性示温材により得られる効果を以
下に示す。
(1) 従来提案されていた可逆性示温材に比べ、は
るかに高い耐熱性を有する。これにより、
●高温に達するため適用が困難であつた箇所へ
可逆性示温材を附加、使用することが可能と
なる。
●釉薬や熱硬化性樹脂などによる塗布法が利用
できるため、加工法の面で制約が少ない。
●熱による褪色を起こしにくく、長期にわたる
安定した特性を有するため、耐久性消費財な
どへの適用も可能である。
等の効果が得られる。
(2) 光や、空気中の酸素による酸化等の影響を受
けにくく、褪色が起こりにくい。
従つて炎天下に曝される箇所に附加、使用す
ることが可能である。
(3) 優れた熱変色性をもつて、従つて
●昇温時と、降温時における変色にヒステリシ
スがなく、温度表示の再現性が良い。
●これらを混混合したり、他の耐熱顔料と混合
することで、色調調製ができる。
等の効果が得られる。[Table] From the diffuse reflection spectra (Figures 1 to 10), it can be seen that the reflection spectrum edges of all the above-mentioned chromic acid compounds shift toward longer wavelengths as the temperature increases. Due to the characteristic that the reflection spectrum edge shifts reversibly with this temperature,
It can be seen that these compounds can be used as reversible temperature indicating materials. As can be seen from the diagrams plotting the Hunter chromaticity coordinate values (Figures 11 to 20) and Table 1, the displayed color tone varies depending on the temperature, from a yellowish color (low temperature range) to a reddish color (high temperature range). area) and discoloration. Furthermore, when these compounds are used as a mixture, they exhibit a color intermediate between the colors of the respective compounds at each temperature. In addition, by mixing heat-resistant pigments that do not change color depending on temperature, the color of each chromic acid compound at each temperature,
It can also be made to exhibit a color intermediate to that of the heat-resistant pigment. Next, as a heat resistance test of the chromic acid compound, a coating test using a glaze was conducted. As mentioned in the section on the prior art, this is to demonstrate the suitability of the reversible temperature indicating material in terms of its processing method, in order to provide it with a wide range of uses. The glaze used contains lead oxide and boron oxide and has a relatively low melting point, with an internal melting point of 580°C. Each chromic acid compound 1
1 part of glaze was placed in a mortar and mixed well to form ink, which was then screen printed on crystallized glass. After drying the coated surface, heat at 580℃10
Baking was carried out under conditions of 1 minute. In addition, for comparison with conventional products, we also attempted to process metal iodides in the same way. The iodides used were lead iodide, silver iodide, and HgAg x Cu (2-x) I 4 , which are well known to have thermostatic properties. As a result, the samples coated with each chromic acid compound had almost the same color tone as the powder, and had good thermochromic properties. On the other hand, the sample coated with iodide
It decomposed thermally and all of it faded to grayish brown or black, and its thermochromic properties were lost. From this, it can be said that the temperature indicating material made of the chromic acid compound shown in the present invention has sufficient resistance to baking at 580°C, which was impossible with conventional materials. In addition to the glazes mentioned above, it can be expected to exhibit sufficient durability against coating methods using glazes with relatively low melting points, thermosetting resins, and the like. Furthermore, regarding Tl 2 CrO 4 , in order to confirm its durability, tests were also conducted to confirm the presence or absence of fading due to ultraviolet irradiation and heat aging. The ultraviolet irradiation test is a test to confirm that pigments do not fade (sunburn) due to sunlight or fluorescent light. The test was conducted in the following manner. Pigment coated on crystallized glass using powdered Tl 2 CrO 4 and glaze was continuously irradiated with ultraviolet light with a wavelength of 365 nm and an intensity of 7 mW for 240 hours. The diffuse reflection spectrum of the ultraviolet irradiated sample was measured and compared with the state before irradiation. As a result of the measurement, a spectrum that was almost the same as before UV irradiation was obtained. Because it showed almost no fading even when exposed to strong ultraviolet irradiation,
In actual use, fading due to sun exposure is considered to be so small as not to be a problem. In addition, a heat aging test was conducted. This test is a test to confirm that discoloration does not occur due to thermal separation or oxidation when relatively high temperature conditions continue. In the test, samples screen-printed on crystallized glass using the method described above were screen-printed for 240 hours.
The temperature was maintained at 400°C, and the color change was examined before and after that temperature. As a result, there was almost no change before and after heat aging, and the temperature characteristics also remained unchanged. Therefore, this reversible temperature-indicating material can be expected to maintain its temperature-indicating properties even in applications where relatively high temperature conditions continue for a long time. (f) Effects of the invention The effects obtained by the reversible temperature indicating material of the invention are shown below. (1) It has much higher heat resistance than previously proposed reversible temperature indicating materials. This makes it possible to add and use reversible temperature-indicating materials in places where it would have been difficult to apply them due to their high temperatures. ●Since coating methods such as glaze and thermosetting resin can be used, there are fewer restrictions in terms of processing methods. ●Because it is resistant to fading due to heat and has stable properties over a long period of time, it can also be applied to durable consumer goods. Effects such as this can be obtained. (2) It is less affected by light and oxidation due to oxygen in the air, and is less prone to fading. Therefore, it can be added and used in areas exposed to the scorching sun. (3) It has excellent thermochromic properties, so there is no hysteresis in discoloration when the temperature rises or falls, and the reproducibility of temperature display is good. ●Color tones can be adjusted by mixing these or mixing with other heat-resistant pigments. Effects such as this can be obtained.
第１図から第１０図は、本発明に係る可逆性示
温材の反射スペクトルを各々示すグラフ図、第１
１図から第２０図は、同じく色状態を各々示すグ
ラフである。
1 to 10 are graphs showing the reflection spectra of the reversible temperature indicating material according to the present invention, and FIG.
1 to 20 are graphs similarly showing color states.
Claims (1)
１／３（Tl2Mg2），１／２（Tl2Sr），１／２
（Tl2Ba）又はPbを示す） で表わされるクロム酸化合物又はこれらの混合物
からなる可逆性示温材。[Claims] 1. The following formula: MCrO 4 (wherein, M is Na 2 , K 2 , Rb 2 , Cs 2 , Sr, Tl 2 ,
1/3 (Tl 2 Mg 2 ), 1/2 (Tl 2 Sr), 1/2
A reversible temperature indicating material made of a chromic acid compound represented by (Tl 2 Ba) or Pb) or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11959987A JPS63284283A (en) | 1987-05-15 | 1987-05-15 | Reversible thermocolor material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11959987A JPS63284283A (en) | 1987-05-15 | 1987-05-15 | Reversible thermocolor material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63284283A JPS63284283A (en) | 1988-11-21 |
| JPH0435514B2 true JPH0435514B2 (en) | 1992-06-11 |
Family
ID=14765377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11959987A Granted JPS63284283A (en) | 1987-05-15 | 1987-05-15 | Reversible thermocolor material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63284283A (en) |
-
1987
- 1987-05-15 JP JP11959987A patent/JPS63284283A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63284283A (en) | 1988-11-21 |
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