JP6671845B2 - Droplet detection sheet - Google Patents
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- JP6671845B2 JP6671845B2 JP2015024136A JP2015024136A JP6671845B2 JP 6671845 B2 JP6671845 B2 JP 6671845B2 JP 2015024136 A JP2015024136 A JP 2015024136A JP 2015024136 A JP2015024136 A JP 2015024136A JP 6671845 B2 JP6671845 B2 JP 6671845B2
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Description
本発明は水分を含む液滴が接触する事によって不可逆的に発色する液滴検知シートに関する。 The present invention relates to a droplet detection sheet that irreversibly develops color when a droplet containing moisture contacts.
従来から水に濡れると発色する様々な液滴検知シートが提案されている。例えば、常態では白色だが水に濡れると濡れた部分の屈折率が変化して下地色が透けて見える水筆紙がある。しかし、可逆性のため付着した水が蒸発すると消色し、保存性に問題がある。これに対して、特許文献1には常態では黄色だが水に濡れると濡れた部分が青色に変化する感水紙を使用した薬剤飛散状況解析方法が開示されている。しかし、「噴霧される薬品の付着に反応する薬品反応紙」や「薬品反応紙は薬品の付着により変色する感水紙」との記載はあるが薬品反応紙や感水紙の構成を含めた詳細な記載はなく、薬品反応紙や感水紙に係る技術内容の詳細は開示されてない。
また、非特許文献1には感水紙試験紙の取扱説明書についての記載、非特許文献2には感水紙の紹介記事、非特許文献3には感水紙を使用した農薬飛散状況に関する実証報告が記載されているが感水紙試験紙や感水紙の技術内容の詳細は開示されてない。
2. Description of the Related Art Conventionally, various droplet detection sheets that develop color when wet with water have been proposed. For example, there is a writing brush paper which is white under normal conditions, but when wet with water, the refractive index of the wetted portion changes and the underlying color can be seen through. However, due to the reversibility, when the attached water evaporates, the color disappears, and there is a problem in storage stability. On the other hand,
In addition, Non-Patent
本発明は上記の実情に鑑みて雨、結露水、噴霧された水分を含む液滴などと接触した履歴が簡単に確認でき、また、農薬などの水分を含む各種薬剤散布時や撒水時の液滴飛散状況を簡便に目視で確認・判断でき、且つ、証拠として保存することが可能な液滴検知シートを提供することを目的とする。 In view of the above circumstances, the present invention can easily confirm the history of contact with rain, dew condensation water, droplets containing sprayed water, and the like, and also spray or spray various kinds of chemicals containing water such as pesticides. It is an object of the present invention to provide a droplet detection sheet that allows the user to easily visually confirm and judge the state of droplet scattering and store the evidence as evidence.
本発明は、下記の[1]〜[6]を提供することにより、上記目的を達成する。
[1] シート状の基材と、該基材の表面に設けられて不可逆的な発色が可能な塗工層とを有する液滴検知シートであって、前記塗工層が、水分を含む液滴に接触すると不可逆的に発色する水溶性染料と水溶性及び/又は吸水性の接着剤(ポリビニルアルコールを除く)とを含有しており、前記接着剤は水系以外の溶媒に溶解する性質を更に備え、前記塗工層に含有される前記水溶性染料の粒径は、JIS K0069−1992に規定されるふるい分け試験法による公称目開き106μmのふるい残分が0.1%以下であり、かつ公称目開き45μmのふるい残分が95%以上の範囲にあり、前記水溶性染料が前記接着剤および溶媒中に分散・保持されている、ことを特徴とする液滴検知シート。
[2] 前記基材が白色または淡色であり、発色後の前記塗工層は濃色系であることを特徴とする[1]に記載の液滴検知シート。
[3] 前記塗工層に含有される前記水溶性染料と前記接着剤との配合比率が、水溶性染料:接着剤=1:99〜70:30(固形分の重量部)であることを特徴とする[1]又は[2]に記載の液滴検知シート。
[4] 前記塗工層が、0.3〜3.0g/m2であることを特徴とする[1]乃至[3]のいずれかに記載の液滴検知シート。
[5] 前記塗工層上に剥離可能な保護フィルムが積層してあることを特徴とする[1]乃至[4]のいずれかに記載の液滴検知シート。
[6] 前記塗工層を設けた面とは反対側の前記基材の表面に粘着剤層を設け、該粘着剤層上に剥離性シート材が積層してあることを特徴とする[1]乃至[5]のいずれかに記載の液滴検知シート。
The present invention achieves the above object by providing the following [1] to [6] .
[1] A droplet detection sheet having a sheet-like base material and a coating layer provided on the surface of the base material and capable of irreversible coloring, wherein the coating layer contains a liquid containing water. It contains a water-soluble dye that irreversibly develops color when contacted with a droplet and a water-soluble and / or water-absorbing adhesive (excluding polyvinyl alcohol), and the adhesive further has a property of dissolving in a solvent other than an aqueous solvent. The particle size of the water-soluble dye contained in the coating layer is such that a sieve residue having a nominal opening of 106 μm according to a sieving test method specified in JIS K0069-1992 is 0.1% or less, and A droplet detection sheet , wherein a sieve residue having a mesh size of 45 μm is in a range of 95% or more, and the water-soluble dye is dispersed and held in the adhesive and the solvent .
[2] The droplet detection sheet according to [1], wherein the base material is white or light-colored, and the coated layer after coloring is a dark-colored system.
[3] The compounding ratio of the water-soluble dye and the adhesive contained in the coating layer is water-soluble dye: adhesive = 1: 99 to 70:30 (parts by weight of solid content). The droplet detection sheet according to [1] or [2], which is a feature.
[4] The droplet detection sheet according to any one of [1] to [3] , wherein the coating layer has a thickness of 0.3 to 3.0 g / m 2 .
[5] The droplet detection sheet according to any one of [1] to [4] , wherein a peelable protective film is laminated on the coating layer.
[6] The pressure-sensitive adhesive layer on a surface of said substrate opposite provided a coating layer provided a surface, wherein the release sheet material to the pressure-sensitive adhesive layer is are stacked [1 ] The droplet detection sheet according to any one of [5] to [5] .
本発明によれば雨、結露水、噴霧された水分を含む液滴などと接触した履歴が簡単に確認でき、また、農薬などの水分を含む各種薬剤散布時や撒水時の液滴飛散状況を簡便に目視で確認・判断でき、且つ、証拠として保存することが可能となる液滴検知シートを提供することができる。また、本発明の液滴検知シートを用いた液滴の検知方法は、水に濡れると色調変化する試薬や複雑な解析装置を使用する従来の方法と比較して、安価・簡便な方法である。
なお、本発明の液滴検知シートは感度が極めて良好であるので、手に付着した汗や測定環境の露等の水分で発色するため取り扱いには綿の手袋などで直接に接触しない様にして取り扱ことが望ましい。本発明の液滴検知シートの表面に保護フィルムを積層することで取り扱いを容易化できる。更にまた、測定時に垂直面や天井面など様々な場所に固定でき、固定する対象物も屋外ではフェンス、塀、外壁等の建造物、岩、樹木、枝葉等の自然物などに固定でき、風などで飛散しない様に裏面に粘着剤を積層した本発明の液滴検知シートによって作業性が格段に簡便化される。
According to the present invention, it is possible to easily confirm the history of contact with rain, dew condensation water, droplets containing sprayed water, etc., and also to observe the state of droplets scattering when spraying or spraying various chemicals containing water such as pesticides. It is possible to provide a droplet detection sheet that can be easily confirmed and judged visually and that can be stored as evidence. Further, the method for detecting a droplet using the droplet detection sheet of the present invention is an inexpensive and simple method as compared with the conventional method using a reagent that changes color when wet with water or a complicated analyzer. .
In addition, since the droplet detection sheet of the present invention has extremely good sensitivity, it is colored by moisture such as sweat attached to the hand or dew in the measurement environment. It is desirable to handle. Handling can be facilitated by laminating a protective film on the surface of the droplet detection sheet of the present invention. In addition, it can be fixed to various places such as vertical surface and ceiling surface at the time of measurement, and the object to be fixed can be fixed outdoors to buildings such as fences, fences, outer walls, rocks, trees, branches and leaves, etc. The workability is remarkably simplified by the droplet detection sheet of the present invention in which an adhesive is laminated on the back surface so as not to scatter.
以下、本発明の実施の形態について詳細に説明する。
本発明の液滴検知シートは、図1に示すように、シート状の基材1と、この基材1の表面に設けられて不可逆的な発色が可能な塗工層2とを有する液滴検知シートであって、前記塗工層2が、水分を含む液滴に接触すると発色する水溶性染料と水溶性及び/又は吸水性の接着剤とを含有することを特徴としている。そして、前記基材が白色または淡色であり、発色後の前記塗工層が濃色系であることが望ましいものである。
本発明の液滴検知シートは、雨や結露水など比較的大きな液滴(水滴)や、スプレーなどで噴霧された薬剤など比較的微細な液滴(薬剤などの化学成分を含む水滴)を高感度で検知するのに好適なシートである。本発明の液滴検知シートでは、液滴との接触によって塗工層内の水溶性染料が瞬時に溶解し、液滴の大きさに応じたスポットで発色する。よって、液滴の有無を検知できるというだけでなく、発生しているスポットの密度、大きさによって液滴の拡散状態等も確認することができる。
なお、不可逆的に発色する水溶性染料を使用することで、発色したスポットは水分が蒸発しても変色や消色する事はなく、目視で確認・判断でき、且つ証拠として保存することができる。このため、本発明の液滴検知シートは、雨、結露水、噴霧水などとの接触履歴や農薬など水分を含む各種薬剤散布時や撒水時の液滴飛散状況を目視で確認・判断できる液滴検知シートとして好適に使用できる。
Hereinafter, embodiments of the present invention will be described in detail.
As shown in FIG. 1, the droplet detection sheet of the present invention has a droplet having a sheet-
The droplet detection sheet of the present invention can increase relatively large droplets (water droplets) such as rain and dew condensation water, and relatively fine droplets (water droplets containing chemical components such as chemicals) such as a medicine sprayed by a spray. This is a sheet suitable for detection with sensitivity. In the droplet detection sheet of the present invention, the water-soluble dye in the coating layer is instantaneously dissolved by contact with the droplet, and color is formed at a spot corresponding to the size of the droplet. Therefore, not only the presence / absence of the droplet can be detected, but also the diffusion state of the droplet can be confirmed based on the density and size of the generated spot.
In addition, by using a water-soluble dye that irreversibly develops, the developed spot does not discolor or discolor even if moisture evaporates, and can be visually confirmed and judged, and can be stored as evidence. . For this reason, the droplet detection sheet of the present invention is a liquid capable of visually confirming and judging the contact history with rain, dew condensation water, spray water and the like, and the state of droplet scattering at the time of spraying or spraying various chemicals containing water such as agricultural chemicals. It can be suitably used as a drop detection sheet.
本発明において、水分を含む液滴が接触すると不可逆的に発色する塗工層の水溶性染料は一般的な黒、赤、緑、藍等の濃色系の水溶性染料が使用される。濃色系の水溶性染料を使用することで、スポット状の発色状態を容易に視認出来る様にすることが可能となる。 In the present invention, as a water-soluble dye of a coating layer which irreversibly develops a color when a droplet containing water contacts, a general water-soluble dye such as black, red, green or indigo is used. By using a dark-colored water-soluble dye, it is possible to easily visually recognize a spot-like coloring state.
また、水溶性染料の粒径は、JIS K0069−1992に規定されるふるい分け試験法による公称目開き106μmのふるい残分が0.1%以下であり、かつ公称目開き45μmのふるい残分が95%以上の範囲にあることが好ましい。 The particle size of the water-soluble dye is 0.1% or less for a sieve residue having a nominal opening of 106 μm according to a sieving test method specified in JIS K0069-1992 and 95% for a sieve residue having a nominal opening of 45 μm. % Is preferable.
公称目開き45μmのふるいを通過する粒径では着色能が大きくなって地色と濡れた時の色のコントラスト差が小さくなり発色スポットの視認性が劣り好ましくない。一方、公称目開き106μmのふるいを通過しない粒径では地色と濡れた時の色のコントラスト差は良好になるが表面にざらつきが発生し、更に塗工工程上ストリークなどの不具合が発生し好ましくない。 When the particle diameter passes through a sieve having a nominal mesh size of 45 μm, the coloring ability becomes large, and the difference in contrast between the ground color and the color when wet becomes small. On the other hand, when the particle size does not pass through a sieve having a nominal opening of 106 μm, the contrast difference between the ground color and the color when wet becomes good, but the surface is roughened, and problems such as streaks occur in the coating process. Absent.
本発明において、水分を含む液滴が接触すると不可逆的に発色する水溶性染料を含む塗工層に含有される接着剤は、水溶性及び/又は吸水性を有しているとともに、エタノール、メタノール、イソプロピルアルコール、酢酸エチル、トルエンなどの水系以外の溶媒に溶解するものであれば特に限定する物ではなく、ポリビニルアルコール、ポリエチレンオキサイド、ポリエチレンオキサイド架橋体、ポリビニルピロリドン等、汎用の接着剤を使用できる。 In the present invention, the adhesive contained in the coating layer containing a water-soluble dye that irreversibly develops color when a droplet containing water contacts, has water-soluble and / or water-absorbing properties, and ethanol, methanol There is no particular limitation as long as it can be dissolved in non-aqueous solvents such as isopropyl alcohol, ethyl acetate, and toluene, and general-purpose adhesives such as polyvinyl alcohol, polyethylene oxide, cross-linked polyethylene oxide, and polyvinylpyrrolidone can be used. .
本発明において、水分を含む液滴が接触すると不可逆的に発色する塗工層の水溶性染料と水溶性及び/又は吸水性の接着剤との配合比率が濃色系の水溶性染料:水溶性及び/又は吸水性の接着剤=1:99〜70:30(重量部)であることが好ましい。 In the present invention, the compounding ratio of the water-soluble dye of the coating layer and the water-soluble and / or water-absorbing adhesive, which irreversibly develops color when contacted with water-containing droplets, is a dark-colored water-soluble dye: water-soluble And / or a water-absorbing adhesive = 1: 99 to 70:30 (parts by weight).
水溶性染料が1重量部以下では絶対量が少なく濡れた時の発色が弱く、検知能力が劣るので好ましくない。70重量部以上では着色能が大きくなって地色と濡れた時の色のコントラスト差が小さくなり発色スポットの視認性が劣るので好ましくない。 When the amount of the water-soluble dye is 1 part by weight or less, the absolute amount is small, the color development when wet is weak, and the detection ability is inferior. When the content is more than 70 parts by weight, the coloring ability is increased, the contrast difference between the ground color and the wet color becomes small, and the visibility of the color spot is deteriorated.
本発明において、水分を含む液滴が接触すると不可逆的に発色する塗工層の重量が0.3〜3.0g/m2であることが好ましい。
1g/m2以下では絶対量が少なく濡れた時の発色が弱く、検知能力が劣るので好ましくない。3g/m2以上では水に濡れない状態で濃く着色し、地色と濡れた時の色のコントラスト差が小さくなり発色スポットの視認性が劣るので好ましくない。
In the present invention, it is preferable that the weight of the coating layer that irreversibly develops a color when a droplet containing water comes into contact is 0.3 to 3.0 g / m 2 .
An amount of 1 g / m 2 or less is not preferable because the absolute amount is small, the coloration when wet is weak, and the detection ability is poor. When it is 3 g / m 2 or more, it is not preferable because it becomes deeply colored without being wet with water, the difference in contrast between the ground color and the color when wet becomes small, and the visibility of the colored spot is inferior.
本発明において、水分を含む液滴が接触すると不可逆的に発色する塗工層は、エタノール、メタノール、イソプロピルアルコール、酢酸エチル、トルエンなどの水以外の溶媒に、上記水溶性染料が溶解せずに分散した状態であり、且つポリビニルアルコール、ポリエチレンオキサイド、ポリエチレンオキサイド架橋体、ポリビニルピロリドン等が分散している塗料(水溶性染料と接着剤との混合物)を基材上に塗工・乾燥して形成するのが好ましい。塗料中に水(水溶性染料を溶解する溶媒)が配合されると、水溶性染料が塗料中で溶解・発色するので水と接触せぬように配慮する必要がある。上記の接着剤としては、水溶性及び/又は吸水性を用いるのが好ましく、その理由は塗料中における水溶性染料の分散性や安定性が良好になり、均一な発色性が得られ、かつ、水分を含む液滴の吸収性に優れるからである。
なお、本発明で採用する水溶性染料については、当該染料自体は一般的な黒、赤、緑、藍等の濃色の化合物であるが、粒径を特定の範囲にすること、および、水溶性及び/又は吸水性の接着剤との配合比を特定の範囲にすることで接着剤と溶媒中に分散・保持されている形態では無色〜淡色を示すため、塗工層は未使用時(すなわち、液滴との未接触時)において、基材の色が反映される無色〜淡色となるのである。
従って発色前における本発明の液滴検知シートの塗工面の色は基材に基づいた色で、液滴に接触したときに水溶性染料が溶解して不可逆的に発色するのである。
In the present invention, the coating layer that irreversibly develops a color when a droplet containing water comes into contact, the water-soluble dye does not dissolve in a solvent other than water such as ethanol, methanol, isopropyl alcohol, ethyl acetate, and toluene. A coating (mixture of a water-soluble dye and an adhesive) in a dispersed state in which polyvinyl alcohol, polyethylene oxide, a crosslinked polyethylene oxide, polyvinyl pyrrolidone, etc. is dispersed is formed on a substrate by coating and drying. Is preferred. If water (a solvent that dissolves a water-soluble dye) is blended in the paint, the water-soluble dye dissolves and develops color in the paint, so care must be taken not to come into contact with water. As the above-mentioned adhesive, it is preferable to use water-soluble and / or water-absorbing agents, because the dispersibility and stability of the water-soluble dye in the coating material are improved, uniform color development is obtained, and This is because the liquid droplets containing water are excellent in absorptivity.
As for the water-soluble dye used in the present invention, the dye itself is a general dark-colored compound such as black, red, green, and indigo. By setting the blending ratio of the adhesive and the water-absorbing adhesive to a specific range, the adhesive and the solvent exhibit a colorless to light color when dispersed and held in a solvent. That is, at the time of non-contact with the droplets), the color changes from colorless to light, which reflects the color of the base material.
Therefore, the color of the coated surface of the droplet detection sheet of the present invention before color development is a color based on the base material, and the water-soluble dye dissolves and irreversibly develops color when it comes into contact with the droplets.
本発明において、水分を含む液滴が接触すると不可逆的な発色が可能な塗工層の下面には発色した後の視認性を良くするため、白色、黄、ピンク、淡青、等の淡色系(蛍光色を含む)の基材を使用するのが好適である。
本発明の液滴検知シートでは、前述したように淡色系の基材表面に、発色後に濃色系となる塗工層を設けた組み合わせとするのが好ましいものである、このような液滴検知シートは汎用性を備え、視認性が向上したものとなるからである。
しかし、これに限る必要はなく、本発明の液滴検知シートは、使用する環境に応じて発色を確認し易い色の組み合わせに適宜に設計してよい。例えば、基材の色を赤や黒の濃色として、塗工層が黄色、青色を発色させるものであってもよい。
In the present invention, in order to improve the visibility after the color is formed on the lower surface of the coating layer capable of irreversible color formation when the droplet containing water contacts, a light color system such as white, yellow, pink, light blue, or the like ( It is preferred to use a substrate (including fluorescent colors).
In the droplet detection sheet of the present invention, as described above, it is preferable to use a combination in which a light-colored base material surface is provided with a coating layer that becomes a dark color system after coloring. This is because the sheet has versatility and has improved visibility.
However, the present invention is not limited to this, and the droplet detection sheet of the present invention may be appropriately designed in a combination of colors in which color development can be easily confirmed according to the environment in which the droplet is used. For example, the color of the substrate may be dark red or black, and the coating layer may emit yellow or blue.
本発明において、上記基材に採用可能なシート状の材料としては、生分解性を有するポリ乳酸系樹脂シート、ポリプロピレン樹脂、耐衝撃性ポリスチレン樹脂、ポリエチレンテレフタレート樹脂、ポリカーボネート樹脂等の汎用のプラスチックシート、合成紙シート、片艶紙、コート紙、アート紙、キャストコート紙などの紙シートが挙げられ、これらシート(基材)を積層複合化した基材でも使用することができる。また、無色・透明のプラスチックシートの表面に一般的な染料や顔料により白色あるいは淡色に着色した層を設けた基材、白色あるいは淡色で不透明性のプラスチックシートを基材として使用することができる。 In the present invention, as the sheet-like material that can be used for the base material, general-purpose plastic sheets such as a polylactic acid-based resin sheet having biodegradability, a polypropylene resin, an impact-resistant polystyrene resin, a polyethylene terephthalate resin, and a polycarbonate resin are used. And paper sheets such as synthetic paper sheets, glazed paper, coated paper, art paper, cast-coated paper, etc., and a base material obtained by laminating and complexing these sheets (base materials) can also be used. Further, a base material in which a colorless or transparent plastic sheet is provided with a layer colored white or pale with a general dye or pigment on the surface thereof, or a white or pale opaque plastic sheet can be used as a base material.
本発明において、基材表面に水分を含む液滴が接触すると不可逆的に発色する水溶性染料を含んでなる塗工層を設ける塗工方法は特に限定されるものではなく、一般的な塗工機が使用できるが塗料特性や塗工量から特にグラビア、マイヤーバーの塗工装置が付いた塗工機が好ましい。 In the present invention, a coating method for providing a coating layer containing a water-soluble dye that irreversibly develops color when a droplet containing water contacts the substrate surface is not particularly limited, and a general coating method is used. Although a coating machine can be used, a coating machine equipped with a gravure or Meyer bar coating device is particularly preferable from the viewpoint of coating characteristics and coating amount.
本発明において、基材は特に限定する物ではないが経済性、汎用性、機能性、環境性の観点から片艶紙、コート紙、アート紙、キャストコート紙が好ましい。これらの基材は原料パルプとして針葉樹晒クラフトパルプ(NBKP)、広葉樹晒クラフトパルプ(LBKP)、針葉樹晒サルファイトパルプ(NBSP)、などの木材パルプを主体とし、これに必要に応じて、麻、竹、ワラ、ケナフ等の非木材パルプを併用することができる。これらの原料パルプに必要に応じてクレー、カオリン、タルク、二酸化チタン、炭酸カルシウム、水酸化アルミニウム粉末等の内添用填料を加え、さらにロジンサイズ剤等のサイズ剤、ポリアクリルアミド等の乾燥紙力増強剤、ポリアミド・ポリアミン・エピクロルヒドリンやメラミン樹脂等の湿潤紙力増強剤、硫酸バンド等の定着剤等の製紙用副資材を適宜添加して紙料を調製し、円網抄紙機、長網抄紙機、ツインワイヤー抄紙機、ヤンキー抄紙機等の抄紙機を使用して常法に従い非塗工紙を得ることができる。 In the present invention, the substrate is not particularly limited, but from the viewpoints of economy, versatility, functionality, and environmental friendliness, preferred are single gloss paper, coated paper, art paper, and cast coated paper. These base materials are mainly wood pulp such as softwood bleached kraft pulp (NBKP), hardwood bleached kraft pulp (LBKP), softwood bleached sulphite pulp (NBSP), and, if necessary, hemp, Non-wood pulp such as bamboo, straw and kenaf can be used in combination. If necessary, fillers such as clay, kaolin, talc, titanium dioxide, calcium carbonate, and aluminum hydroxide powder are added to these raw pulp, and sizing agents such as rosin sizing agents, and dry paper strength such as polyacrylamide are added. A paper stock is prepared by appropriately adding paper strengthening agents, wet paper strength enhancers such as polyamide / polyamine / epichlorohydrin and melamine resins, and auxiliary materials for papermaking such as a fixing agent such as a sulfate band. Uncoated paper can be obtained by a conventional method using a paper machine such as a paper machine, a twin wire paper machine, a Yankee paper machine or the like.
これら非塗工紙の紙面強度を向上させるために、サイズプレス装置等によって、スチレン系樹脂、スチレン・アクリル系樹脂、スチレン・マレイン酸樹脂、アルキルケテンダイマー、澱粉、酸化澱粉、ヒドロキシエチル化澱粉、カルボキシメチル化セルロース、カルボキシメチル化グアーガム、リン酸化グアーガム、酸化グアーガム、ポリビニルアルコール、ポリアクリルアミド等の薬品を表面に塗工することが可能である。 In order to improve the paper surface strength of these uncoated papers, a styrene resin, a styrene / acrylic resin, a styrene / maleic resin, an alkyl ketene dimer, a starch, an oxidized starch, a hydroxyethylated starch, Chemicals such as carboxymethylated cellulose, carboxymethylated guar gum, phosphorylated guar gum, oxidized guar gum, polyvinyl alcohol, and polyacrylamide can be applied to the surface.
これら非塗工紙を原紙としてその表面にカオリン、炭酸カルシウム、二酸化チタン、水酸化アルミニウムなどの顔料とスチレン・ブタジエンラテックス、メチルメタクリレート・ブタジエンラテックス、澱粉、ポリビニルアルコール等の周知の接着剤に分散剤、耐水化剤、防腐剤、防かび剤、等の塗工用の副資材を適宜併用して塗工液を調製し、エアナイフコーター、ブレードコーター、ロールコーター、キャストコーター等の周知のコーターを使用してコート紙、アート紙、キャストコート紙などの塗工紙を得ることができる。 Using these uncoated papers as base paper, pigments such as kaolin, calcium carbonate, titanium dioxide, and aluminum hydroxide and dispersants on well-known adhesives such as styrene / butadiene latex, methyl methacrylate / butadiene latex, starch, and polyvinyl alcohol A coating liquid is prepared by appropriately using auxiliary materials for coating such as a water-proofing agent, a preservative, a fungicide, and the like, and a known coater such as an air knife coater, a blade coater, a roll coater, or a cast coater is used. Thus, coated paper such as coated paper, art paper, cast coated paper, etc. can be obtained.
本発明において、水分を含む液滴が接触すると不可逆的に発色する水溶性染料を含む塗工層を設けてなる液滴検知シートの坪量は特に限定するものではないが40〜300g/m2が好ましく、特に取り扱い性や経済性の点から60〜250g/m2が好適である。 In the present invention, the basis weight of a droplet detection sheet provided with a coating layer containing a water-soluble dye which irreversibly develops color when contacted with droplets containing water is not particularly limited, but is 40 to 300 g / m 2. Is preferable, and from the viewpoints of handleability and economy, 60 to 250 g / m 2 is particularly preferable.
本発明の液滴検知シートは、前述した基材と塗工層とを備えてなるものが基本形態型(図1)であるが、図2に示すように、塗工層2上(表面)に保護フィルム3を更に配置することで、使用前に塗工層が水と接触して発色することを予防しつつ、取扱いが容易な液滴検知シートとすることができる。
塗工層上に積層する保護フィルムは、少なくとも片面に粘着剤層を有するもので、塗工層と接触する上記保護フィルムの粘着剤がその表面を侵すことが無く、且つ保護フィルムを剥がす時に上記粘着剤が塗工層表面を破壊することがないものであれば特に限定するものではなく、汎用の紙製マスキング用粘着シートやフィルム製マスキング用粘着シートが使用できる。ただし、塗工層を水分と接触させないようにするという耐水性の観点からフィルム製マスキング用粘着シートがより好適である。剥離力は特に限定するものではないが取り扱いの観点から20〜200g/15mm程度が好ましい。20g/15mm以下では取り扱い時に液滴検知シートから脱落する可能性があり好ましくない。また、200g/15mm以上では液滴検知シートから剥離する際に表面を破壊する可能性があり好ましくない。
The droplet detection sheet of the present invention is a basic form type (FIG. 1) comprising the above-described base material and coating layer, but as shown in FIG. 2, on the coating layer 2 (surface). By further disposing the
The protective film laminated on the coating layer has a pressure-sensitive adhesive layer on at least one side, and the pressure-sensitive adhesive of the protective film in contact with the coating layer does not attack the surface, and when the protective film is peeled off, There is no particular limitation as long as the pressure-sensitive adhesive does not destroy the coating layer surface, and a general-purpose paper-made masking pressure-sensitive adhesive sheet or a film-made masking pressure-sensitive adhesive sheet can be used. However, an adhesive sheet for masking made of a film is more preferable from the viewpoint of water resistance that the coating layer is not brought into contact with moisture. The peeling force is not particularly limited, but is preferably about 20 to 200 g / 15 mm from the viewpoint of handling. If it is less than 20 g / 15 mm, it may undesirably fall off the droplet detection sheet during handling. On the other hand, when the thickness is 200 g / 15 mm or more, the surface may be broken when peeled from the droplet detection sheet, which is not preferable.
また、本発明の液滴検知シートの基本形態型(図1)に、図3に示すように、塗工層2を設けた面とは反対側の基材1の表面に粘着剤層4を設け、この粘着剤層4上に剥離性シート材5を積層してもよい。これにより粘着剤層を利用して任意の構造物(少なくとも、粘着剤層を接触できる表面部を有する物体)に液滴検知シートを貼り付けることができるようになる。この場合も、塗工層2上に上記保護フィルム3を有する形態が好適な液滴検知シートとなる。
上記好適な液滴検知シートにおいて、粘着剤層は、保護フィルムを積層した液滴検知シートの反対面に設け、剥離シートで保護した所謂、粘着シートの形状である。粘着剤は所望の粘着力が得られれば特に限定するものではなく、汎用のアクリル系粘着剤、ゴム系粘着剤が使用できる。粘着力はフェンス、塀、外壁等の建造物、岩、樹木、枝葉等の自然物、機械・装置等の人工物など固定する対象物に対して充分に接着し、風や振動・衝撃などで容易に剥離・脱落しない程度であれば特に限定するものではないが100〜1000g/15mm程度が好ましい。100g/15mm以下では対象物によって脱落する可能性があり好ましくない。また、1000g/15mm以上では対象物によって剥離不能になったり、対象物の表面を破壊する可能性があり好ましくない。
剥離性シート材は粘着剤に対し適度の剥離性を有するものであれば特に限定するものではなく、シリコーン系剥離剤を塗布した汎用の剥離紙や剥離フィルムを使用できる。
In addition, as shown in FIG. 3, an adhesive layer 4 is formed on the surface of the
In the preferred droplet detection sheet, the pressure-sensitive adhesive layer has a so-called adhesive sheet shape provided on the opposite surface of the droplet detection sheet on which the protective film is laminated and protected by a release sheet. The pressure-sensitive adhesive is not particularly limited as long as a desired adhesive strength is obtained, and a general-purpose acrylic pressure-sensitive adhesive or rubber-based pressure-sensitive adhesive can be used. Adhesion is sufficient to adhere to fixed objects such as fences, fences, exterior walls and other structures, natural objects such as rocks, trees, branches and leaves, and artificial objects such as machines and devices. The thickness is not particularly limited as long as it does not peel or fall off, but is preferably about 100 to 1000 g / 15 mm. If it is less than 100 g / 15 mm, it may fall off depending on the object, which is not preferable. On the other hand, if the thickness is 1000 g / 15 mm or more, there is a possibility that the object cannot be peeled off or the surface of the object may be broken, which is not preferable.
The release sheet material is not particularly limited as long as it has an appropriate release property with respect to the adhesive, and a general-purpose release paper or a release film coated with a silicone release agent can be used.
[実施例1]
水溶性染料粉末(日本化薬製 カヤフェクトブルーNRE)をJIS K0069−1992に規定されるふるい分け試験法により分級し、公称目開き75μmのふるい残分が0.1%以下であり、かつ公称目開き53μmのふるい残分が95%以上の範囲の粉末を分取した。
ポリビニルピロリドン(日本触媒製 K-90)をイソプロピルアルコールに溶解して濃度10重量%のバインダー溶液を調製し、上記の水溶性染料粉末を分散し、イソプロピルアルコールで希釈して、水溶性染料:ポリビニルピロリドン=62:38(固形分重量比)で固形分濃度8.3重量%の水溶性染料分散液を調製した。
表面の平滑度が3000秒のキャストコート紙(日本製紙製 エスプリVW、坪量210g/m2)のキャストコート面に、上記水溶性染料分散液をマイヤーバーで固形分として0.6g/m2塗工し、本発明の液滴感知シートを作製した。
上記キャストコート紙は白色であり、水溶性染料分散液を塗工層として形成してある使用前の液滴感知シート表面の色の様子は若干青みを帯びた白色であった。
上記シートにマイクロシリンジで純水4μlを滴下したところ、水滴滴下部分は濃い青色に発色し、基紙への経時的な吸収、乾燥により水滴直径と同じ円形に青色発色部分が固定化し、水滴の接触を目視により視認でき、かつ発色部分は変形、変色することなく保存することができた。
[Example 1]
The water-soluble dye powder (Kayafect Blue NRE manufactured by Nippon Kayaku) is classified by a sieving test method specified in JIS K0069-1992, and the sieve residue having a nominal opening of 75 μm is 0.1% or less, and the nominal A powder having a sieve residue of 53 μm and a range of 95% or more was collected.
Polyvinylpyrrolidone (K-90, manufactured by Nippon Shokubai) is dissolved in isopropyl alcohol to prepare a binder solution having a concentration of 10% by weight. The water-soluble dye powder is dispersed and diluted with isopropyl alcohol. A water-soluble dye dispersion having a solids concentration of 8.3% by weight was prepared with pyrrolidone = 62: 38 (solids weight ratio).
The above water-soluble dye dispersion was solidified on a cast coat surface of cast coat paper (Nippon Paper Industries Esprit VW, basis weight 210 g / m 2 ) having a smoothness of 3000 seconds with a Meyer bar at a solid content of 0.6 g / m 2. After coating, a droplet sensing sheet of the present invention was prepared.
The cast coated paper was white, and the color of the surface of the droplet sensing sheet before use, in which the water-soluble dye dispersion was formed as a coating layer, was slightly bluish white.
When 4 μl of pure water was dropped on the sheet with a microsyringe, the portion where the water droplet was dropped developed a deep blue color, and the blue coloring portion was fixed in a circle having the same diameter as the diameter of the droplet by absorption over time and drying on the base paper. The contact was visually recognizable, and the colored portion could be stored without being deformed or discolored.
[実施例2]
実施例1において、水溶性染料分散液のポリビニルピロリドンと水溶性染料粉末の配合比を水溶性染料:ポリビニルピロリドン=55:45(固形分重量比)とした以外は実施例1と同様にして本発明の液滴検知シートを作製した。
[Example 2]
The procedure of Example 1 was repeated, except that the mixing ratio of polyvinylpyrrolidone and the water-soluble dye powder in the water-soluble dye dispersion was changed to water-soluble dye: polyvinylpyrrolidone = 55:45 (solid content weight ratio). The droplet detection sheet of the invention was produced.
[実施例3]
実施例1において、水溶性染料粉末の粒子径をJIS K0069−1992に規定されるふるい分け試験法による公称目開き106μmのふるい残分が0.1%以下であり、かつ公称目開き45μmのふるい残分が95%以上の範囲とした以外は、実施例1と同様にして本発明の液滴検知シートを作製した。
[Example 3]
In Example 1, the particle size of the water-soluble dye powder was 0.1% or less for a sieve residue having a nominal opening of 106 μm and a sieve residue having a nominal opening of 45 μm according to a sieving test method specified in JIS K0069-1992. A droplet detection sheet of the present invention was prepared in the same manner as in Example 1, except that the content was in the range of 95% or more.
[実施例4]
粒子径がJIS K0069−1992に規定されるふるい分け試験法による公称目開き75μmのふるい残分が0.1%以下であり、かつ公称目開き45μmのふるい残分が95%以上の範囲である水溶性染料粉末(日本化薬製 カヤフェクトブルーNRE)をイソプロプロピルアルコールに分散した濃度48重量%の水溶性染料分散液と濃度10重量%のポリエチレンオキサイド架橋体(住友精化製 アクアコークTWB)の酢酸エチル溶液とを、水溶性染料粉末/ポリエチレンオキサイド架橋体=1/99(固形分重量比)で配合した固形分濃度10.4重量%の水溶性染料分散液を調製した。
表面の平滑度が3000秒のキャストコート紙(日本製紙製 エスプリV、坪量210g/m2)のキャストコート面に、上記水溶性染料分散液をアプリケーターバーで塗工し、固形分付着量が3g/m2の発色層を塗設し、本発明の液滴検知シートを作製した。
該シートにマイクロシリンジで純水4μlを滴下したところ、水滴滴下部分は濃い青色に発色し、水滴はシート中へ迅速に吸収され、乾燥により水滴直径と同じ円形に青色発色部分が固定化し、水滴の接触を目視により視認でき、かつ発色部分は変形、変色することなく保存することができた。更に、発色した染料はポリエチレンオキサイド架橋体内部に保持されるため発色した染料が手指等に付着することがなく、取扱い易いものであった。
[Example 4]
A water solution having a sieve residue having a nominal opening of 75 μm and a sieve residue having a nominal opening of 45 μm in a range of 95% or more according to a sieving test method specified in JIS K0069-1992. Of a 48% by weight water-soluble dye dispersion obtained by dispersing a water-soluble dye powder (Kayafect Blue NRE manufactured by Nippon Kayaku) in isopropyl alcohol and a 10% by weight crosslinked polyethylene oxide (Aquacork TWB manufactured by Sumitomo Seika) A water-soluble dye dispersion having a solids concentration of 10.4% by weight was prepared by mixing the ethyl acetate solution with a water-soluble dye powder / polyethylene oxide crosslinked product = 1/99 (solids weight ratio).
The above water-soluble dye dispersion was applied to the cast coat surface of a cast coat paper (Nippon Paper Esprit V, basis weight 210 g / m 2 ) having a surface smoothness of 3000 seconds using an applicator bar, and the solids adhesion amount was reduced. A color-forming layer of 3 g / m 2 was applied to prepare a droplet detection sheet of the present invention.
When 4 μl of pure water was dropped on the sheet with a microsyringe, the water drop portion developed a deep blue color, the water droplet was quickly absorbed into the sheet, and the blue color portion was fixed in a circle having the same diameter as the water droplet diameter by drying. Was visually recognizable, and the color-developed portion could be stored without deformation or discoloration. Furthermore, since the colored dye was held inside the crosslinked polyethylene oxide, the colored dye did not adhere to fingers and the like, and was easy to handle.
[実施例5]
実施例1の液滴検知シートの塗工表面に保護フィルム(サンエー化研製 サニテクトY)を圧着ロール方式で積層貼合した。この液滴検知シートの取り扱い時に、塗工層に指が接触するとその部分が手汗で指紋状に発色する虞(おそれ)があるので手袋を着用するのが望ましいものであるが、保護フィルムを積層した場合は直接素手で触っても全く問題が無く簡単に取り扱い作業することが出来た。この時の液滴検知シート表面に対する保護フィルムの剥離力は55g/15mmで表面を破壊することなく容易に剥離することが出来、且つ液滴検知シート表面を侵すことも無く何ら変化は見られなかった。
[Example 5]
A protective film (Sanitect Y manufactured by San-A Kaken Co., Ltd.) was laminated and bonded to the coated surface of the droplet detection sheet of Example 1 by a pressure roll method. When handling the droplet detection sheet, if a finger comes into contact with the coating layer, the part may develop (fear) in the form of a fingerprint due to hand sweat. Therefore, it is desirable to wear gloves. In the case of lamination, handling could be performed easily without any problem even if touched directly with bare hands. At this time, the peeling force of the protective film on the surface of the droplet detection sheet is 55 g / 15 mm, so that the protective film can be easily peeled without breaking the surface, and does not affect the surface of the droplet detection sheet and no change is observed. Was.
[実施例6]
実施例5の液滴検知シートの塗工表面に保護フィルムを積層貼合した基材を表面基材として通常の粘着加工機で剥離紙(リンテック製EK100LT)に粘着剤(綜研化学製SKダイン1035)を塗工量25g/m2(乾燥重量)になるよう塗布し、転写法で液滴検知粘着シートを得た。この時の液滴検知粘着シートの粘着力は500g/15mmで金網フェンスおよびブロック塀の垂直面に充分に固着し、剥離する際には容易に剥離することが出来た。なお、固着対象物が機械装置の塗装面の場合は、液滴検知シートの密着性が高くなる傾向にあったが、この場合も剥離可能であった。
[Example 6]
Using a substrate obtained by laminating a protective film on the coated surface of the droplet detection sheet of Example 5 as a surface substrate, an adhesive (SK Dyne 1035 manufactured by Soken Chemical Co., Ltd.) was applied to release paper (EK100LT manufactured by Lintec) using a normal adhesive processing machine. ) Was applied so as to have a coating amount of 25 g / m 2 (dry weight), and a pressure-sensitive adhesive sheet was obtained by a transfer method. At this time, the adhesive strength of the droplet detection adhesive sheet was 500 g / 15 mm, and the adhesive sheet was sufficiently fixed to the vertical surfaces of the wire mesh fence and the block fence, and could be easily peeled when peeled. When the object to be fixed was a painted surface of a mechanical device, the adhesion of the droplet detection sheet tended to be high, but in this case, it could be peeled off.
[評価]
本発明の液滴検知シートの評価方法は無風の屋内において幅50mm×長さ1.5mのテープ状の液滴検知シートを床上に置き、水を入れたハンドスプレーで高さ1mの地点から液滴検知シートに向かって噴霧し、液滴が接触して発色する際の感度及び視認性、飛散分布状況を定性的に評価した。
[Evaluation]
The evaluation method of the droplet detection sheet of the present invention is as follows. A tape-like droplet detection sheet having a width of 50 mm and a length of 1.5 m is placed on a floor in a windless indoor room, and the liquid is hand sprayed from a point of 1 m in height with water. The liquid was sprayed toward the droplet detection sheet, and the sensitivity, visibility, and scattering distribution when the droplets came into contact and developed color were qualitatively evaluated.
また、保存性は発色スポットの7日後の変化(変色、消色、スポットの大きさ)を目視で確認した。
○:発色スポットの大きさ、色調、コントラストなど感度や視認性の良いもの
×:上記以外のもの
In addition, as for the storage stability, a change (discoloration, decoloration, spot size) of the color spot after 7 days was visually confirmed.
:: Good in sensitivity and visibility such as size, color tone and contrast of color spot ×: Other than the above
1 基材
2 塗工層
3 保護フィルム
4 粘着剤層
5 剥離性シート材
DESCRIPTION OF
Claims (6)
前記塗工層が、水分を含む液滴に接触すると不可逆的に発色する水溶性染料と水溶性及び/又は吸水性の接着剤(ポリビニルアルコールを除く)とを含有しており、前記接着剤は水系以外の溶媒に溶解する性質を更に備え、
前記塗工層に含有される前記水溶性染料の粒径は、JIS K0069−1992に規定されるふるい分け試験法による公称目開き106μmのふるい残分が0.1%以下であり、かつ公称目開き45μmのふるい残分が95%以上の範囲にあり、前記水溶性染料が前記接着剤および溶媒中に分散・保持されている、ことを特徴とする液滴検知シート。 Sheet-shaped substrate, a droplet detection sheet having a coating layer provided on the surface of the substrate and capable of irreversible color development,
The coating layer contains a water-soluble dye and a water-soluble and / or water-absorbing adhesive (excluding polyvinyl alcohol) that irreversibly develops color when it comes into contact with liquid droplets containing water. It further has the property of dissolving in solvents other than aqueous ,
As for the particle size of the water-soluble dye contained in the coating layer, the sieve residue having a nominal opening of 106 μm according to the sieving test method specified in JIS K0069-1992 is 0.1% or less, and the nominal opening is 0.1% or less. A droplet detection sheet having a sieve residue of 45 μm in a range of 95% or more, wherein the water-soluble dye is dispersed and held in the adhesive and the solvent .
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