201243323 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種可藉由顯色而容易地目測濕度之上升 之濕度指示劑、及用於製造該濕度指示劑之濕度指示劑用塗 料。 【先前技術】 先前，作為密封於商品包裝中之乾燥劑，使用有裝有矽膠 之小袋於該小袋内混入有稱為藍色凝膠的含浸氯化鈷之矽 膠作為用以維持乾燥狀態之指示劑。然而，由於銘為重金 屬，故而就環境方面而言期待不含有鈷之濕度指示劑。 專利文獻1中揭示有一種濕度指示劑，該濕度指示劑係使 包含電子供應性顯色化合物、於常溫下為固體之酸性化合 物、潮解物質、及水系樹脂乳液或水溶性高分子化合物之濕 度指示劑用塗料，附著於不織布等載體並進行加熱乾燥而 成。該濕度指示劑不含作為重金屬之钻且對微量之濕度亦敏 銳地產生反應並變色，故而可較佳地用於對濕度要求有嚴格 管理之電子零件之包裝體。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2007-316058號公報 【發明内容】 (發明所欲解決之問題） 100134955 4 201243323 專利文獻1中所揭示之濕度指示劑鄉乾 等顏色，於高濕度下變為無色。相對於& “、顯不藍色 〇俏蚵孓此，亦存在 化的濕 要求 燥時為無色、而於咼濕度下顯色之顯示相反之顏色辨、；〇 度指示劑之意見。又，亦有進一步降低成本之 ， 本發明之課題係鑒於上述要求而更加廉價地提 濕度指示劑 先前同樣地對濕度上升敏銳地產生反應麵供—種與 _ 支化相反之 (解決問題之手段） 本發明之第1發明係-種濕度指示劑，其特徵在於：將濕' 度指示劑用塗料，塗佈於載體並使其乾燥、 一 q考而成，該濕 度指示_塗料至> 具有電子供應⑽色彳lt合物、於常溫下 為固體之酸性化合物、聚乙烯吡咯烷酮及水分，且聚乙烯吡 咯烷酮相對於水分之重量比為0.45〜186。 本發明之第2發明係一種濕度指示劑用塗料，其特徵在 於：至少具有電子供應性顯色化合物、於常，溫下為固體之酸 性化合物、聚乙烯吡咯烷酮及水分，且聚乙烯吡咯烷酮相對 於水分之重量比為0.45〜1.86。 (發明效果） 於本發明中，提供一種與先前同樣地對濕度上升敏銳地產 生反應且藉由顯色來表示濕度上升之濕度指示劑。進而，可 削減作為先前之濕度指示劑用塗料之1成分之潮解物質，因 此可提供製造控制亦變得容易且廉價之濕度指示劑。 100134955 5 201243323 【實施方式】 本發明提供一種濕度指示劑用塗料、及於載體塗佈該塗料 而成之濕度指示劑。並且，於本發明中，濕度指示劑用塗料 之特徵在於：至少具有電子供應性顯色化合物、於常溫下為 固體之酸性化合物、聚乙烯D比洛烧嗣及水分，且聚乙烯吼〇各 烧酮相對於水分之重量比為0.45〜1.86。又，將本發明之濕 度指示劑用塗料塗佈於載體上並進行乾燥而成之塗膜為無 色’藉由在高濕度下吸收濕氣而顯示特定之顏色。 作為本發明所使用之載體，只要為紙或樹脂膜、布、不織 布等可藉由附著水性塗料並進行加熱乾燥而於該載體之表 面或内部承載含有該塗料之成分之塗膜者，則可使用任何素 材。作為樹脂膜，可較佳地使用聚對苯二甲酸乙二酯（PET， Polyethylene terephthalate)或聚丙烯(PP，P〇lypr〇pylene)、聚 乙烯(PE ’ Polyethylene)等之膜或片材。 電子供應性顯色化合物係藉由釋出電子而變色之物質，只 要為藉由與酸性化合物接觸而釋出電子並變色之化合物，則 無特別限定’具體而言可較佳地使用無色染料，例如可使用 由酸性而引起顯色或顏色變化之pH值指示劑、三芳基甲烧 衍生物、熒烷衍生物等。具體而言，例如可列舉：結晶紫内 酯、3-吲哚啉-3-對二甲基胺基苯基_6_二曱基胺基酞内酯、 3-二乙基胺基-7-氣熒烷、2-(2-氟苯基胺基)_6_二乙基胺基熒 烷、2-(2-氟苯基胺基)-6-二正丁基胺基熒烷、3_二乙基胺基 100134955 6 201243323 -7-環己基胺基癸烧、3-二乙基胺基_5_甲基-7-第= 〜丁基榮 烷、3-二乙基胺基-6-曱基-7-苯胺基熒烷、3-二乙基胺芙6 曱基-7-對丁基笨胺基熒烷、3-環己基胺棊_6_氣癸燒、2笨 胺基-3-甲基-6-(N-乙基-對曱苯胺基)_熒螝、3_%d各燒義·6 . 曱基-7-苯胺基熒烷、3-吡咯烷基-7-環己棊胺基熒烷、3 Ν L 曱基環己基胺基甲基-7-苯胺基螢烧、3-N-乙基戍其p其 -6-曱基-7-苯胺基熒烷等。 作為酸性化合物，只要於常溫下為固體則無特別限定，例 如可舉出：乙二酸、丙二酸、檸檬酸、水穑酸、贫m T 酸、 酸'對曱苯磺酸及該等之水合物等。於該等之中， ν 就對水之 溶解度較高之方面而言較佳為乙二酸、丙二酸、對 — 本發明所使用之聚乙烯吡咯烷綱（^^1201243323 SUMMARY OF THE INVENTION Technical Field The present invention relates to a humidity indicator which can easily visually detect an increase in humidity by color development, and a coating material for a humidity indicator for producing the humidity indicator. [Prior Art] Previously, as a desiccant sealed in a commercial package, a sachet containing a silicone was mixed in the pouch with a gelatin containing cobalt chloride called blue gel as an indicator for maintaining a dry state. Agent. However, since it is a heavy metal, it is expected that it does not contain a humidity indicator of cobalt in terms of the environment. Patent Document 1 discloses a humidity indicator which is an indicator of humidity including an electron-donating color-developing compound, an acidic compound which is solid at normal temperature, a deliquescent substance, and an aqueous resin emulsion or a water-soluble polymer compound. The coating material for the agent is attached to a carrier such as a non-woven fabric and dried by heating. The humidity indicator does not contain a drill as a heavy metal and is sensitive to a slight amount of humidity and discolors, so that it can be preferably used for a package of electronic parts having strict management of humidity. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-316058 (Draft of the Invention) (Problem to be Solved by the Invention) 100134955 4 201243323 The humidity indicator agent disclosed in Patent Document 1 The color is equal to color and becomes colorless under high humidity. Relative to & ", not blue, this is also the case, there is also the color of the wet when the dry is required to be colorless, and the color of the display under the humidity of the opposite is the opposite color; the opinion of the indicator. Further, the problem of the present invention is that the humidity indicator is more inexpensively raised in view of the above-mentioned requirements, and the reaction surface is sharply generated in the same manner as the humidity rise in the same manner as the _ branching (the means for solving the problem). According to a first aspect of the present invention, a humidity indicator agent is characterized in that a coating material for a wetness indicator is applied to a carrier and dried, and the humidity indicator _coating to has The electron supply (10) color 彳 合物, an acidic compound which is solid at normal temperature, polyvinylpyrrolidone and water, and the weight ratio of polyvinylpyrrolidone to water is 0.45 to 186. The second invention of the present invention is a humidity indicator A coating material characterized by having at least an electron-donating color-developing compound, an acidic compound which is solid at a constant temperature, polyvinylpyrrolidone and water, and polyvinylpyrrolidone The weight ratio of the water is 0.45 to 1.86. (Effect of the Invention) In the present invention, a humidity indicator which is sensitive to the increase in humidity and which exhibits an increase in humidity by color development is provided in the same manner as before. Further, the humidity indicator can be reduced. As a deliquescent substance of the first component of the coating material for a humidity indicator, it is possible to provide a humidity indicator which is easy and inexpensive to manufacture. 100134955 5 201243323 [Embodiment] The present invention provides a coating material for a humidity indicator, and A moisture indicating agent obtained by coating the coating with a carrier. Further, in the present invention, the coating material for a humidity indicator is characterized in that it has at least an electron-donating coloring compound, an acidic compound which is solid at normal temperature, and a polyethylene D ratio. The ratio of the weight ratio of each of the ketones to the water is 0.45 to 1.86. Further, the coating film for the humidity indicator of the present invention is applied onto a carrier and dried to form a coating film. Colorless 'displays a specific color by absorbing moisture under high humidity. As a carrier used in the present invention, it is only a paper or a resin film A cloth, a non-woven fabric, or the like which can carry a coating film containing a component of the coating on the surface or inside of the carrier by attaching a water-based paint and heating and drying, any material can be used. As the resin film, a poly-pair can be preferably used. Film or sheet of polyethylene terephthalate (PET, Polyethylene terephthalate) or polypropylene (PP, P〇lypr〇pylene), polyethylene (PE 'Polyethylene), etc. Electron supply coloring compounds are released by The substance which is discolored by electrons is not particularly limited as long as it is a compound which releases electrons by discoloration by contact with an acidic compound. Specifically, a leuco dye can be preferably used, for example, coloration or color caused by acidity can be used. Varying pH indicator, triarylmethylate derivative, fluoran derivative, and the like. Specific examples thereof include crystal violet lactone, 3-porphyrin-3-p-dimethylaminophenyl-6-didecylaminolactone, and 3-diethylamino-7. - fluorofluoran, 2-(2-fluorophenylamino)-6-diethylaminofluoran, 2-(2-fluorophenylamino)-6-di-n-butylaminofluoran, 3 _Diethylamino group 100134955 6 201243323 -7-Cyclohexylamine oxime, 3-diethylamino _5-methyl-7- =1 butyl aryl, 3-diethylamino-6- Mercapto-7-anilinofluoran, 3-diethylamine 6-mercapto-7-p-butylaminoamino fluoran, 3-cyclohexylamine 棊6-gas oxime, 2 phenylamino- 3-methyl-6-(N-ethyl-p-anilinoyl)-fluoranthene, 3_%d each, ·6. Indolyl-7-anilinofluoran, 3-pyrrolidin-7-ring Hexylaminofluoran, 3 Ν L-decylcyclohexylaminomethyl-7-anilinofluorene, 3-N-ethylhydrazine, p--6-mercapto-7-anilinofluoran, and the like. The acidic compound is not particularly limited as long as it is a solid at normal temperature, and examples thereof include oxalic acid, malonic acid, citric acid, hydroxamic acid, lean m T acid, acid 'p-toluenesulfonic acid, and the like. Hydrate, etc. Among these, ν is preferably oxalic acid, malonic acid, or the polyvinylpyrrolidine (^^1) used in the present invention in terms of high solubility in water.
Polyvinylpyrrolidone)係水溶性高分子之一種，但— > —右為聚乙烯 醇(PVA ’ Polyvinyl Alcohol)或澱粉等其他水溶性高八 無法獲得與本發明相同之作用效果。於本發明之子，則 用塗料中，PW相對於水分之重量比（卿水^"指示^ 1.86 ’於PVP之重量比未滿Q 45之情， 0·45 、明之效果，若超過則塗料之黏度變得過高2 =發 . 塗佈變得困難。. 士栽體之 可認為本發明中之pvp之作用如下所述。 於濕度指时射，若PVP㈣於 0.45以上，則電子供應性顯色 VJ:之親和性超過 J00134955 201243323 電子供應性顯色化合物與酸性化合物之親和性，於PVP阻 礙電子供應性顯色化合物與酸性化合物接觸之狀態下藉由 乾燥而固化。因此，於乾燥時或於低濕度環境下，電子供應 性顯色化合物與於常溫下為固體之酸性化合物不接觸而顯 示無色。於在該狀態下周圍之濕度上升之情形時，富於保濕 性之PVP係吸收濕氣，其結果使酸性化合物可於pvp内自 由移動並與電子供應性顯色化合物接觸而顯色。然而，於濕 度指示劑用塗料中，於pvp相對於水分之重量比未滿〇 45 之情形時’於電子供應性顯色化合物與酸性化合物在塗料中 接觸而顯色之狀4下乾燥、固化，故而於乾燥時或於低濕度 環境下直接齡’PVP於高濕度環境下吸收濕氣，其結果酸 性化合物於PVP所㈣之水分+糾，與好供應性顯色 化合物之接觸變弱，從而成為無色。 又，可認為，於使用除Pvp以外之水溶性高分子之情形 時，由於與電子供應性顯色化合物之親和性較pvp差，故 而電子供應性顯色化合物與酸性化合物於塗料中接觸而顯 色，並於該狀態下乾燥、固化。又，不使用潮解物質而使用 PVP以外之水溶性高分子軸濕度指示#1，即便置於高濕度 下’亦無pvp之保濕性，故而無法吸收周圍之濕氣，無法 表現出濕度檢測功能。 再者，於本發明之濕度指示劑用塗料中，為了提高與載體 之接著力’亦可添加水系樹脂乳液，可較佳地使用丙烯酸醋 100134955 8 201243323 乳液。 又，為了提高印刷適應性(黏度調整、葷料之裂縫防止、 塗料之分散性提高等），亦可適當添加有機溶劑或消泡劑、 防腐劑等。作為該有機溶劑，較佳可使用對水之溶解度為5 ml/100 ml以上且藉由加熱而揮發之極性寧劑。具體而古， 可較佳地使用曱醇、乙醇、1_丙醇、2-丙醇（異丙醇， IPA(IsopropylAlcohol))、1-丁醇、2-丁醇、2-甲基小丙醇、 第二丁醇、甲基乙基酮、乙酸乙酯、四氫呋喃、環己酮、丙 酮、乙腈中之一種，或包含至少一種之混合溶劑。若考慮較 短之乾燥時間、塗料之相溶性、廉價，則較佳為lpA、曱醇、 乙醇，尤佳為IPA。 作為IPA之添加量，考慮電子供應性顯色化合物之分散 性，較佳為將以重量計電子供應性顯色化命物之5〜丨〇〇倍 添加於塗料中。 於本發明中，藉由使上述濕度指示劑用塗料附著於載體並 進行加熱乾燥，而獲得該塗料中所含之電子供應性顯色化合 物、酸性化合物、pvp承載於該載體之濕度指示劑。作為使 上述塗料附著於載體之方法’只要可使所需要之量之塗料附 著於载體，則無特別限定，可根據載體或塗料之組成而適當 選擇例如將载體浸潰於塗料中之方法、利用線棒或輥式塗佈 機等進行塗佈之方法、利用噴霧等噴附之方法等。 作為加熱方法，可適當使用烘箱等。加熱萆度及加熱時間 100134955 9 201243323 亦由載體之素材或塗料之組成而決定’較佳為於40〜15(rc： 下，更佳為於50〜130°C下，較佳為加熱10〜600秒。又， 亦可反覆進行複數次塗料之附著與加熱乾燥而承載特定量 之塗料。乾燥後之塗膜之量例如對於膜等平板載體較佳為 0.3 〜20 g/m2。 本發明之濕度指示劑係使水性塗料附著於紙或膜等載體 而獲得，故而藉由在大面積之載體塗佈塗料並於乾燥後進行 切割，可容易地批量生產所需之大小之指示劑。再者，若於 載體預先利用印刷、顏料之捏合等方法著色成與塗膜之濕度 檢測後之色調不同之色調’則可容易地識別塗膜之顏色變 化，因此較為便利。 以上述方式獲得之本發明之濕度指示劑即便於檢測出濕 度且塗膜顯色後，亦可藉由利用烘箱等進行加熱而容易地^ 復無色。 本發明之濕度指示劑可直接用於雪i爲疮您Tm t uPolyvinylpyrrolidone) is one type of water-soluble polymer, but -> - right other polyvinyl alcohol (PVA ' Polyvinyl Alcohol) or starch, and other water-soluble high eight can not obtain the same effect as the present invention. In the present invention, the weight ratio of PW to water in the paint is used (Qingshui^"Indication ^ 1.86 'The weight ratio of PVP is less than Q 45, 0.45, the effect of Ming, if it exceeds the coating The viscosity becomes too high 2 = hair. The coating becomes difficult. The effect of the pvp in the present invention is as follows. In the case of humidity, when the PVP (four) is above 0.45, the electron supply property Color development VJ: Affinity exceeds J00134955 201243323 The affinity of an electron-donating chromogenic compound to an acidic compound is cured by drying when PVP hinders contact of an electron-donating chromogenic compound with an acidic compound. Or in a low-humidity environment, the electron-donating color-developing compound exhibits no color when it is not in contact with an acidic compound which is solid at normal temperature. When the humidity around the state rises in this state, the moisture-retaining PVP absorbs the wet. Gas, as a result, the acidic compound can move freely within the pvp and develop color upon contact with the electron-donating chromogenic compound. However, in the coating for the humidity indicator, the weight of pvp relative to the moisture When it is less than 〇45, it is dried and solidified in the case where the electron-donating chromogenic compound and the acidic compound are brought into contact with the paint to develop color. Therefore, the direct age of PVP is high at the time of drying or in a low humidity environment. In the humidity environment, the moisture is absorbed, and as a result, the acidic compound is weakened by the moisture of the PVP (4), and the contact with the good supply coloring compound becomes weak, thereby becoming colorless. Moreover, it is considered that the water solubility other than Pvp is high. In the case of a molecule, since the affinity with the electron-donating chromogenic compound is inferior to that of pvp, the electron-donating chromogenic compound and the acidic compound are brought into contact with the coating to develop color, and are dried and solidified in this state. When the deliquescent substance is used and the water-soluble polymer axis humidity indicator #1 other than PVP is used, even if it is placed under high humidity, there is no moisture retention of pvp, so the surrounding moisture cannot be absorbed, and the humidity detection function cannot be exhibited. In the coating for a humidity indicator of the present invention, in order to increase the adhesion to the carrier, an aqueous resin emulsion may be added, and acrylic vinegar 100134955 8 2 may preferably be used. In order to improve the printing suitability (viscosity adjustment, crack prevention of the coating, improvement of dispersibility of the coating material, etc.), an organic solvent, an antifoaming agent, a preservative, etc. may be added as appropriate. A polar agent which has a solubility in water of 5 ml/100 ml or more and which is volatilized by heating can be used. Specifically, decyl alcohol, ethanol, 1-propanol, 2-propanol (isopropyl) can be preferably used. Alcohol, IPA (Isopropyl Alcohol), 1-butanol, 2-butanol, 2-methylpropanol, second butanol, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, cyclohexanone, acetone, acetonitrile One of them, or contains at least one mixed solvent. In view of a short drying time, compatibility with a coating material, and low cost, lpA, decyl alcohol, and ethanol are preferred, and IPA is particularly preferred. As the addition amount of the IPA, in consideration of the dispersibility of the electron-donating chromogenic compound, it is preferred to add 5 to 丨〇〇 times the electron-donating color-developing material by weight to the coating material. In the present invention, the coating agent for a humidity indicator is attached to a carrier and dried by heating to obtain an electron-donating color-developing compound, an acidic compound, and a humidity indicator which pvp is supported on the carrier. The method of attaching the above-mentioned coating material to the carrier is not particularly limited as long as the required amount of the coating material can be attached to the carrier, and the method of impregnating the carrier into the coating material can be appropriately selected depending on the composition of the carrier or the coating material. A method of coating by a wire bar or a roll coater, a method of spraying by spraying or the like, or the like. As the heating method, an oven or the like can be suitably used. Heating temperature and heating time 100134955 9 201243323 It is also determined by the material of the carrier or the composition of the coating. Preferably, it is preferably 40 to 15 (rc: more preferably 50 to 130 ° C, preferably 10 °). 600 seconds. Further, a plurality of times of coating adhesion and heat drying may be repeatedly carried to carry a specific amount of the coating material. The amount of the coating film after drying is preferably 0.3 to 20 g/m 2 for a flat plate carrier such as a film. The humidity indicator is obtained by attaching the aqueous coating material to a carrier such as paper or film, so that the coating agent of the desired size can be easily mass-produced by coating the coating on a large-area carrier and cutting it after drying. When the carrier is colored in a color tone different from the color tone after the humidity detection of the coating film by a method such as printing or pigment kneading, the color change of the coating film can be easily recognized, which is convenient. The present invention obtained in the above manner The humidity indicator can be easily and colorlessly heated by using an oven or the like even after the humidity is detected and the color of the coating film is developed. The humidity indicator of the present invention can be directly used for the snow sore. Tm t u
之濕氣而延遲變色速度。 作為此種速度調整樹脂層，只要使用 只要使用具有適宜之透谒柹夕Moisture delays the speed of discoloration. As such a speed adjusting resin layer, as long as it is used as long as it is suitable for use
’藉由將使樹脂細溶解絲散於溶劑中而 進仃盒佈塗料並乾燥之載體，再加熱乾燥、 100134955 10 201243323 或利用層壓等於載體上積層樹脂片材或膜而形成。 作為該樹脂素材，只要為於樹脂層形成後顯示適當之透濕 性與透明性者即可使用。於本發明中，速度調整樹脂層之透 濕性係於厚度12/zm之PET膜上形成測定用樹脂層，並利 用水蒸氣穿透率測定装置（MOCON公司製造之 「PERMATRAN-W 3/33系列」)進行測定，具以透濕度(g/m2 · day)表示。 作為速度調整樹脂層之透濕度，只要可獲得速度調整作 用，則無特別限定，較佳為〇.5〜50 g/m2 · ^ay。若透濕度未 滿〇. 5 g/m2. day，則由於透濕性過低，故而郎使檢測出濕氣， 變色速度亦變得過慢。又，若超過5〇 g/m)?.day，則透濕性 過高而無法獲得變色速度抑制之效果。 具體而言，作為樹脂素材，可使用聚對笨二曱酸乙二醋、 丁越樹脂、聚醋_胺基曱酸_、聚酿胺、聚偏二氣乙稀、笨 ^烯化％氧樹脂、環氧樹脂、笨氧樹脂、聚g旨樹脂、氣化乙 酸乙酯、丙烯酸酯樹脂、硝化纖維素等。 該速度調整樹脂層只要覆蓋塗膜而形成即可，於載體如不 ，布般具有通氣性之情形時，較佳為設置於與塗佈塗料之側 •呈相反側’自該相反側抑制塗獏所吸收之溽氣。 於對本發明之濕度指示劑要求对光性之情形時，亦可 ^速度調整樹脂層中添加紫外線吸收劑_氧化劑。 [貫施例] 100134955 201243323 (實施例1-1) 將PVp(K：e30，和光純藥工業（股）製造）溶解於純水中而 獲得35重量°/。之PVP水溶液。於該PVP水溶液100重量份 中添加電子供應性顯色化合物（「RED-20」’山本化成（股) 製造)4重量份、乙二酸二水合物(和光純藥（股）製造)2重量 份、IPA 20重量份，進行擾拌以使其均勻。使用線棒#4將 該塗料塗敷於作為載體之PET膜（東洋紡績（股）製造，25 之厚度），於80°C下乾燥5分鐘而獲得濕度指示劑。 將所得之濕度指示劑放置於20%RH〜90%RH之各環境 下’24小時後以目測確認顏色之變化，評價濕度檢測功能。 又’將濕度指示劑浸潰於水中，抽出濕度指示劑並於排淨水 之狀態下以目測確認顏色之變化。將結果示於表1中。 (實施例1-2〜1-4) 將PVP水溶液之濃度分別設為40重量％、60重量％、65 重量％，除此以外與實施例Μ同樣地製作濕度指示劑，與 實施例1-1同樣地評價濕度檢測功能。將結果示於表1中。 (比較例Μ) 使用水系丙烯酸酯乳液（「DICNAL E-8203WH」，大日本 油墨(股)製造，固形份：45重量％)代替PVP水溶液，除此 以外與實施例Μ同樣地製作濕度指示劑，與實施例Μ同 樣地評價濕度檢測功能。將結果示於表1中。 (比較例1-2) 100134955 12 201243323 使用以整體計100重量份之IPA代替Pvp水溶液，除此 以外與實施例1-1同樣地製作濕度指示劑，與實施例1-1同 樣地評價濕度檢測功能。將結果示於表1中。 (比較例1-3) 將PVP水溶液之濃度設為30重量％，除此以外與實施例 1-1同樣地製作濕度指示劑，與實施例1-1同樣地評價濕度 檢測功能。將結果示於表1中。 100134955 13 201243323 【1<】 實施例1-4 寸 〇 100 2.99 v〇 1 1.86 1 無色| |無色| |無色1 |無色| |粉紅| |粉紅| 粉紅 濃粉紅 |濃粉紅1 濃粉紅 實施例1-3 寸 CN 〇 〇 I 2.77 I S 1.50 無色| 無色| |無色| |無色| 粉紅 |粉紅j 粉紅 I濃粉紅 |濃粉紅1 濃粉紅 實施例1-2 寸 〇 100 一1」97 I Ο 0.67 無色 無色 I無色 粉紅 粉紅 粉紅1 濃粉紅 濃粉紅 濃粉紅 濃粉紅 實施例1-1 寸 CS 〇 100 1—— 1.76— I m 0.54 無色| 無色| I無色| |粉紅| 粉紅 |濃粉紅| |濃粉紅 |濃粉紅 |濃粉紅| 濃粉紅 比較例1-3 寸 CN 〇 100 [1.55 | ο m 1 0.43 1 粉紅 |粉紅| 粉紅 |粉紅| |粉紅| |粉紅 I粉紅 |粉紅 |淡粉紅 無色 比較例1-2 寸 <N 〇 〇 〇 | 0.32 | 1 1 |淡粉紅| |淡粉紅| |淡粉紅| |淡粉紅| |淡粉紅| 淡粉紅 淡粉紅 淡粉紅 |淡粉紅 1 比較例1-1 CS 〇 〇 1 2.56 | I 1 |濃粉紅 |濃粉紅| |濃粉紅 |濃粉紅 I濃粉紅 濃粉紅 |濃粉紅 |濃粉紅 |濃粉紅| 濃粉紅 RED-20 乙二酸二水合物 DICNALE-8203WH (固形份：45重量％) JIPA PVP水溶液 羞 Μ PVP水溶液濃度(重量％) PVP/水(重量比） 乾燥時 20%RH 30%RH 40%RH 50%RH 60%RH 70%RH 80%RH 90%RH 浸潰於水中時 塗料之組成 濕度指示劑之顏色 寸 I S6S001 201243323 於實施例1-4中，於將濕度指示劑用蜜料塗佈於PET膜 上時，由於塗料之黏度較高，故而若干塗敷不適當。因此判 斷，若PVP之濃度變得更高，則塗敷變得困難。又，於比 較例1-2中，於將濕度指示劑浸潰於水中時，塗料溶出。 (實施例2-1〜2-3) 將IPA之添加量分別設為0重量份、10:0重量份、400重 量份，除此以外與實施例1-1同樣地製作濞度指示劑，與實 施例1-1同樣地評價濕度檢測功能。將結果示於表2中。 如表2所示，濕度檢測功能未根據添加之IPA之量而變 化，可見伴隨於IPA之添加量增加而高濕庋下之顯色程度變 小之傾向。又，由於在實施例2-1中未添加IPA，故而於電 子供應性顯色化合物之塗料中之分散較差，攪拌需耗費時 間。 100134955 15 201243323 [表2] 實施例2-1 實施例2-2 實施例2-3 塗料之組成 RED-20 4 4 4 乙二酸二水合 物 2 2 2 IPA 0 100 400 PVP水溶液 100 100 100 塗膜厚度(g/m2) 2.08 1.07 0.43 PVP水溶液濃度（重量％) 35 35 35 PVP/水（重量比） 0.54 0.54 0.54 濕度指示劑之顏 色 乾燥時 無色 無色 無色 20%RH 無色 無色 無色 30%RH 無色 無色 無色 40%RH 濃粉色 粉色 淡粉色 50%RH 濃粉色 粉色 淡粉色 60%RH 濃粉色 粉色 淡粉色 70%RH 濃粉色 粉色 淡粉色 80%RH 濃粉色 粉色 淡粉色 90%RH 濃粉色 粉色 淡粉色 浸潰於水中時 濃粉色 粉色 淡粉色 (實施例3-1、3-2) 將RED-20之添加量分別增加至5重量份、20重量份，除 此以外與實施例1-1同樣地製作濕度指示劑，與實施例1-1 同樣地評價濕度檢測功能。將結果示於表3中。 (實施例3-3、3-4) 將乙二酸二水合物之添加量分別增加至3重量份、10重 量份，除此以外與實施例1-1同樣地製作濕度指示劑，與實 施例1-1同樣地評價濕度檢測功能。將結果示於表3中。 100134955 16 201243323 [表3] 實施例3-1 實施例3-:2 實施例3-3 實施例3-4 塗料之組成 RED-20 5 20 ' 4 4 乙二酸二水合物 2 2 3 10 ΓΡΑ 20 20 20 20 PVP水溶液 100 100 100 100 塗膜厚度(g/m2) 1.76 2.13 1.76 1.97 PVP水溶液濃度(重量％) 35 35 35 35 PVP/水(重量比） 0.54 0.54 0.54 0.54 塗料中之固形份(重量％) 33 40 33 37 固形份中之PVP比率(重量％) 83 61 83 71 濕度指示劑之顏色 乾燥時 無色 無色 無色 無色 20%RH 無色 無色 無色 無色 30%RH 無色 無色： 無色 無色 40%RH 粉色 濃粉色_ 濃粉色 濃粉色 50%RH 濃粉色 濃粉色： 濃粉色 濃粉色 60%RH 濃粉色 濃粉色' 濃粉色 濃粉色 70%RH 濃粉色 濃粉色： 濃粉色 濃粉色 80%RH 濃粉色 濃粉色 濃粉色 濃粉色 90%RH 濃粉色 濃粉色丨 濃粉色 濃粉色 浸潰於水中時 濃粉色 濃粉色； 濃粉色 濃粉色 如表3所示，即使增加RED-20或乙二酸丨二水合物之添加 量，濕度檢測功能亦無變化。因此，可知塗料之固形份量或 固形份中之PVP之比率對濕度檢測功能無影響。又，於將 RED-20進一步增加至20重量部之情形、或將乙二酸二水合 物進一步增加至10重量份之情形時，塗料中之分散性降低 而產生溶潰。 (實施例4-1〜4-3、比較例4-1、4-2) 於實施例1-1之濕度指示劑用塗料中分別進一步添加比 較例1 -1中所使用之水系丙烯酸S旨乳液5韋量份、10重量 份、20重量份、31.5重量份、50重量份，除此以外與實施 例1-1同樣地製作濕度指示劑，與實施例1-1同樣地評價濕 100134955 17 201243323 度檢測功能。將結果示於表4中。 100134955 18 201243323 【寸<〕 比較例4-2 寸 CS 〇 1—Η 1.92 m 0.38 m ^Γ) 粉色 粉色 粉色 粉色 |粉色| 粉色 1 1^3 |粉色| 粉色 無色 |比較例4-1 寸 CN 1 31.5 100 1.86 cn 0.43 m ΓΛ ν〇 |粉色_I 粉色 [粉色| 粉色 粉色 |粉色| 粉色 !粉色 粉色 無色 實施例4-3 寸 (N 100 1.81 m 0.46 芝 ο 無色 無色 粉色 粉色 粉色 粉色 翁色— 粉色 粉色 粉色 實施例4-2 寸 <N 〇 100 1.76 cn 0.50 m m c^- 無色 無色 無色 粉色 粉色 1粉色1 粉-色 粉色 濃粉色 濃粉色 實施例4-1 寸 CN 100 1.76 iT) m 1 0.52 1 m ro 無色 無色 無色 粉色 粉色 粉色 —粉色 濃粉色 濃粉色 濃粉色 RED-20 乙二酸二水合物 ttW § 'W g'备 Q® IPA PVP水溶液 PVP水溶液濃度(重量％) PVP/水(重量比） 塗料中之固形份(重量％) 固形份中之PVP比率(重量％) 乾燥時 20%RH 30%RH 40%RH 50%RH 60%RH 70%RH 80%RH 90%RH 浸潰於水中時 塗料之組成 濕度指示劑之顏色The carrier is formed by dispersing the resin finely dispersed in a solvent into a solvent and drying the carrier, and then heating and drying, 100134955 10 201243323 or by laminating to form a laminated resin sheet or film on the carrier. The resin material can be used as long as it exhibits appropriate moisture permeability and transparency after the resin layer is formed. In the present invention, the moisture permeability of the speed-adjusting resin layer is formed on a PET film having a thickness of 12/zm to form a resin layer for measurement, and a water vapor permeability measuring device ("PERMATRAN-W 3/33" manufactured by MOCON Corporation is used. The series") was measured and expressed in terms of moisture permeability (g/m2 · day). The moisture permeability of the speed-adjusting resin layer is not particularly limited as long as the speed adjustment effect can be obtained, and is preferably 〇5 to 50 g/m2 · ^ay. If the moisture permeability is less than 5 g/m2.day, the moisture permeability is too low, so that the moisture is detected and the discoloration speed is too slow. On the other hand, if it exceeds 5 〇 g/m)?.day, the moisture permeability is too high, and the effect of suppressing the discoloration speed cannot be obtained. Specifically, as the resin material, poly-p-butyl phthalate, butyl rubber, polyacetic acid amide, polystyrene, polyvinylidene chloride, polyethylene oxide, and oxygen can be used. Resin, epoxy resin, oxo resin, polyg resin, vaporized ethyl acetate, acrylate resin, nitrocellulose, and the like. The speed adjusting resin layer may be formed by coating the coating film. When the carrier is air-permeable like a cloth, it is preferably provided on the side opposite to the side of the coating material. The suffocating sputum. When the humidity indicator of the present invention is required to be optical, the ultraviolet absorbing agent_oxidizing agent may be added to the speed adjusting resin layer. [Examples] 100134955 201243323 (Example 1-1) PVp (K: e30, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to obtain 35 weight%. A PVP aqueous solution. 4 parts by weight of an electron-donating coloring compound ("RED-20", manufactured by Yamamoto Kasei Co., Ltd.), and oxalic acid dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 2 parts by weight, in an amount of 100 parts by weight of the PVP aqueous solution. Part by weight, IPA 20 parts by weight, and spoiled to make it uniform. This paint was applied to a PET film (manufactured by Toyobo Co., Ltd., thickness 25) as a carrier using a wire bar #4, and dried at 80 ° C for 5 minutes to obtain a humidity indicator. The obtained humidity indicator was placed in an environment of 20% RH to 90% RH. After 24 hours, the change in color was visually confirmed to evaluate the humidity detecting function. Further, the humidity indicator was immersed in water, the humidity indicator was taken out, and the change in color was visually confirmed in the state of draining water. The results are shown in Table 1. (Examples 1-2 to 1-4) A humidity indicator was prepared in the same manner as in Example 将 except that the concentration of the PVP aqueous solution was 40% by weight, 60% by weight, and 65% by weight, respectively. 1 The humidity detection function was evaluated in the same manner. The results are shown in Table 1. (Comparative Example) A humidity indicator was prepared in the same manner as in Example 使用 except that a water-based acrylate emulsion ("DICNAL E-8203WH", manufactured by Dainippon Ink Co., Ltd., solid content: 45% by weight) was used instead of the PVP aqueous solution. The humidity detecting function was evaluated in the same manner as in Example 。. The results are shown in Table 1. (Comparative Example 1-2) 100134955 12 201243323 A humidity indicator was prepared in the same manner as in Example 1-1 except that 100 parts by weight of IPA was used instead of the Pvp aqueous solution, and humidity measurement was evaluated in the same manner as in Example 1-1. Features. The results are shown in Table 1. (Comparative Example 1-3) A humidity indicator was prepared in the same manner as in Example 1-1 except that the concentration of the PVP aqueous solution was changed to 30% by weight, and the humidity detecting function was evaluated in the same manner as in Example 1-1. The results are shown in Table 1. 100134955 13 201243323 [1<] Example 1-4 inch 〇100 2.99 v〇1 1.86 1 colorless | | colorless | | colorless 1 | colorless | | pink | | pink | pink thick pink | thick pink 1 thick pink example 1 -3 inch CN 〇〇I 2.77 IS 1.50 colorless | colorless | | colorless | | colorless | pink | pink j pink I thick pink | thick pink 1 thick pink example 1-2 inch 〇 100 a 1" 97 I Ο 0.67 colorless Colorless I colorless pink pink pink 1 thick pink thick pink thick pink thick example 1-1 inch CS 〇100 1 - 1.76 — I m 0.54 colorless | colorless | I colorless | | pink | pink | thick pink | | thick pink | Thick Pink | Thick Pink | Thick Pink Comparative Example 1-3 Inch CN 〇100 [1.55 | ο m 1 0.43 1 Pink | Pink | Pink | Pink | | Pink | | Pink I Pink | Pink | Light Pink Colorless Comparative Example 1 -2 inch<N 〇〇〇| 0.32 | 1 1 |Pale Pink| |Pale Pink| |Pale Pink| |Pale Pink| |Pale Pink | Pale Pink Pale Pink Pale Pink|Pale Pink 1 Comparative Example 1-1 CS 〇〇1 2.56 | I 1 | thick pink | thick pink | | thick pink | thick pink I thick pink thick pink | thick pink | Pink|Thick Pink|Thick Pink RED-20 Oxalic Acid Dihydrate DICNALE-8203WH (Solid Form: 45% by Weight) JIPA PVP Aqueous Solution PVP Aqueous Solution Concentration (% by Weight) PVP/Water (Weight Ratio) 20% when dry RH 30%RH 40%RH 50%RH 60%RH 70%RH 80%RH 90%RH Composition of the coating when immersed in water Humidity indicator color I S6S001 201243323 In Example 1-4, the humidity is When the indicator is applied to the PET film with a honey material, since the viscosity of the coating material is high, some coatings are not appropriate. Therefore, it is judged that if the concentration of PVP becomes higher, coating becomes difficult. Further, in Comparative Example 1-2, when the humidity indicator was immersed in water, the coating was eluted. (Examples 2-1 to 2-3) A twist indicator was produced in the same manner as in Example 1-1, except that the amount of IPA added was changed to 0 parts by weight, 10:0 parts by weight, and 400 parts by weight, respectively. The humidity detecting function was evaluated in the same manner as in Example 1-1. The results are shown in Table 2. As shown in Table 2, the humidity detecting function was not changed depending on the amount of IPA added, and it was seen that the degree of coloration under high wetness tends to decrease as the amount of addition of IPA increases. Further, since IPA was not added in Example 2-1, the dispersion in the coating of the electron-donating chromogenic compound was poor, and stirring took time. 100134955 15 201243323 [Table 2] Example 2-1 Example 2-2 Example 2-3 Composition of coating RED-20 4 4 4 oxalic acid dihydrate 2 2 2 IPA 0 100 400 PVP aqueous solution 100 100 100 Coating Film thickness (g/m2) 2.08 1.07 0.43 PVP aqueous solution concentration (% by weight) 35 35 35 PVP/water (weight ratio) 0.54 0.54 0.54 Humidity indicator color is colorless, colorless, colorless, 20% RH, colorless, colorless, colorless, 30% RH, colorless Colorless and colorless 40%RH Thick pink pink pale pink 50%RH Thick pink pink pale pink 60%RH Thick pink pink pale pink 70%RH Thick pink pink pale pink 80%RH Thick pink pink pale pink 90%RH Thick pink pink pale pink In the same manner as in Example 1-1, the amount of the RED-20 was increased to 5 parts by weight and 20 parts by weight, respectively. A humidity indicator was prepared, and the humidity detection function was evaluated in the same manner as in Example 1-1. The results are shown in Table 3. (Examples 3-3 and 3-4) A humidity indicator was prepared and prepared in the same manner as in Example 1-1 except that the amount of the oxalic acid dihydrate added was changed to 3 parts by weight and 10 parts by weight, respectively. In Example 1-1, the humidity detecting function was evaluated in the same manner. The results are shown in Table 3. 100134955 16 201243323 [Table 3] Example 3-1 Example 3-: 2 Example 3-3 Example 3-4 Composition of paint RED-20 5 20 ' 4 4 oxalic acid dihydrate 2 2 3 10 ΓΡΑ 20 20 20 20 PVP aqueous solution 100 100 100 100 Coating thickness (g/m2) 1.76 2.13 1.76 1.97 PVP aqueous solution concentration (% by weight) 35 35 35 35 PVP/water (weight ratio) 0.54 0.54 0.54 0.54 Solid content in the coating ( Weight %) 33 40 33 37 PVP ratio in solids (% by weight) 83 61 83 71 Humidity indicator color is dry, colorless, colorless, colorless, colorless, 20%RH, colorless, colorless, colorless, colorless, 30%RH, colorless, colorless: colorless, colorless, 40%RH Pink thick pink _ thick pink thick pink 50% RH thick pink thick pink: thick pink thick pink 60% RH thick pink thick pink ' thick pink thick pink 70% RH thick pink thick pink: thick pink thick pink 80% RH thick pink thick Pink thick pink thick pink 90% RH thick pink thick pink thick pink thick pink dipped in water when thick pink thick pink; thick pink thick pink as shown in Table 3, even increase RED-20 or oxalate dihydrate Addition amount, humidity detection Nor can change. Therefore, it is understood that the solid content of the coating or the ratio of PVP in the solid portion has no effect on the humidity detecting function. Further, in the case where RED-20 is further increased to 20 parts by weight or when oxalic acid dihydrate is further increased to 10 parts by weight, the dispersibility in the coating is lowered to cause dissolution. (Examples 4-1 to 4-3, Comparative Examples 4-1 and 4-2) In the coating material for a humidity indicator of Example 1-1, water-based acrylic acid S used in Comparative Example 1-1 was further added. A humidity indicator was prepared in the same manner as in Example 1-1 except that the amount of the emulsion was 5 parts by weight, 10 parts by weight, 20 parts by weight, 31.5 parts by weight, and 50 parts by weight, and wet 100134955 was evaluated in the same manner as in Example 1-1. 201243323 degree detection function. The results are shown in Table 4. 100134955 18 201243323 [Inch <] Comparative Example 4-2 Inch CS 〇1—Η 1.92 m 0.38 m ^Γ) Pink Pink Pink Pink | Pink | Pink 1 1^3 | Pink | Pink Colorless | Comparative Example 4-1 Inch CN 1 31.5 100 1.86 cn 0.43 m ΓΛ ν〇|Pink _I Pink [Pink | Pink Pink | Pink | Pink! Pink Pink Colorless Example 4-3 inch (N 100 1.81 m 0.46 芝 ο colorless colorless pink pink pink pink 翁Color - Pink Pink Pink Example 4-2 Inch <N 〇100 1.76 cn 0.50 mmc^- Colorless, colorless, colorless, pink, pink, pink 1, pink, pink, pink, pink, pink, pink, Example 4-1, inch CN 100 1.76 iT) m 1 0.52 1 m ro colorless, colorless, colorless, pink, pink, pink, pink, pink, pink, pink, pink, RED-20, oxalic acid dihydrate, ttW § 'W g', Q® IPA PVP, aqueous solution, PVP, aqueous solution (% by weight) PVP/water (Weight ratio) Solid content in the coating (% by weight) PVP ratio in the solid portion (% by weight) 20% RH when dry 30% RH 40% RH 50% RH 60% RH 70% RH 80% RH 90% RH Dip The color of the composition of the humidity indicator when the paint collapses in water
61 S500I 201243323 如表4所示，若伴隨丙烯酸酯乳液之增加，而濕度指示劑 用塗料中之PVP相對於水分之重量比未滿0.45，則無法進 行高濕度下之檢測，損害濕度檢測功能。 (比較例5-1〜5-5) 將PVA(和光純藥（股）製造）溶解於純水中，分別獲得10 重量％、20重量％、35重量％之水溶液。又，將澱粉(和光 純藥（股）製造)溶解於純水中，分別獲得10重量％、20重量 %、40重量％之水溶液。使用該PVA水溶液或殿粉水溶液 代替PVP水溶液，除此以外與實施例1-1同樣地製作濕度 指示劑，與實施例1-1同樣地評價濕度檢測功能。將結果示 於表5中。 100134955 20 201243323 【lo<】 比較例5-6 寸 CN 〇 〇 I 〇 濃粉色 濃粉色| 濃粉色 濃粉色| 濃粉色 濃粉色| 濃粉色 濃粉色 濃粉色 粉色 比較例5-5 , 寸 CN 〇 〇 ” i I Lj農粉色1 |濃粉色| 濃粉色 濃粉色 濃粉色 濃粉色| 濃粉色 濃粉色 濃粉色 粉色 _〇 寸 (N 〇 〇 I 〇 1濃粉色| I濃粉色」 |濃粉色」 濃粉色 濃粉色| 濃粉色 濃粉色| 濃粉色 濃粉色 粉色 比較例5-3 j 寸 CN 〇 Ο in m 1 1濃粉色| |濃粉色| I濃粉色| I濃粉色| 濃粉色 I濃粉色| 濃粉色| 濃粉色 濃粉色 無色 比較例5-2 寸 CN 〇 ο 宕 1 1濃粉色 |濃粉色| |濃粉色| 濃粉色 |濃粉色| 濃粉色 濃粉色 濃粉色| 濃粉色 無色 比較例5-1 寸 (N 〇 ο ο 1 1濃粉色 |濃粉色| |濃粉色| 濃粉色| ί濃粉色| 濃粉色| 濃粉色| 濃粉色 濃粉色 無色 RED-20 乙二酸二水合物 IPA PVA水溶液 澱粉水溶液 PVA水溶液濃度(重量％) 澱粉水溶液濃度(重量％) 乾燥時 20%RH 30%RH 40%RH [50%RH 60%RH 70%RH 80%RH 90%RH 浸潰於水中時 塗料之組成 1 濕度指示劑之顏色 13 gg6t7-00l 201243323 如表5所示，於使用PVP以外之水溶性高分子之情形時， 即使於高濕度下亦與乾燥時相同，未發現出濕度檢測功能。 100134955 2261 S500I 201243323 As shown in Table 4, if the weight ratio of PVP to moisture in the humidity indicator coating is less than 0.45 with the increase of the acrylate emulsion, the detection under high humidity cannot be performed, and the humidity detection function is impaired. (Comparative Examples 5-1 to 5-5) PVA (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to obtain aqueous solutions of 10% by weight, 20% by weight, and 35% by weight, respectively. Further, starch (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to obtain an aqueous solution of 10% by weight, 20% by weight, and 40% by weight, respectively. A humidity indicator was prepared in the same manner as in Example 1-1 except that the PVA aqueous solution or the aqueous solution of the aqueous solution was used instead of the PVP aqueous solution, and the humidity detecting function was evaluated in the same manner as in Example 1-1. The results are shown in Table 5. 100134955 20 201243323 [lo<] Comparative Example 5-6 inch CN 〇〇I 〇 thick pink thick pink | thick pink thick pink | thick pink thick pink | thick pink thick pink thick pink pink comparison example 5-5, inch CN 〇〇 i I Lj 农粉1 | thick pink | thick pink thick pink thick pink | thick pink thick pink thick pink _ 〇 inch (N 〇〇I 〇1 thick pink | I thick pink) | thick pink" thick pink Thick pink | thick pink thick pink | thick pink thick pink pink comparison example 5-3 j inch CN 〇Ο in m 1 1 thick pink | | thick pink | I thick pink | I thick pink | thick pink I thick pink | Thick pink thick pink colorless comparison example 5-2 inch CN 〇ο 宕1 1 thick pink | thick pink | | thick pink | thick pink | thick pink | thick pink thick pink thick pink | thick pink colorless comparison example 5-1 inch (N 〇ο ο 1 1 thick pink | thick pink | | thick pink | thick pink | ί thick pink | thick pink | thick pink | thick pink thick pink colorless RED-20 oxalic acid dihydrate IPA PVA aqueous starch solution PVA Aqueous solution concentration (% by weight) aqueous starch concentration (heavy %) 20% RH when dry 30%RH 40%RH [50%RH 60%RH 70%RH 80%RH 90%RH Composition of the coating when immersed in water 1 Humidity indicator color 13 gg6t7-00l 201243323 As shown in Fig. 5, in the case of using a water-soluble polymer other than PVP, the humidity detecting function was not found even in the case of drying under high humidity. 100134955 22