JP5243014B2 - Marking sheet manufacturing method and display body - Google Patents
Marking sheet manufacturing method and display body Download PDFInfo
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- JP5243014B2 JP5243014B2 JP2007330141A JP2007330141A JP5243014B2 JP 5243014 B2 JP5243014 B2 JP 5243014B2 JP 2007330141 A JP2007330141 A JP 2007330141A JP 2007330141 A JP2007330141 A JP 2007330141A JP 5243014 B2 JP5243014 B2 JP 5243014B2
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- Prior art keywords
- colored
- film
- layer film
- sheet
- laminated sheet
- Prior art date
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Illuminated Signs And Luminous Advertising (AREA)
- Laminated Bodies (AREA)
Description
本発明はマーキングシート及び表示体に関し、さらに詳しくは、色が異なる着色上層フィルムと着色下層フィルムとから構成される積層シートであって、反射光で見る場合と透過光で見る場合の色が異なり、特に電飾看板などに好適に用いられるマーキングシート及びそれが被着体に貼付された表示体に関するものである。 The present invention relates to a marking sheet and a display body. More specifically, the present invention relates to a laminated sheet composed of a colored upper layer film and a colored lower layer film having different colors, and the colors are different when viewed with reflected light and transmitted light. In particular, the present invention relates to a marking sheet suitably used for an electric decoration signboard and a display body on which the marking sheet is attached to an adherend.
屋外広告などに用いられている電飾看板は、透明又は乳白色の透光性材料で形成された組み立て体の内部に電球や蛍光灯などの光源を設置し、組み立て体の表面に着色マーキングシートが貼付され用いられている。これらは昼間のような太陽光などの外光による視認状態においては、反射光による視認となり、夜は電飾看板内の光源による透過光による視認となる。
この電飾看板に用いられるマーキングシートは、昼でも夜でも同様な視認状態を得られるようなものが多く、例えば透過光により黄味、赤味、緑味又は青味のいずれかをもつ色彩を表出する着色フィルム層と、該着色フィルム層にこの着色フィルム層の該当する黄味、赤味、緑味又は青味のいずれかと補色関係にある色彩の補色層を有するマーキングフィルムが知られている（例えば、特許文献１参照）。
また、昼間と夜間とで色が異なる標識効果の大きいマーキングフィルムとして、透光性合成樹脂１００重量部に対してカーボンブラック０.４〜０.７重量部を含有する合成樹脂フィルムで、光透過率が４０〜５０％であることを特徴とするマーキングフィルム（例えば、特許文献２参照）、あるいは反射条件下ではほとんど黒く又は暗色に見えるような隠蔽性を有する着色フィルムであって、比較的明るい環境照明のもとでも見えないようにフィルムの下にイメージを効果的に隠すことができ、内照条件では明るいイメージを視認可能にする光透過着色フィルム（例えば、特許文献３参照）などが開示されている。
しかしながら、特許文献２及び３は確かに昼と夜で色が異なるが、白色(透過光の色)と黒色についてのものであり、それ以外の色の異なることについては言及されていない。
Many of the marking sheets used for this electric signboard can obtain a similar visual state at daytime or at night, for example, a yellowish, reddish, greenish or bluedish color by transmitted light. A marking film having a colored film layer to be exposed and a complementary color layer having a color complementary to any of the yellowish, reddish, greenish or bluedish corresponding to the colored film layer is known. (For example, refer to Patent Document 1).
In addition, as a marking film having a large labeling effect that is different in color between daytime and nighttime, it is a synthetic resin film containing 0.4 to 0.7 parts by weight of carbon black with respect to 100 parts by weight of light-transmitting synthetic resin. A marking film characterized by a rate of 40 to 50% (for example, see Patent Document 2), or a colored film having a concealing property that looks almost black or dark under reflective conditions, and is relatively bright Disclosed is a light-transmitting colored film (for example, see Patent Document 3) that can effectively hide an image under the film so that it cannot be seen even under ambient lighting, and that makes a bright image visible under internal lighting conditions. Has been.
However,
本発明は、このような事情のもとで、白及び黒以外の有彩色において、反射光で見る場合と透過光で見る場合の色が異なり、特に電飾看板などに好適に用いられるマーキングシート及びそれが被着体に貼付された表示体を提供することを目的としてなされたものである。 Under such circumstances, the present invention is different in color when viewed with reflected light and when viewed with transmitted light in chromatic colors other than white and black, and is particularly suitable for an electric signboard or the like. And it is made for the purpose of providing the display body affixed on the to-be-adhered body.
本発明者らは、前記の好ましい性質を有するマーキングシートを開発すべく鋭意研究を重ねた結果、色が異なる着色上層フィルムと着色下層フィルムとから構成される積層シートであって、該積層シートの反射光での色相と透過光での色相の差が特定の関係にあり、かつ全光線透過率がある値未満のマーキングシートが、その目的に適合し得ることを見出した。また、上記マーキングシートにおける着色下層フィルムの裏面側に、あるいは着色上層フィルムの被着体側に、それぞれ粘着剤層を設け、特定の全光線透過率を有する透光性被着体それぞれに、該粘着剤層を介してマーキングシートを貼布することにより、目的とする表示体が得られることを見出した。
本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
［１］互いに色が異なる着色上層フィルムと着色下層フィルムを、ゾルキャスト法によって、二層積層して積層シートを形成し、該積層シートにおける前記着色下層フィルム側に粘着剤層を設ける製造方法であって、前記ゾルキャスト法に用いるオルガノゾル塗工液は、０．０１μｍ以上０．５μｍ未満の範囲の小さい平均粒径の樹脂微粒子と、０．５μｍ以上５μｍ以下の範囲の大きい平均粒径の樹脂微粒子とが混合されたものであり、前記ゾルキャスト法により、工程フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して、前記着色上層フィルムを形成し、当該着色上層フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して前記着色下層フィルムを形成し、前記積層シートを得る工程、または、前記ゾルキャスト法により、工程フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して、前記着色下層フィルムを形成し、当該着色下層フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して前記着色上層フィルムを形成し、前記積層シートを得る工程を有し、前記二層積層シートの全光線透過率が２０％未満であり、かつ積層シートの反射光での色相と透過光での色相の差が、ＪＩＳ Ｚ ８７２９−１９９４によるＬ＊ａ＊ｂ＊表色系におけるａｂ色相角（ｈａｂ）で１０以上であり、前記粘着剤層を構成する粘着剤は、ブチルアクリレート単位、及び又は２−エチルヘキシルアクリレート単位を主体とする樹脂成分と、イソシアナート系架橋剤とを含むアクリル系粘着剤であることを特徴とするマーキングシートの製造方法、
［２］積層シートにおける着色上層フィルムの反射光と透過光のａｂ色相角（ｈａｂ）の差が、着色下層フィルムの反射光と透過光のａｂ色相角（ｈａｂ）の差よりも大きい上記［１］項に記載のマーキングシートの製造方法、
［３］該積層シートの着色上層フィルムと着色下層フィルムの色の組み合わせが、赤／紫、橙／赤、青／緑、紫／青（上層／下層）である上記［１］又は［２］項に記載のマーキングシートの製造方法、
［４］全光線透過率が２０％以上の透光性被着体に、上記［１］〜［３］項のいずれかに記載のマーキングシートの製造方法によって製造されたマーキングシートが、前記粘着剤層を介して貼付されていることを特徴とする表示体、及び
［５］全光線透過率が７０％以上の透光性被着体に、上記［１］〜［３］項のいずれかに記載のマーキングシートの製造方法によって製造されたマーキングシートが、前記粘着剤層を介して貼付されていることを特徴とする表示体、を提供するものである。
As a result of intensive studies to develop a marking sheet having the above-mentioned preferable properties, the present inventors have obtained a laminated sheet composed of a colored upper layer film and a colored lower layer film having different colors, It has been found that a marking sheet having a specific relationship between a hue of reflected light and a hue of transmitted light and having a total light transmittance of less than a certain value can meet the purpose. In addition, an adhesive layer is provided on the back side of the colored lower layer film in the marking sheet or on the adherend side of the colored upper layer film, and the adhesive layer has a specific total light transmittance. It discovered that the target display body was obtained by sticking a marking sheet through an agent layer.
The present invention has been completed based on such findings.
That is, the present invention
[1] a colored lower layer film and the colored layer films mutually different colors, depending on zone le casting, a laminated sheet formed by laminating two layers, providing an adhesive layer on the colored lower film side of the laminated sheet production The organosol coating liquid used in the sol-cast method is a resin particle having a small average particle diameter in the range of 0.01 μm or more and less than 0.5 μm and a large average particle diameter in the range of 0.5 μm or more and 5 μm or less. The resin fine particles are mixed, and by the sol-cast method, the organosol coating liquid is applied on the process film and dried to form the colored upper layer film, on the colored upper layer film, Applying and drying the organosol coating solution to form the colored lower layer film to obtain the laminated sheet, or by the sol casting method, The organosol coating solution is applied onto a film and dried to form the colored lower layer film. On the colored lower layer film, the organosol coating solution is applied and dried to form the colored upper layer film. A step of obtaining the laminated sheet, wherein the total light transmittance of the two-layer laminated sheet is less than 20%, and the difference in hue between reflected light and transmitted light of the laminated sheet is JIS Z 8729- der 10 or more ab hue angle in the L * a * b * color system by 1994 (hab) is, pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, and the metallic butyl acrylate units, and or the 2-ethylhexyl acrylate units method for producing a marking sheet to the resin component, wherein the acrylic adhesive der Rukoto comprising an isocyanate-based crosslinking agent,
[2] The difference in the ab hue angle (hab) between the reflected light and the transmitted light of the colored upper layer film in the laminated sheet is greater than the difference between the reflected light and the ab hue angle (hab) of the transmitted light of the colored lower layer film [1 A method for producing the marking sheet according to the item ,
[ 3 ] The above [1] or [ 2 ], wherein the color combination of the colored upper layer film and the colored lower layer film of the laminated sheet is red / purple, orange / red, blue / green, purple / blue (upper layer / lower layer). A method for producing the marking sheet according to the item ,
[ 4 ] A marking sheet produced by the method for producing a marking sheet according to any one of [1] to [3] above is applied to the translucent adherend having a total light transmittance of 20% or more. display body characterized by being attached bonded through an adhesive layer, and [5] the transparent adherend total light transmittance of 70% or more, any of the above [1] to [3], wherein marking sheet produced by the manufacturing method of marking sheet crab described, display body, characterized in that are attached bonded via the adhesive layer, there is provided a.
本発明によれば、色が異なる着色上層フィルムと着色下層フィルムとから構成される積層シートであって、反射光で見る場合と透過光で見る場合の色が異なり、反射光では着色上層フィルムの色が視認でき、透過光では着色下層シートの色を強調して視認することができ、特に電飾看板などに好適に用いられるマーキングシート及びそれが被着体に貼付された表示体を提供することができる。 According to the present invention, a laminated sheet composed of a colored upper layer film and a colored lower layer film having different colors, the colors when viewed with reflected light and when viewed with transmitted light are different. Provided is a marking sheet that can be visually recognized by highlighting the color of the colored lower layer sheet with transmitted light, and is particularly suitable for an electric signboard, and a display body on which the label is attached to an adherend. be able to.
本発明のマーキングシートは、色が異なる着色上層フィルムと着色下層フィルムとから構成される積層シートである。
本発明のマーキングシートにおいて、積層シートを構成する着色上層フィルム及び着色下層フィルムのフィルム素材としては、特に制限はなく、従来電飾看板などに用いられているマーキングシートに使用されている各種樹脂の中から、任意のものを適宜選択することができる。例えば、アクリル樹脂、塩化ビニル樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、ポリオレフィン樹脂、ポリエステル樹脂、ポリカーボネート樹脂などを用いることができる。これらの中でも、アクリル樹脂、塩化ビニル樹脂が好適である。
着色上層フィルム及び着色下層フィルムは、フィルム素材として、同じ樹脂を用いたものであってもよく、異なる樹脂を用いたものであってもよい。
この着色上層フィルム及び着色下層フィルムとしては、前記樹脂に、顔料や染料などの着色剤を含有させた通常の各種着色フィルムを使用できる。
これらのフィルムを積層するには、着色フィルムを接着剤などを用いて他の着色フィルムに積層する方法や、ゾルキャスト法、押出し法等の標準的フィルム形成法によるもの全てが可能であり、特にその形成方法は問わないがゾルキャスト法、すなわち着色オルガノゾルをコーティングした後に乾燥、ゲル化させるフィルム成形法で、着色フィルムと他の着色フィルムを二層積層する方法が薄いフィルムとして形成できるので好ましい。
The marking sheet of the present invention is a laminated sheet composed of a colored upper layer film and a colored lower layer film having different colors.
In the marking sheet of the present invention, as the film material of the colored upper layer film and the colored lower layer film constituting the laminated sheet, there is no particular limitation, and various types of resins used in marking sheets conventionally used for electric decoration signs and the like. Any one can be appropriately selected from the inside. For example, acrylic resin, vinyl chloride resin, polystyrene resin, ABS resin, polyolefin resin, polyester resin, polycarbonate resin, or the like can be used. Among these, acrylic resins and vinyl chloride resins are preferable.
The colored upper layer film and the colored lower layer film may use the same resin as the film material, or may use different resins.
As the colored upper layer film and the colored lower layer film, various ordinary colored films in which the resin contains a colorant such as a pigment or a dye can be used.
In order to laminate these films, a method of laminating a colored film on another colored film using an adhesive or the like, and a standard film forming method such as a sol cast method and an extrusion method are all possible. The formation method is not limited, but a sol-cast method, that is, a film forming method in which a colored organosol is coated and then dried and gelled, and a method of laminating a colored film and another colored film in two layers is preferable because it can be formed as a thin film.
オルガノゾル塗工液は、樹脂の微粒子が溶媒中に分散されているペースト状の高粘度流体組成物である。その樹脂としては、例えば、塩化ビニル樹脂、アクリル樹脂などが好ましく挙げられる。
オルガノゾル塗工液中の樹脂微粒子の平均粒径としては、０.０１〜５μｍが好ましい。また、その樹脂微粒子は、小さい平均粒径の樹脂微粒子と、大きい平均粒径の樹脂微粒子が混合されたものが好ましい。すなわち、粒度分布のピークが小さいものと大きいものの２つが存在するものが好ましい。このような樹脂微粒子は、凝集物が発生し難く、また、溶融ゲル化し易い。なお、粒度分布のピークは、３つ以上存在してもよい。小さい平均粒径は、０.０１μｍ以上から０.５μｍ未満の範囲が好ましい。大きい平均粒径は、０.５μｍ以上から５μｍの範囲が好ましい。０.０１μｍ以上から０.５μｍ未満の範囲の小さい平均粒径の樹脂微粒子と、０.５μｍ以上から５μｍの範囲の大きい平均粒径の樹脂微粒子との混合割合は、質量比で１：９〜９：１が好ましく、２：８〜８：２がより好ましく、３：７〜７：３が特に好ましい。
樹脂微粒子の形状は、球形が好ましい。また、樹脂微粒子は、表面が平滑で、内部が緻密なものが好ましい。このような樹脂微粒子はオルガノゾルの流動性に必要な可塑剤量が少なく、オルガノゾルの熟成粘度変化が小さい。
The organosol coating liquid is a paste-like high viscosity fluid composition in which resin fine particles are dispersed in a solvent. Preferred examples of the resin include vinyl chloride resin and acrylic resin.
The average particle size of the resin fine particles in the organosol coating liquid is preferably 0.01 to 5 μm. The resin fine particles are preferably a mixture of resin fine particles having a small average particle diameter and resin fine particles having a large average particle diameter. That is, it is preferable that the particle size distribution has a small peak and a large peak. Such resin fine particles are unlikely to generate aggregates and are easily melted and gelled. Three or more peaks in the particle size distribution may exist. The small average particle diameter is preferably in the range of 0.01 μm or more and less than 0.5 μm. The large average particle diameter is preferably in the range of 0.5 μm to 5 μm. The mixing ratio of the resin fine particles having a small average particle diameter ranging from 0.01 μm to less than 0.5 μm and the resin fine particles having a large average particle diameter ranging from 0.5 μm to 5 μm is from 1: 9 to mass ratio. 9: 1 is preferable, 2: 8 to 8: 2 is more preferable, and 3: 7 to 7: 3 is particularly preferable.
The shape of the resin fine particles is preferably spherical. The resin fine particles preferably have a smooth surface and a dense interior. Such resin fine particles require a small amount of plasticizer necessary for the fluidity of the organosol, and the aging viscosity change of the organosol is small.
樹脂微粒子は、適切な粒度分布が得られ、また形状が球形であるには、乳化重合により製造されたものが好ましい。樹脂の重量平均重合度は、塩化ビニル樹脂については、５００〜４,０００が好ましく、アクリル樹脂については、２,０００〜４０,０００が好ましい。アクリル樹脂の微粒子は、良好な粘度貯蔵安定性を得るには、コア／シェルタイプの構造を有するものが好ましい。
当該オルガノゾルには、柔軟性を付与するために、通常可塑剤が用いられるが、この可塑剤は、低比重かつ低粘度でオルガノゾルに優れた流動性を付与し、低揮発性であって、樹脂に常温で初期親和性を示し、熟成中は樹脂への浸透及び膨潤が少なく、溶融工程で迅速に溶融ゲル化するものが好ましい。好適な具体例としては、ポリエステル系可塑剤が挙げられる。このポリエステル系可塑剤の重量平均分子量は、２,０００〜６,０００の範囲が好ましい。可塑剤の含有量は、樹脂微粒子１００質量部に対し５〜４０質量部が好ましい。
オルガノゾル塗工液における分散溶媒としては、常温で樹脂をわずかに膨潤して分散を助長し、高温加熱工程で溶融ゲル化を促進する溶媒が好ましく、好適な具体例としては、ジイソブチルケトン、メチルイソブチルケトンなどのケトン類、酢酸ブチルなどのエステル類、グリコールエーテル類などが挙げられる。これらの溶媒は単独で用いてもよく、２種以上を混合して用いてもよい。
また、オルガノゾル塗工液には、粘度を調整するために、希釈溶媒を含有させることができる。希釈溶媒としては、樹脂に対して不溶性で、ゾル粘度を下げ、分散溶媒の膨潤性を抑制する溶媒が好ましく、好適な具体例としては、パラフィン系炭化水素、ナフテン系炭化水素、芳香族炭化水素、テルペン系炭化水素などが挙げられる。
また、分散溶媒及び希釈溶媒は、沸点が１８０℃以下のものが好ましく、沸点の下限値は、８０℃以上が好ましく、１１０℃以上が特に好ましい。
The resin fine particles are preferably produced by emulsion polymerization in order to obtain an appropriate particle size distribution and to have a spherical shape. The weight average polymerization degree of the resin is preferably 500 to 4,000 for the vinyl chloride resin, and preferably 2,000 to 40,000 for the acrylic resin. In order to obtain good viscosity storage stability, the acrylic resin fine particles preferably have a core / shell type structure.
In order to impart flexibility to the organosol, a plasticizer is usually used. However, this plasticizer imparts excellent fluidity to the organosol with low specific gravity and low viscosity, is low in volatility, and is a resin. It is preferable to have an initial affinity at room temperature, which has little penetration and swelling into the resin during aging and rapidly melts and gels in the melting step. A specific example is a polyester plasticizer. The polyester plasticizer preferably has a weight average molecular weight in the range of 2,000 to 6,000. The content of the plasticizer is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the resin fine particles.
The dispersion solvent in the organosol coating liquid is preferably a solvent that slightly swells the resin at room temperature and promotes dispersion, and promotes melt gelation in a high-temperature heating process. Preferred examples include diisobutyl ketone and methyl isobutyl. Examples include ketones such as ketones, esters such as butyl acetate, glycol ethers, and the like. These solvents may be used alone or in combination of two or more.
In addition, the organosol coating liquid may contain a diluting solvent in order to adjust the viscosity. As the dilution solvent, a solvent that is insoluble in the resin, lowers the sol viscosity, and suppresses the swelling property of the dispersion solvent is preferable, and specific examples include paraffin hydrocarbons, naphthene hydrocarbons, aromatic hydrocarbons. And terpene hydrocarbons.
Further, the dispersion solvent and the dilution solvent preferably have a boiling point of 180 ° C. or lower, and the lower limit of the boiling point is preferably 80 ° C. or higher, particularly preferably 110 ° C. or higher.
また、オルガノゾル塗工液には、必要に応じて、熱安定剤、紫外線吸収剤、充填剤、ゲル化剤等の添加剤を含有させることができる。
熱安定剤は、特に塩化ビニル樹脂に用いられるものであり、塩化ビニル樹脂はその構造中に不規則構造を持っているので高温での成形加工時や使用時に熱、光、酸素などにより脱塩化水素反応を主とする分解劣化を起こし、着色を生じることがあり、それを防止するために使用される。好適な具体例としては、鉛塩系熱安定剤、金属セッケン系熱安定剤、有機スズ化合物系熱安定剤、非金属系熱安定剤等が挙げられる。熱安定剤の含有量は、樹脂微粒子１００質量部に対し０.５〜１０質量部が好ましい。
紫外線吸収剤としては、例えば、サリチル酸系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアゾール系紫外線吸収剤などが挙げられる。紫外線吸収剤の含有量は、樹脂微粒子１００質量部に対し０.１〜１０質量部が好ましい。
充填剤は、増量によるコスト切り下げ（カサを稼ぐ）とオルガノゾルの流動特性を調整するためのものなどが挙げられ、具体例としては、炭酸カルシウム、クレー、シリカ、マイカ、ケイソウ土などが挙げられる。
ゲル化剤は、オルガノゾルの粘度、降伏値を高め、チクソトロピー化することで、オルガノゾルの流動特性を改良するためのものなどが挙げられ、具体例としては、金属石ケン類、炭酸カルシウム、ケイ酸カルシウム、シリカエアロゲル、アミン処理ベントナイト、カーボンブラックなどが挙げられる。
In addition, the organosol coating liquid may contain additives such as a heat stabilizer, an ultraviolet absorber, a filler, and a gelling agent as necessary.
Thermal stabilizers are used in particular for vinyl chloride resins. Since vinyl chloride resins have an irregular structure in their structure, they are dechlorinated by heat, light, oxygen, etc. during molding and use at high temperatures. It is used in order to prevent decomposition by causing decomposition and deterioration mainly due to hydrogen reaction. Preferable specific examples include lead salt heat stabilizers, metal soap heat stabilizers, organotin compound heat stabilizers, non-metal heat stabilizers, and the like. The content of the heat stabilizer is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin fine particles.
Examples of the UV absorber include salicylic acid UV absorbers, benzophenone UV absorbers, and triazole UV absorbers. As for content of a ultraviolet absorber, 0.1-10 mass parts is preferable with respect to 100 mass parts of resin fine particles.
Examples of the filler include cost reduction by increasing the amount (making money) and adjusting the flow characteristics of the organosol, and specific examples include calcium carbonate, clay, silica, mica, and diatomaceous earth.
Gelling agents include those for improving the flow characteristics of organosols by increasing the viscosity and yield value of organosols and thixotropy. Specific examples include metal soaps, calcium carbonate, silicic acid. Examples include calcium, silica airgel, amine-treated bentonite, and carbon black.
本発明においては、オルガノゾル塗工液は、上層と下層において色の異なるものを用いる。 透過光における視認性の点から色は、有色透明色であるものが好ましい。オルガノゾル塗工液を有色にするには、着色剤を含有させる。
着色剤としては、種々の顔料、染料が使用できるが、可塑剤と無機系及び／又は有機系顔料を練り合わせてペースト状にした着色剤トナーが、樹脂との分散性に優れるため、好ましい。
本発明においては、工程フィルム上にまず着色上層フィルムとなるオルガノゾル塗工液を塗布後、予備乾燥し溶媒分を揮発させて着色上層フィルムを形成する。その後、該着色上層フィルムの上に着色下層フィルムとなるオルガノゾル塗工液を塗布し、溶媒分を揮発後、加熱溶融してゲル化させ、着色上下層構成の積層フィルムを作製する方法が好ましい。なお、後述する表示体によっては、先に着色下層フィルムを形成する場合もある。
工程フィルムとしては、耐熱性の樹脂フィルムが好ましく挙げられ、例えば、ポリエチレンテレフタレート樹脂フィルム、ポリブチレンテレフタレート樹脂フィルム等のポリエステル樹脂フィルムなどが挙げられる。工程フィルムの厚みは、特に制限ないが、通常２５〜１００μｍ程度である。
工程フィルムは、表面が剥離処理されているものが好ましい。表面の剥離処理に用いられる剥離処理剤の代表例としては、アルキッド系樹脂、ウレタン系樹脂、オレフィン系樹脂、シリコーン系樹脂などが挙げられる。
キャスト製膜は、ロールナイフコーター、リバースロールコーターなどの塗工機を用い、工程フィルムと塗工機の隙間にオルガノゾル塗工液を送り出し、一定の厚みのキャスト膜を形成することが好ましい。工程フィルムは、連続したものを使用し、連続的に送り出すことが好ましい。
In the present invention, the organosol coating liquids having different colors are used for the upper layer and the lower layer. From the viewpoint of visibility in transmitted light, the color is preferably a colored transparent color. In order to color the organosol coating liquid, a colorant is contained.
As the colorant, various pigments and dyes can be used. However, a colorant toner obtained by kneading a plasticizer and an inorganic and / or organic pigment to form a paste is preferable because of its excellent dispersibility with the resin.
In the present invention, an organosol coating solution to be a colored upper layer film is first applied on the process film, and then preliminarily dried to evaporate the solvent and form a colored upper layer film. Thereafter, an organic sol coating liquid to be a colored lower layer film is applied on the colored upper layer film, and after the solvent is volatilized, it is heated and melted to be gelled to prepare a laminated film having a colored upper and lower layer structure. In addition, depending on the display body mentioned later, a colored lower layer film may be formed previously.
As a process film, a heat resistant resin film is mentioned preferably, For example, polyester resin films, such as a polyethylene terephthalate resin film and a polybutylene terephthalate resin film, etc. are mentioned. The thickness of the process film is not particularly limited, but is usually about 25 to 100 μm.
The process film is preferably one whose surface is subjected to a release treatment. Typical examples of the release treatment agent used for the surface release treatment include alkyd resins, urethane resins, olefin resins, silicone resins, and the like.
Cast film formation is preferably performed using a coating machine such as a roll knife coater or a reverse roll coater, and sending an organosol coating solution into the gap between the process film and the coating machine to form a cast film having a constant thickness. It is preferable to use a continuous process film and continuously feed it out.
加熱溶融のゲル化温度は、樹脂の種類により異なるが、塩化ビニル樹脂の場合は、１８０〜２１０℃が好ましく、１８５〜２００℃が特に好ましい。また、樹脂がアクリル樹脂である場合は、１３０〜１９０℃が好ましく、１４０〜１７０℃が特に好ましい。加熱溶融のゲル化時間は、特に制限なく、ゲル化の速度により適宜選定すればよいが、通常１０秒間〜１０分間であればよい。
なお、加熱溶融のゲル化に先立って、予備乾燥することが好ましい。予備乾燥の温度は、１１０〜１７０℃が好ましく、１２０〜１５０℃が特に好ましい。予備乾燥の時間は、特に制限なく、適宜選定すればよいが、通常１０秒間〜１０分間であればよい。
上層着色フィルム及び下層着色フィルムのゲル化後の厚みは、それぞれ通常２０〜１００μｍが好ましく、２５〜７０μｍが特に好ましい。積層シートの厚さとしては、通常４０〜２００μｍが好ましく、５０〜１４０μｍが特に好ましい。
このようにして形成された色の異なる着色上層フィルムと着色下層フィルムとから構成される積層シートは、厚さ８０μｍにおける全光線透過率が２０％未満であり、好ましくは０.２〜１５％である。２０％以上だと反射光と透過光での色が変化しにくく、また０.２％未満だと色の確認がしにくい。
なお、上記全光線透過率の測定方法については、後で説明する。
The gelation temperature for heating and melting varies depending on the type of resin, but in the case of a vinyl chloride resin, 180 to 210 ° C is preferable, and 185 to 200 ° C is particularly preferable. Moreover, when resin is an acrylic resin, 130-190 degreeC is preferable and 140-170 degreeC is especially preferable. The gelation time for heating and melting is not particularly limited and may be appropriately selected depending on the gelation speed, but is usually 10 seconds to 10 minutes.
In addition, it is preferable to pre-dry before gelation of heat melting. The temperature for preliminary drying is preferably 110 to 170 ° C, particularly preferably 120 to 150 ° C. The time for preliminary drying is not particularly limited and may be appropriately selected. However, it may be usually 10 seconds to 10 minutes.
The thickness of the upper colored film and the lower colored film after gelation is usually preferably 20 to 100 μm and particularly preferably 25 to 70 μm. As thickness of a lamination sheet, 40-200 micrometers is usually preferred, and 50-140 micrometers is especially preferred.
The laminated sheet composed of the colored upper layer film and the colored lower layer film having different colors thus formed has a total light transmittance at a thickness of 80 μm of less than 20%, preferably 0.2 to 15%. is there. If it is 20% or more, the color of the reflected light and transmitted light hardly changes, and if it is less than 0.2%, it is difficult to confirm the color.
The method for measuring the total light transmittance will be described later.
本発明のマーキングシートにおいては、着色上層フィルムと着色下層フィルムが積層された積層シートにおいて、反射光での色相と透過光での色相の差が、ＪＩＳ Ｚ ８７２９−１９９４によるＬ*ａ*ｂ*表色系におけるａｂ色相角（ｈａｂ）で１０以上であることを要す。反射光と透過光の色相の差が、ａｂ色相角（ｈａｂ）で１０以上であれば、反射光と透過光での色の違いが良好で、しかもはっきりと色の違いを視認することができる。該色相の差は、ａｂ色相角（ｈａｂ）で、好ましくは１２以上である。
本発明においては、当該積層シートにおける着色上層フィルムの反射光と透過光のａｂ色相角（ｈａｂ）の差が、着色下層フィルムの反射光と透過光のａｂ色相角（ｈａｂ）の差よりも大きいことが、本発明の効果の点から好ましい。
本発明のマーキングシートにおいて、着色上層フィルムと着色下層フィルムとの組合わせとしては、赤／紫、橙／赤、青／緑又は紫／青（上層／下層）が好適である。
In the marking sheet of the present invention, in the laminated sheet in which the colored upper layer film and the colored lower layer film are laminated, the difference in hue between reflected light and transmitted light is L * a * b * according to JIS Z 8729-1994 . The ab hue angle (hab) in the color system must be 10 or more. If the difference in hue between reflected light and transmitted light is 10 or more in ab hue angle (hab), the difference in color between reflected light and transmitted light is good, and the difference in color can be clearly seen. . The difference in hue is an ab hue angle (hab), and is preferably 12 or more.
In the present invention, the difference in the ab hue angle (hab) between the reflected light and the transmitted light of the colored upper layer film in the laminated sheet is larger than the difference in the ab hue angle (hab) between the reflected light and the transmitted light of the colored lower layer film. It is preferable from the viewpoint of the effect of the present invention.
In the marking sheet of the present invention, the combination of the colored upper layer film and the colored lower layer film is preferably red / purple, orange / red, blue / green or purple / blue (upper layer / lower layer).
次に、前述したマーキングシートが、透光性被着体に貼付されてなる本発明の表示体について説明する。図１及び図２は、それぞれ本発明の表示体の異なる態様の例を示す説明図である。
例えば、本発明のマーキングシートを電飾看板などにおける透光性被着体に貼付する場合、すなわち図１に示すように、透明又は乳白色などの透光性被着体１ａの光源の反対側に本発明のマーキングシート１０ａを貼付(いわゆる外貼り)する場合には、積層シート５における着色下層フィルム３の裏面側に粘着剤層４を設ける。また、透光性被着体１ｂの特定位置に貼付する場合、すなわち図２に示すように、透光性被着体１ｂの光源側に本発明のマーキングシート１０ｂを貼付(いわゆる内貼り)する場合には、積層シート５における着色上層フィルム２の透光性被着体１ｂ側に粘着剤層４を設ける。
ここで、透光性被着体１ａは、全光線透過率が、通常２０％以上、好ましくは２５％以上の透明及び乳白色などの被着体であり、具体的にはアクリル樹脂板、ポリカーボネート板、ポリ塩化ビニル板、硝子板、それと内照用看板では看板の主組み立て体となるフレキシブルフェイスなどである。一方、透光性被着体１ｂは、全光線透過率が、通常７０％以上、好ましくは７５％以上の被着体であり、具体的にはアクリル樹脂板、ポリカーボネート板、ポリ塩化ビニル板、硝子板などである。
Next, the display body of the present invention in which the above-described marking sheet is attached to a translucent adherend will be described. 1 and 2 are explanatory diagrams showing examples of different aspects of the display body of the present invention.
For example, when the marking sheet of the present invention is attached to a translucent adherend in an electric signboard or the like, that is, as shown in FIG. 1, on the opposite side of the light source of the translucent adherend 1a such as transparent or milky white. When sticking the marking
Here, the translucent adherend 1a is an adherend such as transparent and milky white having a total light transmittance of usually 20% or more, preferably 25% or more, specifically an acrylic resin plate or a polycarbonate plate. For example, a polyvinyl chloride plate, a glass plate, and a signboard for internal lighting, such as a flexible face that is the main assembly of the signboard. On the other hand, the translucent adherend 1b is an adherend having a total light transmittance of usually 70% or more, preferably 75% or more. Specifically, an acrylic resin plate, a polycarbonate plate, a polyvinyl chloride plate, It is a glass plate.
粘着剤層に使用できる粘着剤としては、特に制限されることなく、種々の粘着剤が使用できるが透明なものが好ましい。例えば、アクリル系粘着剤、ポリエステル系粘着剤、又はシリコーン系粘着剤を主剤とする粘着剤などが挙げられる。なお、耐候性、コストの点からアクリル系粘着剤が好ましく用いられる。 The pressure-sensitive adhesive that can be used in the pressure-sensitive adhesive layer is not particularly limited, and various pressure-sensitive adhesives can be used, but a transparent one is preferable. For example, an acrylic pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, or a pressure-sensitive adhesive mainly containing a silicone-based pressure-sensitive adhesive can be used. An acrylic pressure-sensitive adhesive is preferably used in terms of weather resistance and cost.
アクリル系の粘着剤としては、アルキル基の炭素数が４〜１２の(メタ)アクリル酸アルキルエステルモノマーを主成分とし、これに共重合可能な他のビニル系モノマーを共重合して得られるものが適当である。
アルキル基の炭素数が４〜１２の(メタ)アクリル酸アルキルエステルモノマーとしては、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、２−エチルヘキシル(メタ)アクリレート、イソオクチル(メタ)アクリレート、デシル(メタ)アクリレートなどが挙げられる。これに共重合されるビニル系モノマーは、得られる粘着剤の粘着力や凝集力を調節するために用いられるものであり、具体的にはアルキル基の炭素数が１〜３の(メタ)アクリル酸アルキルエステル；水酸基含有(メタ)アクリル酸アルキルエステル；(メタ)アクリル酸、クロトン酸、マレイン酸等のα,β−不飽和カルボン酸；アクリルアミド；アクリロニトリル；スチレン；酢酸ビニル；ビニルピロリドン等を例示することができる。
Acrylic pressure-sensitive adhesive is obtained by copolymerizing (meth) acrylic acid alkyl ester monomers having 4 to 12 carbon atoms in the alkyl group as main components and copolymerizing with other vinyl monomers copolymerizable therewith. Is appropriate.
Examples of the (meth) acrylic acid alkyl ester monomer having 4 to 12 carbon atoms in the alkyl group include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) ) Acrylate, decyl (meth) acrylate, and the like. The vinyl monomer copolymerized therewith is used to adjust the adhesive strength and cohesive strength of the resulting adhesive, and specifically, a (meth) acrylic alkyl group having 1 to 3 carbon atoms. Acid alkyl ester; hydroxyl group-containing (meth) acrylic acid alkyl ester; (meth) acrylic acid, crotonic acid, maleic acid and other α, β-unsaturated carboxylic acid; acrylamide; acrylonitrile; styrene; vinyl acetate; can do.
これらのモノマー混合物は、溶液重合法、乳化重合法、懸濁重合法、塊状重合法等の従来公知の方法により共重合できるが、重合が容易である点で溶液重合が望ましい。重合に用いられる溶媒としては、トルエン、ヘキサン、ヘプタン、酢酸エチル、アセトン、メチルエチルケトン、メタノール等を例示することができる。
重合開始剤としては、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、メチルエチルケトンパーオキサイド等の過酸化物系開始剤、アゾビスイソブチロニトリル、アゾビスシアノバレリン酸、アゾビスシアノペンタン等のアゾ系開始剤を例示することができる。重合開始剤量は、使用するモノマー全量１００質量部に対し、０.０５〜０.８質量部が好ましく、特に０.２〜０.５質量部が好ましい。
上記の粘着剤には、イソシアナート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤、アジリジン系架橋剤等の架橋剤を配合することができるが、特にイソシアナート系架橋剤が好ましい。
架橋剤の配合量は、必要とする粘着特性を得るためには、アクリル系粘着剤１００質量部に対して０.５〜５質量部が好ましく、特に1〜３.５質量部が好ましい（いずれも固形分換算値）。
These monomer mixtures can be copolymerized by a conventionally known method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or the like, but the solution polymerization is desirable in terms of easy polymerization. Examples of the solvent used for polymerization include toluene, hexane, heptane, ethyl acetate, acetone, methyl ethyl ketone, methanol and the like.
Examples of the polymerization initiator include peroxide initiators such as benzoyl peroxide, lauroyl peroxide, and methyl ethyl ketone peroxide, and azo initiators such as azobisisobutyronitrile, azobiscyanovaleric acid, and azobiscyanopentane. It can be illustrated. The amount of the polymerization initiator is preferably 0.05 to 0.8 parts by mass, particularly preferably 0.2 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of monomers used.
The pressure-sensitive adhesive may contain a crosslinking agent such as an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a metal chelate-based crosslinking agent, or an aziridine-based crosslinking agent, and an isocyanate-based crosslinking agent is particularly preferable.
The blending amount of the crosslinking agent is preferably 0.5 to 5 parts by mass, particularly 1 to 3.5 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive in order to obtain the required adhesive properties. Is also a solid content conversion value).
前記イソシアナート系架橋剤としては、例えば、トリレンジイソシアナート、ジフェニルメタンジイソシアナート、キシリレンジイソシアナートなどの芳香族ポリイソシアナート、ヘキサメチレンジイソシアナートなどの脂肪族ポリイソシアナート、イソホロンジイソシアナート、水素添加ジフェニルメタンジイソシアナートなどの脂環式ポリイソシアナートなど、及びそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油などの低分子活性水素含有化合物との反応物であるアダクト体などを挙げることができる。これらの架橋剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
本発明においては、粘着剤として、ブチルアクリレート単位、及び又は２−エチルヘキシルアクリレート単位を主体とする樹脂成分を含むアクリル系粘着剤が好ましく、イソシアナート系架橋剤を使用したアクリル系粘着剤が好ましく、耐候性、被着体への追従性に優れる点で、特に好ましい。
Examples of the isocyanate-based crosslinking agent include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and isophorone diisocyanate. , Cycloaliphatic polyisocyanates such as hydrogenated diphenylmethane diisocyanate and the like, and biurets, isocyanurates, and low molecular activities such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. The adduct body etc. which are a reaction material with a hydrogen containing compound can be mentioned. These crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, the pressure-sensitive adhesive is preferably an acrylic pressure-sensitive adhesive containing a resin component mainly composed of a butyl acrylate unit and / or a 2-ethylhexyl acrylate unit, and is preferably an acrylic pressure-sensitive adhesive using an isocyanate cross-linking agent. It is particularly preferable in terms of excellent weather resistance and followability to the adherend.
粘着剤中に、必要に応じて粘着性付与剤、充填剤、酸化防止剤、熱安定剤、紫外線吸収剤、光安定剤、着色剤、難燃剤、帯電防止剤等の従来より配合されることのある各種添加剤を含有させることは任意であるが、粘着剤層の透明性を損なわない範囲で配合することが好ましい。
粘着剤層の厚み（乾燥後）は、十分な粘着性（タック）や粘着力を得るには１０μｍ以上とすることが好ましく、フィルム端部からの糊のはみ出しや、ゴミの付着、さらに、剥離する際に粘着剤層が凝集破壊を起こして、糊残りを生じることを防ぐためには、５０μｍ以下であることが好ましい。すなわち、粘着剤層の厚みは通常１０〜５０μｍであり、特に２０〜４０μｍが好ましい。
In the pressure-sensitive adhesive, if necessary, a tackifier, a filler, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a colorant, a flame retardant, an antistatic agent and the like are conventionally blended. Although it is optional to contain various additives, it is preferable to add them in a range that does not impair the transparency of the pressure-sensitive adhesive layer.
The thickness of the pressure-sensitive adhesive layer (after drying) is preferably 10 μm or more in order to obtain sufficient tackiness (tack) and adhesive strength. Adhesion of glue from the film edge, adhesion of dust, and peeling In order to prevent the pressure-sensitive adhesive layer from causing cohesive failure and causing adhesive residue, it is preferably 50 μm or less. That is, the thickness of the pressure-sensitive adhesive layer is usually 10 to 50 μm, and particularly preferably 20 to 40 μm.
粘着剤層を設ける方法は、工程フィルム付き積層シートに直接塗付してもよく、また、剥離シートに粘着剤を塗布した後、粘着剤層を積層シート面と貼り合わせてもよい。
なお、工程フィルムは、粘着剤層を形成した後、使用形態に応じて、適当な段階で除去するのが適当であるが、工程フィルムを除去した積層シートに粘着剤層を形成しても差し支えない。
粘着剤の塗布方法としては、特に制限なく種々の方法を用いることができ、例えば、エアーナイフコーター、ブレードコーター、バーコーター、グラビアコーター、ロールコーター、ロールナイフコーター、カーテンコーター、ダイコーター、ナイフコーター、スクリーンコーター、マイヤーバーコーター、キスコーターなどが挙げられる。
The method of providing the pressure-sensitive adhesive layer may be applied directly to the laminated sheet with the process film, or after the pressure-sensitive adhesive is applied to the release sheet, the pressure-sensitive adhesive layer may be bonded to the laminated sheet surface.
In addition, it is appropriate to remove the process film at an appropriate stage after forming the pressure-sensitive adhesive layer, depending on the form of use. However, the pressure-sensitive adhesive layer may be formed on the laminated sheet from which the process film has been removed. Absent.
There are no particular restrictions on the method of applying the adhesive, and various methods can be used, such as air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater. , Screen coater, Meyer bar coater, kiss coater and the like.
剥離シートとしては、特に制限はなく、従来より公知の剥離シートを適宜選択して用いることができる。
例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィンフィルムや、クレーコート紙、グラシン紙、再生紙等の紙基材、これらの紙基材にポリエチレンなどの熱可塑性樹脂をラミネートしたラミネート紙などの片面に離型処理されているものが用いられる。離型処理剤としては、シリコーン系樹脂、長鎖アルキル系樹脂、フッ素系樹脂等を例示することができる。
剥離シートの厚さとしては特に制限はないが、通常１０〜１５０μｍが好ましい。
There is no restriction | limiting in particular as a peeling sheet, A conventionally well-known peeling sheet can be selected suitably and used.
For example, polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyolefin films such as polyethylene, polypropylene, polymethylpentene, paper base materials such as clay coated paper, glassine paper, recycled paper, these paper base materials In other words, a laminate paper or the like laminated with a thermoplastic resin such as polyethylene is used which has been subjected to a mold release treatment. Examples of the mold release treatment agent include silicone resins, long chain alkyl resins, fluorine resins, and the like.
Although there is no restriction | limiting in particular as thickness of a peeling sheet, Usually, 10-150 micrometers is preferable.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られたマーキングシート（粘着剤層が設けられていない、着色上層フィルムと着色下層フィルムとからなる積層シート）、単層フィルムの光学特性及び透光性被着体の全光線透過率は、以下に示す方法に従って測定した。また、マーキングシートの官能テストは以下に示す方法で行った。
（１）全光線透過率
ＪＩＳ Ｋ ７３６１−１（全光線透過率の試験方法、１９９７年度版）に規定される測定方法に準拠し、ヘイズメーター［日本電色工業社製、機種名「ＮＤＨ２０００」］にて、フィルムシートの全光線透過率を測定した。
（２）反射光及び透過光測定時のＬ*ａ*ｂ*表示における明度（Ｌ*）、ａｂクロマ（ｃ*）、ａｂ色相角（ｈａｂ）(ＳＣＩ方式、Ｄ６５光源／１０°視野測定時)
ＪＩＳ Ｚ ８７２２（色の測定方法−反射及び透過物体色、１９９４年度版）に規定される測定方法に準拠し、分光光度計［データカラーインターナショナル社製、機種名「ＳＦ６００ＰＬＵＳ」］にて、測定した分光反射率及び分光透過率を、ＪＩＳ Ｚ ８７２９（色の表示方法−Ｌ*ａ*ｂ*表色系、１９９４年度版）における明度（Ｌ*）、ａｂクロマ（ｃ*）、ａｂ色相角（ｈａｂ）で表示した。
（３）マーキングシートの官能テスト
実施例及び比較例で作製した粘着剤層が設けられていない積層シート（１０ｃｍ×５ｃｍ）を観察者１０人に渡し、室内蛍光灯下において、積層シートを反射光で見る場合と透過光で見る場合の状態を確認した。１０人の確認結果の平均を下記のように評価した。
○・・・反射光と透過光で異なる色が明確に確認できる。
△・・・反射光と透過光で異なる色が少し確認できる。
×・・・反射光と透過光で異なる色が確認できない。
（４）透光性被着体の全光線透過率
ＪＩＳ Ｋ ７３６１−１（全光線透過率の試験方法、１９９７年度版）に規定される測定方法に準拠し、ヘイズメーター［日本電色工業社製、機種名「ＮＤＨ２０００」］にて測定した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the marking sheet (the laminated sheet which consists of a colored upper layer film and a colored lower layer film which is not provided with an adhesive layer) obtained in each example, the optical characteristics of the single layer film, and the total light of the translucent adherend The transmittance was measured according to the method shown below. Moreover, the sensory test of the marking sheet was performed by the method shown below.
(1) Total light transmittance In accordance with a measurement method defined in JIS K 7361-1 (Test method for total light transmittance, 1997 edition), a haze meter [manufactured by Nippon Denshoku Industries Co., Ltd., model name “NDH2000” ], The total light transmittance of the film sheet was measured.
(2) Lightness (L * ), ab chroma (c * ), ab hue angle (hab) in L * a * b * display when measuring reflected light and transmitted light (SCI method, when measuring D65 light source / 10 ° field of view) )
Measured with a spectrophotometer [Model name “SF600PLUS” manufactured by Data Color International Co., Ltd.] in accordance with a measurement method defined in JIS Z 8722 (color measurement method—reflection and transmission object color, 1994 edition). Spectral reflectance and spectral transmittance were measured in terms of lightness (L * ), ab chroma (c * ), ab hue angle in JIS Z 8729 (color display method—L * a * b * color system, 1994 edition). hab).
(3) Sensory test of marking sheet The laminated sheet (10 cm × 5 cm) provided with the adhesive layer prepared in Examples and Comparative Examples was handed to 10 observers, and the laminated sheet was reflected under indoor fluorescent lamps. We confirmed the situation when we see with transmitted light and when we see with transmitted light. The average of the confirmation results of 10 people was evaluated as follows.
○: Different colors can be clearly confirmed between reflected light and transmitted light.
Δ: A slightly different color can be confirmed between the reflected light and the transmitted light.
X: Different colors cannot be confirmed between reflected light and transmitted light.
(4) Total light transmittance of translucent adherend: Haze meter [Nippon Denshoku Industries Co., Ltd.] in accordance with the measurement method specified in JIS K 7361-1 (Test method for total light transmittance, 1997 edition) Manufactured, model name “NDH2000”].
製造例１ 赤色オルガノゾル塗工液の製造
平均粒径が０.１μｍと平均粒径が０.８μｍの２種類の塩化ビニル樹脂微粒子を同量混合した塩化ビニル樹脂微粒子［Ｂ．Ｆ．グッドリッチ社製、商品名「ＧＥＯＮ１７８」、重量平均重合度１８００、樹脂微粒子の形状は球形である。］１００質量部、アジピン酸ポリエステル系可塑剤［大日精化工業社製、商品名「ファインサイザーＮＳ−４０７０」、重量平均分子量４０００］１３質量部、金属セッケン系熱安定剤［勝田加工社製、商品名「ＳＢ−９３０１」］４質量部、ベンゾフェノン系紫外線吸収剤［サイテック社製、商品名「サイアソーブ ＵＶ−５３１」］４質量部、赤色着色剤［大日精化工業社製、商品名「ＶＴＳＫ−９３３１レッド」］２０質量部、分散溶媒［ゴードー溶剤社製、商品名「ブチルセロソルブ」、グリコールエーテル類］２３.５質量部、及び希釈分散溶媒［ゴードー溶剤社製、商品名「ＳＳ−１００」、芳香族炭化水素系溶剤］２３.５質量部を混合して、赤色の塩化ビニル樹脂オルガノゾル塗工液を調製した。配合組成を第１表に示す。
Production Example 1 Production of Red Organosol Coating Liquid Vinyl chloride resin fine particles obtained by mixing equal amounts of two types of vinyl chloride resin fine particles having an average particle size of 0.1 μm and an average particle size of 0.8 μm [B. F. Goodrich, product name “GEON178”, weight average polymerization degree 1800, and resin fine particles are spherical. ] 100 parts by mass, adipic acid polyester plasticizer [manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “Fine Sizer NS-4070”, weight average molecular weight 4000] Product name “SB-9301”] 4 parts by mass, benzophenone UV absorber [made by Cytec, product name “Siasorb UV-531”] 4 parts by mass, red colorant [Daiichi Seika Kogyo Co., Ltd., product name “VTSK” -9331 Red "] 20 parts by mass, dispersion solvent [manufactured by Gordo Solvent Co., Ltd., trade name" butyl cellosolve ", glycol ethers] 23.5 parts by mass, and diluted dispersion solvent [manufactured by Gordo Solvents, trade name" SS-100 " Aromatic hydrocarbon solvent] 23.5 parts by mass were mixed to prepare a red vinyl chloride resin organosol coating solution. The composition is shown in Table 1.
製造例２ 橙色オルガノゾル塗工液の製造
赤色着色剤に代えて橙色着色剤［大日精化工業社製、商品名「ＶＴＳＫ−９３２９オレンジ」］を用いた以外は、製造例１の赤色オルガノゾル塗工液の製造と同様にして、第１表に記載されている配合組成で混合して、橙色の塩化ビニル樹脂オルガノゾル塗工液を調製した。配合組成を第１表に示す。
製造例３ 黄色オルガノゾル塗工液の製造
赤色着色剤に代えて黄色着色剤［大日精化工業社製、商品名「ＶＴＳＫ−９３２３イエロー」］を用いた以外は、製造例１の赤色オルガノゾル塗工液の製造と同様にして、第１表に記載されている配合組成で混合して、黄色の塩化ビニル樹脂オルガノゾル塗工液を調製した。配合組成を第１表に示す。
製造例４ 緑色オルガノゾル塗工液の製造
赤色着色剤に代えて緑色着色剤［大日精化工業社製、商品名「ＶＴＳＫ−９３２４グリーン」］を用いた以外は、製造例１の赤色オルガノゾル塗工液の製造と同様にして、第１表に記載されている配合組成で混合して、緑色の塩化ビニル樹脂オルガノゾル塗工液を調製した。配合組成を第１表に示す。
製造例５ 青色オルガノゾル塗工液の製造
赤色着色剤に代えて青色着色剤［大日精化工業社製、商品名「ＶＴＳＫ−９３０５ブルー」］を用いた以外は、製造例１の赤色オルガノゾル塗工液の製造と同様にして、第１表に記載されている配合組成で混合して、青色の塩化ビニル樹脂オルガノゾル塗工液を調製した。配合組成を第１表に示す。
製造例６ 紫色オルガノゾル塗工液の製造
赤色着色剤に代えて紫色着色剤［大日精化工業社製、商品名「ＶＴＳＫ−９４００バイオレット」］を用いた以外は、製造例１の赤色オルガノゾル塗工液の製造と同様にして、第１表に記載されている配合組成で混合して、紫色の塩化ビニル樹脂オルガノゾル塗工液を調製した。配合組成を第１表に示す。
Production Example 2 Production of Orange Organosol Coating Liquid The red organosol coating of Production Example 1 was used except that an orange colorant [manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “VTSK-9329 Orange”] was used instead of the red colorant. In the same manner as in the production of the liquid, an orange vinyl chloride resin organosol coating liquid was prepared by mixing with the composition described in Table 1. The composition is shown in Table 1.
Production Example 3 Production of yellow organosol coating liquid Red organosol coating of Production Example 1 except that a yellow colorant [manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “VTSK-9323 Yellow”] was used instead of the red colorant. In the same manner as in the production of the liquid, mixing was carried out with the blending composition described in Table 1 to prepare a yellow vinyl chloride resin organosol coating liquid. The composition is shown in Table 1.
Production Example 4 Production of Green Organosol Coating Liquid Red organosol coating of Production Example 1 except that a green colorant [manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “VTSK-9324 Green”] was used instead of the red colorant. In the same manner as in the production of the liquid, a green vinyl chloride resin organosol coating liquid was prepared by mixing with the composition described in Table 1. The composition is shown in Table 1.
Production Example 5 Production of Blue Organosol Coating Liquid The red organosol coating of Production Example 1 except that a blue colorant [manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “VTSK-9305 Blue”] was used instead of the red colorant. In the same manner as in the production of the liquid, a blue vinyl chloride resin organosol coating liquid was prepared by mixing with the composition described in Table 1. The composition is shown in Table 1.
Production Example 6 Production of Purple Organosol Coating Liquid The red organosol coating of Production Example 1 except that a purple colorant [manufactured by Dainichi Seika Kogyo Co., Ltd., trade name “VTSK-9400 Violet”] was used instead of the red colorant. In the same manner as in the production of the liquid, the mixture was mixed with the composition described in Table 1 to prepare a purple vinyl chloride resin organosol coating liquid. The composition is shown in Table 1.
参考例１〜６
工程フィルム［三菱ポリエステル社製、商品名「ＰＥＴ７５Ｔ−１００Ｅ」、剥離処理をしたポリエチレンテレフタレート樹脂製フィルム、厚み７５μｍ］の剥離処理面側に、赤色オルガノゾル、橙色オルガノゾル、黄色オルガノゾル、緑色オルガノゾル、青色オルガノゾル及び紫色オルガノソルの各塗工液を、それぞれ塗布、１４０℃で１分間予備乾燥して溶媒分を揮発させたのち、１９０℃で２分間加熱溶融ゲル化して、厚さ４０μｍの赤色、橙色、黄色、緑色、青色及び紫色の各フィルムを製膜した。各フィルムの光学特性を第２表に示す。
Reference Examples 1-6
Red organosol, orange organosol, yellow organosol, green organosol, blue organosol on the side of the release film of the process film [Mitsubishi Polyester, trade name “PET75T-100E”, release film of polyethylene terephthalate resin, thickness 75 μm] And purple organosol were applied, pre-dried at 140 ° C. for 1 minute to volatilize the solvent, and then heated, melted and gelled at 190 ° C. for 2 minutes, and red, orange, yellow with a thickness of 40 μm. Green, blue and purple films were formed. The optical properties of each film are shown in Table 2.
実施例１
工程フィルム［三菱ポリエステル社製、商品名「ＰＥＴ７５Ｔ−１００Ｅ」、剥離処理をしたポリエチレンテレフタレート樹脂製フィルム、厚み７５μｍ］の剥離処理面側に、赤色オルガノゾル塗工液を塗布、１４０℃で１分間予備乾燥して溶媒分を揮発させ厚さ４０μｍの着色上層フィルムを形成した。次に得られた着色上層フィルム上に、着色下層フィルムとなる紫色オルガノゾル塗工液を同様にして塗布し、１４０℃で１分間予備乾燥し、溶媒分を揮発させたのち、１９０℃で２分間加熱溶融ゲル化して着色積層シートを製膜した。着色下層フィルムの厚さは４０μｍであり、積層シートとしての厚さは８０μｍであった。
次に、剥離シート［リンテック社製、商品名「ＳＰ−１１ＰＭ」］の剥離処理面にアクリル系粘着剤［リンテック社製、商品名「Ｐ３２０Ｅ」］を塗布、乾燥させ透明粘着剤層（厚み３０μｍ）を形成した後、その剥離シート付き粘着剤層と上記得られた積層シートの着色下層フィルム側と貼り合わせて、粘着剤層付きマーキングシートを作製した。
Example 1
A red organosol coating solution is applied to the side of the release surface of the process film [Mitsubishi Polyester, trade name “PET75T-100E”, release-treated polyethylene terephthalate resin film, thickness 75 μm], preliminarily at 140 ° C. for 1 minute. After drying, the solvent content was volatilized to form a colored upper film having a thickness of 40 μm. Next, on the obtained colored upper layer film, a purple organosol coating solution to be a colored lower layer film was applied in the same manner, preliminarily dried at 140 ° C. for 1 minute, and the solvent was volatilized, and then at 190 ° C. for 2 minutes. A colored laminated sheet was formed by heat-melting gelation. The thickness of the colored lower layer film was 40 μm, and the thickness as a laminated sheet was 80 μm.
Next, an acrylic pressure-sensitive adhesive [product name “P320E” manufactured by LINTEC Co., Ltd.] is applied to the release-treated surface of the release sheet [product name “SP-11PM” manufactured by LINTEC Co., Ltd.] and dried to form a transparent pressure-sensitive adhesive layer (thickness 30 μm Then, the pressure-sensitive adhesive layer with the release sheet and the colored lower layer film side of the obtained laminated sheet were bonded together to prepare a marking sheet with the pressure-sensitive adhesive layer.
実施例２
赤色オルガノゾル塗工液を用いて着色上層フィルムを形成し、橙色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
実施例３
橙色オルガノゾル塗工液を用いて着色上層フィルムを形成し、赤色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
実施例４
緑色オルガノゾル塗工液を用いて着色上層フィルムを形成し、青色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
実施例５
青色オルガノゾル塗工液を用いて着色上層フィルムを形成し、緑色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
実施例６
青色オルガノゾル塗工液を用いて着色上層フィルムを形成し、紫色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
実施例７
紫色オルガノゾル塗工液を用いて着色上層フィルムを形成し、青色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
Example 2
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a red organosol coating solution and a colored lower layer film was formed using an orange organosol coating solution.
Example 3
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using an orange organosol coating solution and a colored lower layer film was formed using a red organosol coating solution.
Example 4
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a green organosol coating solution and a colored lower layer film was formed using a blue organosol coating solution.
Example 5
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a blue organosol coating solution and a colored lower layer film was formed using a green organosol coating solution.
Example 6
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a blue organosol coating solution and a colored lower layer film was formed using a purple organosol coating solution.
Example 7
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a purple organosol coating solution and a colored lower layer film was formed using a blue organosol coating solution.
比較例１
橙色オルガノゾル塗工液を用いて着色上層フィルムを形成し、黄色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
比較例２
黄色オルガノゾル塗工液を用いて着色上層フィルムを形成し、橙色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
比較例３
黄色オルガノゾル塗工液を用いて着色上層フィルムを形成し、緑色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
比較例４
緑色オルガノゾル塗工液を用いて着色上層フィルムを形成し、黄色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
比較例５
紫色オルガノゾル塗工液を用いて着色上層フィルムを形成し、赤色オルガノゾル塗工液を用いて着色下層フィルムを形成した以外は、実施例１と同様にしてマーキングシートを作製した。
前記実施例１〜７及び比較例１〜５で得られたマーキングシート（着色上層フィルムと着色下層フィルムからなる積層シート）について、光学特性を測定すると共に、官能テストを行った。結果を第３表に示す。
Comparative Example 1
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using an orange organosol coating solution and a colored lower layer film was formed using a yellow organosol coating solution.
Comparative Example 2
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a yellow organosol coating solution and a colored lower layer film was formed using an orange organosol coating solution.
Comparative Example 3
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a yellow organosol coating liquid and a colored lower layer film was formed using a green organosol coating liquid.
Comparative Example 4
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a green organosol coating solution and a colored lower layer film was formed using a yellow organosol coating solution.
Comparative Example 5
A marking sheet was prepared in the same manner as in Example 1 except that a colored upper layer film was formed using a purple organosol coating solution and a colored lower layer film was formed using a red organosol coating solution.
About the marking sheet (laminated sheet which consists of a colored upper layer film and a colored lower layer film) obtained in the said Examples 1-7 and Comparative Examples 1-5, while measuring an optical characteristic, the sensory test was done. The results are shown in Table 3.
実施例８
実施例１で作製した粘着マーキングシートの剥離シートを除去し、透光性被着体としてフレキシブルフェイス［泉社製、商品名「コスモフェイスＣＳ−５０１Ｆ」、乳白色、全光線透過率２５.８％］に貼付した。その後工程フィルムを剥離し、写真用ライトボックス(色温度５０００°Ｋ)上にフレキシブルフェイスが当接するように置き、外貼り型の電飾看板様の表示体を作製した。この表示体について反射光（外光）と透過光（内部照明）による目視テストを行った。
内部照明を消し、反射光のみの観察では、マーキングシートは赤く目視でき、内部照明を点灯し、透過光での観察では紫色に目視された。
Example 8
The release sheet of the adhesive marking sheet prepared in Example 1 was removed, and a flexible face [trade name “Cosmo Face CS-501F” manufactured by Izumi Co., Ltd., milky white, total light transmittance of 25.8% as a translucent adherend. ]. Thereafter, the process film was peeled off and placed on a photographic light box (color temperature 5000 ° K) so that the flexible face was in contact with it, and an externally-attached display board-like display body was produced. The display body was visually tested with reflected light (external light) and transmitted light (internal illumination).
When the internal illumination was turned off and only the reflected light was observed, the marking sheet was visible in red, the internal illumination was turned on, and the observation with transmitted light was visible in purple.
実施例９
温度計、撹拌機、還流冷却管、窒素ガス導入管を備えた反応装置を用い、ブチルアクリレート５０質量部、２−エチルヘキシルアクリレート４０質量部、酢酸ビニル１０質量部、アクリル酸５質量部、酢酸エチル７５質量部及びトルエン７５質量部を仕込み、アゾビスイソブチロニトリル０.３質量部を加え、窒素ガス雰囲気下８０℃で８時間重合した。反応終了後、質量平均分子量５０万である共重合体を得た。次いで該共重合体１００質量部にイソシアナート系架橋剤［東洋インキ製造社製、商品名「ＢＨＳ８５１５」］３質量部を配合し、トルエンで希釈し十分に撹拌して固形分４０質量％の透明アクリル系粘着剤の塗布剤とした。
実施例１で使用した工程フィルムの剥離処理面側に、赤色オルガノゾル塗工液を塗布、１４０℃で１分間予備乾燥して溶媒分を揮発させ厚さ４０μｍの着色下層フィルムを形成した。次に得られた着色下層フィルム上に、着色上層フィルムとなる橙色オルガノゾル塗工液を同様にして塗布し、１４０℃で１分間予備乾燥し、溶媒分を揮発させたのち、１９０℃で２分間加熱溶融ゲル化して着色積層シートを製膜した。着色上層フィルムの厚さは４０μｍであり、積層シートとしての厚さは８０μｍであった。
次に、剥離シート［リンテック社製、商品名「ＳＰ−１１ＰＭ」］の剥離処理面に上記粘着剤を塗布、乾燥させ透明粘着剤層（厚み３０μｍ）を形成した後、その剥離シート付き粘着剤層と上記得られた積層シートの着色上層フィルム側と貼り合わせて、粘着マーキングシートを作製した。
このようして作製した粘着マーキングシートの剥離シートを除去し、全光線透過率９３％、厚さ３ｍｍの透明アクリル樹脂板に貼付した。
その後工程フィルムを剥離し、写真用ライトボックス(色温度５０００°Ｋ)上に着色下層フィルムが当接するように置き、内貼り型の電飾看板様の表示体を作製した。この表示体について反射光（外光）と透過光（内部照明）による目視テストを行った。
内部照明を消し、反射光のみの観察では、マーキングシートは橙色に目視でき、内部照明を点灯し、透過光での観察では赤色に目視された。
Example 9
Using a reactor equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction tube, 50 parts by mass of butyl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of vinyl acetate, 5 parts by mass of acrylic acid, ethyl acetate 75 parts by mass and 75 parts by mass of toluene were charged, 0.3 part by mass of azobisisobutyronitrile was added, and polymerization was performed at 80 ° C. for 8 hours in a nitrogen gas atmosphere. After completion of the reaction, a copolymer having a mass average molecular weight of 500,000 was obtained. Next, 100 parts by mass of the copolymer is blended with 3 parts by mass of an isocyanate-based cross-linking agent [trade name “BHS8515” manufactured by Toyo Ink Manufacturing Co., Ltd.], diluted with toluene, sufficiently stirred, and transparent with a solid content of 40% by mass. It was set as the coating agent of acrylic adhesive.
A red organosol coating solution was applied to the side of the peel-treated surface of the process film used in Example 1 and preliminarily dried at 140 ° C. for 1 minute to evaporate the solvent and form a colored underlayer film having a thickness of 40 μm. Next, on the obtained colored lower layer film, an orange organosol coating liquid to be a colored upper layer film was applied in the same manner, preliminarily dried at 140 ° C. for 1 minute, and the solvent was volatilized, and then at 190 ° C. for 2 minutes. A colored laminated sheet was formed by heat-melting gelation. The thickness of the colored upper layer film was 40 μm, and the thickness as a laminated sheet was 80 μm.
Next, the pressure-sensitive adhesive was applied to the release-treated surface of a release sheet [manufactured by LINTEC, trade name “SP-11PM”] and dried to form a transparent pressure-sensitive adhesive layer (thickness 30 μm). The adhesive marking sheet was produced by laminating the layer and the colored upper film side of the obtained laminated sheet.
The release sheet of the pressure-sensitive adhesive marking sheet thus prepared was removed and attached to a transparent acrylic resin plate having a total light transmittance of 93% and a thickness of 3 mm.
Thereafter, the process film was peeled off, and placed on a photographic light box (color temperature 5000 ° K) so that the colored lower layer film was in contact therewith, thereby producing an internally-attached electric signboard-like display. The display body was visually tested with reflected light (external light) and transmitted light (internal illumination).
When the internal illumination was turned off and the observation was made only with the reflected light, the marking sheet was visible in orange, the internal illumination was turned on, and the observation with transmitted light was visible in red.
本発明のマーキングシートは、屋外広告などに用いられる電飾看板として、あるいは種々の物品の装飾・表示素材などとして使用することができる。 The marking sheet of the present invention can be used as an electric signboard used for outdoor advertising or as a decoration / display material for various articles.
１ａ 透光性被着体
１ｂ 透光性被着体
２ 着色上層フィルム
３ 着色下層フィルム
４ 粘着剤層
５ 積層シート
１０ａ マーキングシート
１０ｂ マーキングシート
DESCRIPTION OF SYMBOLS 1a Translucent adherend 1b Translucent adherend 2 Colored
Claims (5)
前記ゾルキャスト法に用いるオルガノゾル塗工液は、０．０１μｍ以上０．５μｍ未満の範囲の小さい平均粒径の樹脂微粒子と、０．５μｍ以上５μｍ以下の範囲の大きい平均粒径の樹脂微粒子とが混合されたものであり、
前記ゾルキャスト法により、工程フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して、前記着色上層フィルムを形成し、当該着色上層フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して前記着色下層フィルムを形成し、前記積層シートを得る工程、または、前記ゾルキャスト法により、工程フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して、前記着色下層フィルムを形成し、当該着色下層フィルム上に、前記オルガノゾル塗工液を塗布、乾燥して前記着色上層フィルムを形成し、前記積層シートを得る工程を有し、
前記二層積層シートの全光線透過率が２０％未満であり、かつ積層シートの反射光での色相と透過光での色相の差が、ＪＩＳ Ｚ ８７２９−１９９４によるＬ＊ａ＊ｂ＊表色系におけるａｂ色相角（ｈａｂ）で１０以上であり、
前記粘着剤層を構成する粘着剤は、ブチルアクリレート単位、及び又は２−エチルヘキシルアクリレート単位を主体とする樹脂成分と、イソシアナート系架橋剤とを含むアクリル系粘着剤であることを特徴とするマーキングシートの製造方法。 Colors and different colored top film a colored lower layer film together, depending on zone le casting, a manufacturing method of a laminated sheet formed by laminating two layers, providing an adhesive layer on the colored lower film side of the laminated sheet And
The organosol coating liquid used in the sol-cast method comprises resin fine particles having a small average particle diameter in the range of 0.01 μm or more and less than 0.5 μm, and resin fine particles having a large average particle diameter in the range of 0.5 μm or more and 5 μm or less. Are mixed,
By the sol-cast method, the organosol coating solution is applied onto the process film and dried to form the colored upper layer film, and the organosol coating solution is applied onto the colored upper layer film and dried. Forming the colored lower layer film, obtaining the laminated sheet, or applying the organosol coating liquid on the process film by the sol casting method and drying to form the colored lower layer film, On the film, the organosol coating solution is applied and dried to form the colored upper layer film, and the step of obtaining the laminated sheet is obtained.
The bilayer total light transmittance of the laminated sheet is less than 20%, and a color difference in hue and transmitted light in the reflected light of the laminated sheet, according to JIS Z 8729-1994 L * a * b * color specification Ri der 10 or more ab hue angle (hab) in the system,
Pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is characterized and a resin component that butyl acrylate units, and or the 2-ethylhexyl acrylate units and mainly, an acrylic adhesive der Rukoto comprising an isocyanate-based crosslinking agent Manufacturing method of marking sheet.
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