TWI664095B - Latent image printed matter of solid formulation, imaging method thereof and method for inspecting edible material - Google Patents
Latent image printed matter of solid formulation, imaging method thereof and method for inspecting edible material Download PDFInfo
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Abstract
本發明提供一種固體製劑的潛影印刷物及固體製劑的潛影印刷物之攝影方法,前述固體製劑的潛影印刷物於表面設置有潛影,該潛影可藉由特定之波長區域之紫外線照射而顯影化。 The invention provides a latent image printed matter of a solid preparation and a photographic method of the latent image printed matter of the solid preparation. The latent image printed matter of the solid preparation is provided with a latent image on a surface, and the latent image can be developed by ultraviolet radiation in a specific wavelength region. Into.
本發明之固體製劑的潛影印刷物係於表面的至少一部分設置有潛影之固體製劑10的潛影印刷物;其特徵在於,至少具有:潛影區域A,藉由潛影墨層11而形成有潛影,前述潛影墨層11吸收波長區域為200nm以上且未達400nm之範圍之紫外線;以及非潛影區域B,至少使上述波長區域之紫外線反射及/或發出螢光;並且對潛影區域A及非潛影區域B照射可見光之情形時之潛影區域A相對於非潛影區域B之階度值之差未達5,對潛影區域A及非潛影區域B照射至少包含上述波長區域之紫外線之光之情形時之潛影區域A相對於非潛影區域B之階度值之差為5以上。 The latent image printed matter of the solid preparation of the present invention is a latent image printed matter of the solid preparation 10 provided with the latent image on at least a part of the surface; it is characterized by having at least: a latent image area A formed by the latent image ink layer 11. The latent image, the aforementioned latent image ink layer 11 absorbs ultraviolet rays in a wavelength range of 200 nm to 400 nm; and the non-latent image region B, at least reflects and / or emits ultraviolet light in the aforementioned wavelength region; and When the area A and the non-latent image area B are irradiated with visible light, the difference between the order value of the latent image area A and the non-latent image area B is less than 5, and the exposure of the latent image area A and the non-latent image area B includes at least the above In the case of the ultraviolet light in the wavelength region, the difference between the order values of the latent image region A and the non-latent image region B is 5 or more.
Description
本發明係關於一種固體製劑的潛影印刷物及固體製劑的潛影印刷物之攝影方法,更詳細而言,係關於一種印刷有潛影之固體製劑的潛影印刷物及固體製劑的潛影印刷物之攝影方法,前述潛影可藉由特定之波長區域之紫外線照射而顯影化。另外,本發明係關於一種可食用物的檢查方法,更詳細而言,係關於一種於醫藥品等可食用物印刷有潛影之可食用物的檢查方法,前述潛影可藉由特定之波長區域之紫外線照射而顯影化。 The invention relates to a latent image printed matter of a solid preparation and a photographic method of a latent image printed matter of a solid preparation. More specifically, the present invention relates to a latent image printed matter of a solid preparation printed with a latent image and a latent image printed matter of a solid preparation. In the method, the aforementioned latent image can be developed by ultraviolet irradiation in a specific wavelength region. In addition, the present invention relates to a method for inspecting an edible substance, and more specifically, it relates to an inspection method for an edible substance having a latent image printed on the edible substance such as a pharmaceutical product. The area is developed by ultraviolet irradiation.
近年來,對於醫藥品等錠劑,以直接噴墨方式印刷藥劑名而表示之情況不斷增多。尤其是,噴墨方式可實現可變印刷(variable printing),亦即,對每個被記錄媒體印刷不同資訊,因此對於錠劑,除藥劑名以外,亦嘗試可變地印刷錠劑之批號或錠劑之使用期限、用於防止假藥之安全 碼等。 In recent years, there has been an increase in the number of pharmaceutical products such as pharmaceuticals that are indicated by direct inkjet printing. In particular, the inkjet method can achieve variable printing, that is, different information is printed for each recorded medium. Therefore, in addition to the drug name, for the tablet, an attempt has been made to variably print the batch number of the tablet or Expiry date of tablets, security code to prevent counterfeit medicines, etc.
另一方面,藥劑名以外之製品資訊通常係無需一般消費者或患者認識之資訊。因此,例如較理想為於可見光下通常不被一般消費者等視認。作為可實現此種印刷之墨(ink),例如可列舉可食用性墨,該可食用性墨包含核黃素類等,僅於被紫外線照射之情形時發生色相變化而可識別印刷圖像(參照下述專利文獻1)。另外,亦可列舉:將可食用性螢光染料溶解於溶媒而成之墨;或者色澱顏料墨,係使該螢光染料對於溶媒成為不溶性而色澱化,從而作為色澱有機顏料分散於溶媒中而成。 On the other hand, product information other than the name of the medicament is usually information that does not require general consumer or patient knowledge. Therefore, for example, it is preferable that it is generally not recognized by ordinary consumers under visible light. Examples of inks that can realize such printing include edible inks, which contain riboflavin and the like, and can recognize printed images only when the hue changes when they are irradiated with ultraviolet rays ( Refer to the following patent document 1). In addition, an ink obtained by dissolving an edible fluorescent dye in a solvent or a lake pigment ink is used to dissolve the fluorescent dye insolubilizing the solvent and dissolve it as a lake organic pigment. Made in solvent.
但是,該等墨存在如下問題:與使用氧化鐵等無機顏料之可食用性墨相比,耐光性較差。 However, these inks have a problem that they have poor light resistance compared to edible inks using inorganic pigments such as iron oxide.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2011-241312號公報。 [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-241312.
本發明係鑒於上述問題而完成,本發明之第一目的在於提供一種固體製劑的潛影印刷物及固體製劑的潛影印刷物之攝影方法,前述固體製劑於表面設置有潛影,該潛影 可藉由特定之波長區域之紫外線照射而顯影化。另外,本發明之第二目的在於提供一種可食用物的檢查方法,對於設置有潛影之可食用物,可以低成本簡便地進行該潛影之檢查或判別等。 The present invention has been made in view of the above problems, and a first object of the present invention is to provide a latent image print of a solid preparation and a photographic method of the latent image print of the solid preparation. The solid preparation is provided with a latent image on the surface, and the latent image can be borrowed. It is developed by irradiation with ultraviolet rays in a specific wavelength region. In addition, a second object of the present invention is to provide a method for inspecting an edible substance, and for an edible substance provided with a latent image, the latent image can be easily inspected or discriminated at a low cost.
本案發明者等為了解決上述問題,而對固體製劑的潛影印刷物、固體製劑的潛影印刷物之攝影方法及可食用物的檢查方法進行了研究,結果發現,藉由採用下述構成,可解決上述問題,從而完成了本發明。 In order to solve the above-mentioned problems, the inventors of the present case studied the latent image printed matter of the solid preparation, the photographic method of the latent image printed matter of the solid preparation, and the inspection method of the edible matter. The above problems have thus completed the present invention.
亦即,為了解決上述課題,本發明之固體製劑的潛影印刷物中,上述固體製劑於表面的至少一部分設置有潛影;上述固體製劑的潛影印刷物的特徵在於,至少具有:潛影區域,藉由吸收波長區域為200nm以上且未達400nm之範圍之紫外線的潛影墨層而形成有前述潛影;以及非潛影區域,至少使上述波長區域之紫外線反射及/或發出螢光;對上述潛影區域及上述非潛影區域照射可見光之情形時之上述潛影區域相對於上述非潛影區域之階度值之差未達5,對上述潛影區域及上述非潛影區域照射至少包含上述波長區域之紫外線之光之情形時之上述潛影區域相對於上述非潛影區域之階度值之差為5以上。 That is, in order to solve the above-mentioned problem, in the latent image print of the solid preparation of the present invention, at least a portion of the surface of the solid preparation is provided with a latent image; the latent image print of the solid preparation is characterized by having at least: a latent image region, The aforementioned latent image is formed by a latent image ink layer that absorbs ultraviolet rays in a wavelength range of 200 nm to 400 nm; and a non-latent image region that reflects at least the ultraviolet rays in the above wavelength region and / or emits fluorescence; When the latent image area and the non-latent image area are irradiated with visible light, the difference between the order value of the latent image area and the non-latent image area is less than 5; the latent image area and the non-latent image area are irradiated at least In the case where the ultraviolet light of the wavelength region is included, the difference in the order value of the latent image region with respect to the non-latent image region is 5 or more.
根據上述之構成,關於潛影區域,於對該潛影區域及 非潛影區域照射可見光(波長區域400nm至760nm)之情形時,該潛影區域相對於非潛影區域之階度值之差成為未達5。因此,於固體製劑的表面設置有潛影區域,該潛影區域藉由於可見光照射下難以視認之潛影墨層而形成有潛影。另一方面,潛影區域係由潛影墨層構成之區域,該潛影墨層吸收波長區域為200nm以上且未達400nm之範圍之紫外線。另外,非潛影區域係使上述波長區域之紫外線反射及/或將該紫外線吸收並轉換波長為其他紫外線區域或可見光區域而發出螢光之區域。進而,關於潛影區域,於對該潛影區域及非潛影區域照射紫外線之情形時,該潛影區域相對於該非潛影區域之階度值之差成為5以上。因此,潛影區域於紫外線照射下可使藉由潛影墨層所形成之潛影以良好的對比度顯影化。 According to the above configuration, regarding the latent image region, when the latent image region and the non-latent image region are irradiated with visible light (wavelength region 400 nm to 760 nm), the difference in the degree value of the latent image region with respect to the non-latent image region Become less than 5. Therefore, a latent image region is provided on the surface of the solid preparation, and the latent image region is formed by a latent image ink layer which is difficult to recognize under visible light irradiation. On the other hand, the latent image region is a region composed of a latent image ink layer, and the latent image ink layer absorbs ultraviolet rays in a wavelength range of 200 nm or more and less than 400 nm. In addition, the non-latent image region is a region that reflects ultraviolet rays in the above-mentioned wavelength region and / or absorbs and converts the ultraviolet rays to other ultraviolet regions or visible light regions to emit fluorescence. Furthermore, regarding the latent image region, when the latent image region and the non-latent image region are irradiated with ultraviolet rays, the difference in the degree value of the latent image region with respect to the non-latent image region becomes 5 or more. Therefore, the latent image area can be developed with a good contrast with the latent image formed by the latent image ink layer under the irradiation of ultraviolet rays.
於上述之構成中,較佳為於上述表面進一步設置有藉由吸收前述可見光之可見墨層而形成有可見圖像的其他非潛影區域,對上述非潛影區域及上述其他非潛影區域照射上述可見光之情形時之上述其他非潛影區域相對於上述非潛影區域之階度值之差為5以上。 In the above configuration, it is preferable that another non-latent image region where a visible image is formed by absorbing the visible ink layer of the visible light is further provided on the surface. When the visible light is irradiated, the difference between the order values of the other non-latent image regions and the non-latent image regions when the visible light is irradiated is 5 or more.
根據上述之構成,其他非潛影區域係藉由吸收可見光之可見墨層而形成有可見圖像之區域,對非潛影區域及其他非潛影區域照射可見光之情形時,其他非潛影區域相對於非潛影區域之階度值之差成為5以上。因此,於可見光照 射下可以良好的對比度視認由可見墨層構成之可見圖像。相對於此,藉由潛影油墨層所形成之潛影於可見光照射下難以視認,但另一方面,藉由潛影油墨層所形成之潛影於上述波長區域之紫外線照射下可以良好的對比度視認。因此,若為上述構成,則可根據資訊的內容等,以潛影或可見圖像之形式將資訊記錄於固體製劑表面,從而可提高資訊之記錄方法之自由度。 According to the above configuration, other non-latent image areas are areas where a visible image is formed by the visible ink layer absorbing visible light. When the non-latent image area and other non-latent image areas are irradiated with visible light, other non-latent image areas The difference in the gradation value with respect to the non-latent image area becomes 5 or more. Therefore, a visible image composed of a visible ink layer can be viewed with good contrast under visible light. In contrast, the latent image formed by the latent image ink layer is difficult to recognize under visible light irradiation, but on the other hand, the latent image formed by the latent image ink layer can have good contrast under ultraviolet radiation in the above-mentioned wavelength region. Recognize. Therefore, according to the above structure, information can be recorded on the surface of a solid preparation in the form of a latent image or a visible image according to the content of the information, etc., thereby improving the freedom of the method of recording the information.
進而,於上述之構成中,較佳為上述可見墨層係使上述波長區域之紫外線透過或反射之層,對上述非潛影區域及上述其他非潛影區域照射包含上述波長區域之紫外線之光之情形時之上述其他非潛影區域相對於上述非潛影區域之階度值之差未達5。 Furthermore, in the above configuration, it is preferable that the visible ink layer is a layer that transmits or reflects ultraviolet rays in the wavelength region, and irradiates the non-latent image region and the other non-latent image regions with ultraviolet light including the wavelength region. In this case, the difference between the order values of the other non-latent image areas and the non-latent image areas is less than 5.
根據上述之構成,可使於可見光之照射下能夠視認之可見圖像成為於包含紫外線之光之照射下難以視認之圖像。另外,潛影於可見光之照射下雖難以視認,但另一方面,潛影於包含紫外線之光之照射下藉由顯影化而能夠視認。因此,藉由變更所照射之光之波長區域,可實現可見圖像與潛影之反轉表示。結果,即便固體製劑上之可印刷之區域的面積小時仍可將更多的資訊記錄於該固體製劑表面。 According to the above configuration, a visible image that can be viewed under irradiation with visible light can be an image that is difficult to be viewed under irradiation with light including ultraviolet rays. In addition, although the latent image is difficult to see under the irradiation of visible light, on the other hand, the latent image can be seen by being developed under the irradiation of light containing ultraviolet rays. Therefore, by changing the wavelength region of the irradiated light, it is possible to realize the inverse representation of the visible image and the latent image. As a result, even if the area of the printable area on the solid preparation is small, more information can be recorded on the surface of the solid preparation.
於上述構成中,較佳為上述潛影墨層至少含有作為顏 料之氧化鈦粒子及/或氧化鋅粒子。藉由使潛影墨層中至少含有作為顏料之氧化鈦粒子及/或氧化鋅粒子,可使該潛影墨層表現出對紫外線之良好的光吸收性。另外,氧化鈦及氧化鋅符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準,因此生物致害性低。結果,可於醫藥品或食品等錠劑等固體製劑直接印刷潛影。進而,與使用染料之墨層相比,亦可謀求提高耐光性。 In the above configuration, the latent image ink layer preferably contains at least titanium oxide particles and / or zinc oxide particles as a pigment. By containing at least titanium oxide particles and / or zinc oxide particles as pigments in the latent image ink layer, the latent image ink layer can exhibit good light absorption to ultraviolet rays. In addition, titanium oxide and zinc oxide meet the standards of pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations stipulated in the Japanese Pharmacopoeia Law, and therefore have low biological hazards. As a result, latent images can be printed directly on solid preparations such as pharmaceuticals and tablets. Furthermore, compared with the ink layer using a dye, the light resistance can also be improved.
另外,於上述之構成中,較佳為上述潛影墨層對上述可見光具有光透過性或光反射性。藉由潛影墨層對可見光具有光透過性,可進一步減小對潛影區域及非潛影區域照射可見光之情形時之潛影區域相對於非潛影區域之階度值之差。結果,可進一步降低潛影區域之可見光照射下之識別性。另外,例如於非潛影區域為使可見光之至少一部分反射之區域之情形等,亦可藉由潛影墨層具有光反射性而降低可見光照射下之識別性。 Moreover, in the said structure, it is preferable that the said latent image ink layer has light transmittance or light reflectivity with respect to the said visible light. The latent image ink layer has light transmittance to visible light, which can further reduce the difference between the order values of the latent image area and the non-latent image area when the visible light is irradiated to the latent image area and the non-latent image area. As a result, the visibility under the visible light irradiation of the latent image region can be further reduced. In addition, for example, in a case where the non-latent image area is an area that reflects at least a portion of visible light, the visibility of the latent image ink layer can be reduced by the light reflectivity of the latent image ink layer.
為了解決上述之課題,本發明之固體製劑的潛影印刷物之攝影方法中,上述固體製劑係於表面的至少一部分設置有潛影;其特徵在於,上述固體製劑至少具有:潛影區域,設置吸收波長區域為200nm以上且未達400nm之範圍之紫外線之潛影墨層,藉由上述潛影墨層而形成有上述潛影;以及非潛影區域,至少使上述波長區域之紫外線反射及 /或發出螢光;對上述潛影區域及上述非潛影區域照射可見光之情形時之上述潛影區域相對於上述非潛影區域之階度值之差未達5,對上述潛影區域及上述非潛影區域照射包含上述波長區域之紫外線之光之情形時之上述潛影區域相對於上述非潛影區域之階度值之差為5以上;上述固體製劑的潛影印刷物之攝影方法包括:顯影化步驟,對上述潛影區域及上述非潛影區域照射至少包含上述波長區域之紫外線之照射光,使上述潛影區域之上述潛影顯影化;以及攝影步驟,接收上述照射光於上述非潛影區域所反射之反射光及/或於上述非潛影區域所產生之螢光,而對上述顯影化步驟中顯影化之上述潛影區域及上述非潛影區域進行攝影。 In order to solve the above-mentioned problem, in the method for photographing a latent image printed matter of the solid preparation of the present invention, the solid preparation is provided with a latent image on at least a part of the surface; the solid preparation has at least: a latent image area and is provided with absorption The latent image ink layer of the ultraviolet latent image ink layer having a wavelength range of 200 nm or more and less than 400 nm is formed with the latent image by the latent image ink layer; and the non-latent image region reflects at least the ultraviolet light in the wavelength region and / or Fluorescent light is emitted; when the latent image area and the non-latent image area are irradiated with visible light, the difference between the order value of the latent image area and the non-latent image area is less than 5; When the latent image area is irradiated with ultraviolet light including the wavelength range, the difference between the order value of the latent image area and the non-latent image area is 5 or more; the photography method of the latent image printed matter of the solid preparation includes: developing A step of irradiating the latent image region and the non-latent image region with irradiation light including at least the ultraviolet ray in the wavelength region to make the latent image Development of the latent image in the field; and a photographing step, receiving reflected light reflected by the irradiated light on the non-latent image area and / or fluorescent light generated on the non-latent image area, and developing the developing step. The above-mentioned latent image area and the non-latent image area are photographed.
根據上述構成,於成為攝影對象之固體製劑的表面設置有潛影區域,該潛影區域於可見光照射下相對於非潛影區域之階度值之差未達5。因此,潛影區域可形成於可見光照射下難以視認該潛影區域之潛影。另外,潛影區域係吸收波長區域為200nm以上且未達400nm之範圍之紫外線之區域。另一方面,非潛影區域係使上述波長區域之紫外線反射及/或發出螢光之區域。並且,潛影區域構成為:當對該潛影區域及非潛影區域照射包含上述波長區域之紫外線之光時,該潛影區域相對於該非潛影區域之階度值之差成為5以上。因此,於上述構成中,藉由對潛影區域及非潛影區域照射至少包含上述波長區域之紫外線之照射光,可 使該潛影區域以良好的對比度顯影化(顯影化步驟)。並且,於上述構成中,接收照射光於非潛影區域所反射之反射光及/或於非潛影區域所產生之螢光,而對經顯影化之潛影區域及非潛影區域進行攝影(攝影步驟)。藉此,例如為了防止製造偽造製品等,可藉由對以潛影形式形成有製品資訊等之固體製劑的印刷物,照射上述波長區域之紫外線,而使潛影容易地顯影化,從而可良好地進行該潛影之判別或檢查等。 According to the above configuration, a latent image region is provided on the surface of the solid preparation to be photographed, and the difference between the order values of the latent image region and the non-latent image region under visible light irradiation is not more than 5. Therefore, the latent image region can be formed in a latent image in which it is difficult to recognize the latent image region under visible light. The latent image region is a region that absorbs ultraviolet rays in a wavelength range of 200 nm or more and less than 400 nm. On the other hand, the non-latent image region is a region that reflects and / or emits ultraviolet light in the above-mentioned wavelength region. In addition, the latent image region is configured such that when the latent image region and the non-latent image region are irradiated with ultraviolet light including the above-mentioned wavelength region, a difference in the degree value of the latent image region with respect to the non-latent image region becomes 5 or more. Therefore, in the above configuration, the latent image region and the non-latent image region are irradiated with the irradiation light including at least the ultraviolet rays in the above-mentioned wavelength region, so that the latent image region can be developed with a good contrast (development step). Further, in the above configuration, the reflected light reflected from the non-latent image area and / or the fluorescent light generated from the non-latent image area are received, and the developed latent image area and the non-latent image area are photographed. (Photographing steps). Therefore, for example, in order to prevent the manufacture of fake products, the printed matter in which solid information such as product information is formed in the form of a latent image can be irradiated with ultraviolet rays in the above-mentioned wavelength region, so that the latent image can be easily developed. The identification or inspection of the latent image is performed.
於上述之構成中,較佳為上述顯影化步驟係僅使用波長區域為200nm以上且未達400nm之範圍之紫外線作為上述照射光之步驟。潛影墨層係吸收波長區域為200nm以上且未達400nm之範圍之紫外線之層,因此藉由將顯影化步驟中所使用之照射光設為僅有該波長區域之紫外線,可進一步增大潛影區域相對於非潛影區域之階度值之差,從而可以更良好的對比度謀求顯影化。 In the above configuration, it is preferable that the developing step is a step of using only ultraviolet rays having a wavelength range of 200 nm or more and less than 400 nm as the irradiation light. The latent image ink layer is a layer that absorbs ultraviolet rays in a wavelength range of 200 nm to less than 400 nm. Therefore, by setting the irradiation light used in the development step to only ultraviolet rays in the wavelength range, the potential can be further increased. The difference in the degree value of the shadow area with respect to the non-latent image area can be developed with better contrast.
另外,於上述之構成中,較佳為上述顯影化步驟中之上述照射光中所包含之上述紫外線之波長區域與上述攝影步驟中所接收之上述反射光及/或上述螢光之波長區域至少一部分重疊。藉此,可謀求攝影步驟中之受光量之增大,從而可對潛影區域及非潛影區域以良好的對比度進行攝影。 In addition, in the above configuration, it is preferable that the wavelength range of the ultraviolet light included in the irradiation light in the developing step and the wavelength range of the reflected light and / or the fluorescent light received in the photographing step are at least Some overlap. Thereby, the amount of light received in the photographing step can be increased, and the latent image area and the non-latent image area can be photographed with good contrast.
於上述之構成中,上述固體製劑進一步具有藉由吸收上述可見光之可見墨層而形成有可見圖像的其他非潛影區域,對上述非潛影區域及上述其他非潛影區域照射可見光之情形時之上述其他非潛影區域相對於上述非潛影區域之階度值之差為5以上,上述攝影步驟可設為亦對上述其他非潛影區域進行攝影之步驟。 In the above configuration, the solid preparation further has other non-latent image regions in which a visible image is formed by the visible ink layer absorbing the visible light, and the non-latent image region and the other non-latent image regions are irradiated with visible light. At that time, the difference between the order values of the other non-latent image areas and the non-latent image areas is 5 or more. The above-mentioned photographing step may be a step of also photographing the other non-latent image areas.
根據上述構成,亦可將於固體製劑的表面藉由吸收可見光之可見墨層而進一步形成有可見圖像者設為攝影對象。並且,於可見墨層例如為於上述波長區域之紫外線之照射下亦能夠視認之墨層之情形時,於攝影步驟中亦對設置有該可見墨層之其他非潛影區域進行攝影,藉此可進行可見墨層之檢查等。 According to the above configuration, a person who has a visible image formed on the surface of the solid preparation by absorbing a visible ink layer to form a visible image can be set as a photographic subject. In addition, when the visible ink layer is, for example, an ink layer that can be recognized even under the irradiation of ultraviolet rays in the above-mentioned wavelength region, other non-latent image regions provided with the visible ink layer are also photographed in the photographing step, thereby Can check the visible ink layer.
進而,於上述之構成中,較佳為上述可見墨層係使上述波長區域之紫外線透過或反射之層,對上述非潛影區域及上述其他非潛影區域照射包含上述波長區域之紫外線之光之情形時之上述其他非潛影區域相對於上述非潛影區域之階度值之差未達5,上述顯影化步驟係藉由亦對上述其他非潛影區域照射至少包含上述波長區域之紫外線之照射光,而使上述其他非潛影區域之可見圖像潛影化之步驟,上述攝影步驟係亦對上述顯影化步驟中潛影化之其他非潛影區域進行攝影之步驟。 Furthermore, in the above configuration, it is preferable that the visible ink layer is a layer that transmits or reflects ultraviolet rays in the wavelength region, and irradiates the non-latent image region and the other non-latent image regions with ultraviolet light including the wavelength region. In this case, the difference between the step values of the other non-latent image regions and the non-latent image regions is less than 5, and the developing step is also irradiating the other non-latent image regions with ultraviolet rays including at least the wavelength region. The step of irradiating light to latentize the visible images of the other non-latent image areas. The photographing step is also a step of photographing other non-latent image areas that are latently imaged in the developing step.
根據上述構成,其他非潛影區域藉由形成使上述波長區域之紫外線透過或反射之可見墨層,而於包含該紫外線之光之照射下使其他非潛影區域相對於非潛影區域之階度值之差成為未達5。因此,其他非潛影區域可於顯影化步驟中潛影化,而難以視認該其他非潛影區域。藉此,於攝影步驟中,可僅對顯影化步驟中經顯影化之潛影進行攝影,從而可防止該潛影之判別或檢查等受可見圖像阻礙。 According to the above configuration, by forming a visible ink layer that transmits or reflects ultraviolet rays in the above-mentioned wavelength region, the other non-latent image regions make other non-latent image regions relative to the non-latent image regions under the irradiation of light including the ultraviolet rays. The difference in degrees becomes less than 5. Therefore, other non-latent image regions can be latently imaged in the developing step, and it is difficult to recognize the other non-latent image regions. Thereby, in the photographing step, only the developed latent image in the developing step can be photographed, thereby preventing the identification or inspection of the latent image from being obstructed by visible images.
另外,於上述之構成中,較佳為使用上述潛影墨層中至少含有作為顏料之氧化鈦粒子及/或氧化鋅粒子者作為上述固體製劑。藉此,潛影墨層表現出對紫外線之良好的光吸收性,因此對潛影區域及非潛影區域照射至少包含200nm以上且未達400nm之波長區域之紫外線之照射光時,可實現該潛影區域之紫外線照射下之顯影化。另外,氧化鈦及氧化鋅符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準,因此生物致害性低。結果,可於醫藥品或食品等錠劑等固體製劑直接印刷潛影。進而,與使用染料之墨層相比,亦可謀求提高耐光性。 Moreover, in the said structure, it is preferable to use the said latent image ink layer as a solid preparation which contains at least a titanium oxide particle and / or a zinc oxide particle as a pigment. As a result, the latent image ink layer exhibits good light absorption to ultraviolet light. Therefore, when the latent image area and the non-latent image area are irradiated with ultraviolet light having a wavelength range of at least 200 nm and less than 400 nm, this can be achieved Development in the latent image area under ultraviolet irradiation. In addition, titanium oxide and zinc oxide meet the standards of pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations stipulated in the Japanese Pharmacopoeia Law, and therefore have low biological hazards. As a result, latent images can be printed directly on solid preparations such as pharmaceuticals and tablets. Furthermore, compared with the ink layer using a dye, the light resistance can also be improved.
另外,於上述之構成中,較佳為上述潛影墨層對可見光具有光透過性或光反射性。藉由潛影墨層對可見光具有光透過性,可進一步減小對潛影區域及非潛影區域照射可見光之情形時之潛影區域相對於非潛影區域之階度值之差 。結果,可進一步降低潛影區域之可見光照射下之識別性。另外,例如於非潛影區域為使可見光之至少一部分反射之區域之情形等,亦可藉由潛影墨層具有光反射性而降低可見光照射下之識別性。 Moreover, in the said structure, it is preferable that the said latent image ink layer has light transmittance or light reflectivity with respect to visible light. The latent image ink layer has light transmittance to visible light, which can further reduce the difference between the order values of the latent image area and the non-latent image area when the visible light is irradiated to the latent image area and the non-latent image area. As a result, the visibility under the visible light irradiation of the latent image region can be further reduced. In addition, for example, in a case where the non-latent image area is an area that reflects at least a portion of visible light, the visibility of the latent image ink layer can be reduced by the light reflectivity of the latent image ink layer.
為了解決上述之課題,本發明之可食用物的檢查方法中,上述可食用物係於表面的至少一部分設置有潛影;本發明之可食用物的檢查方法的特徵在於,上述可食用物至少具有:潛影區域,藉由潛影墨層而形成有上述潛影,前述潛影墨層吸收波長區域為200nm以上且未達400nm之範圍之紫外線;以及非潛影區域,藉由上述波長區域之紫外線之照射而發出可見光區域之螢光;上述可食用物的檢查方法包括:顯影化步驟,藉由對上述潛影區域及上述非潛影區域照射至少包含上述波長區域之紫外線之照射光,而於上述非潛影區域產生上述螢光,並且於上述潛影區域之潛影墨層吸收上述紫外線,藉此使該潛影區域之上述潛影顯影化;以及檢查步驟,以目視或藉由受光波長為可見光區域之攝影機構對上述顯影化步驟中顯影化之上述潛影進行攝影而進行檢查。 In order to solve the above problems, in the edible matter inspection method of the present invention, the edible matter is provided with a latent image on at least a part of the surface; the edible matter inspection method of the present invention is characterized in that the edible matter is at least a part The latent image region has the latent image formed by the latent image ink layer, and the latent image ink layer absorbs ultraviolet rays in a wavelength range of 200 nm to 400 nm; and a non-latent image region through the wavelength region. The ultraviolet light emits fluorescence in the visible light region; the inspection method of the edible material includes a developing step, and irradiates the latent image region and the non-latent image region with ultraviolet light including at least the wavelength region, The fluorescent light is generated in the non-latent image area, and the ultraviolet light is absorbed in the latent image ink layer in the latent image area, thereby developing the latent image in the latent image area; and an inspection step for visually or by The imaging mechanism whose light-receiving wavelength is in the visible light region photographs and inspects the latent image developed in the developing step.
根據上述構成,於成為檢查對象之可食用物的表面設置有非潛影區域及潛影區域,前述非潛影區域係於前述波長區域之紫外線照射之情形時,產生可見光區域之螢光之區域,前述潛影區域係藉由吸收波長區域為200nm以上且 未達400nm之範圍之紫外線之潛影墨層而形成有潛影。因此,於紫外線之照射下,以目視進行觀察,或使用受光波長為可見光區域(400nm至760nm)之攝影機構進行攝影之情形時,於非潛影區域產生螢光,因此作為亮度較高之區域被識別。另一方面,於潛影區域中,由於紫外線被吸收,故而未進行螢光激發。因此,於潛影區域未產生螢光,作為與非潛影區域相比亮度較低之區域被識別。因此,若對潛影區域及非潛影區域照射紫外線,則可使潛影區域之潛影以良好的對比度顯影化(顯影化步驟),於之後進行檢查步驟中可實現簡便的檢查。此處,顯影化步驟係藉由使非潛影區域中產生可見光區域之螢光而使潛影顯影化,因此於檢查步驟中可以目視進行潛影之檢查。或者,可使用受光波長為可見光區域之攝影機構進行。因此,無需使用紫外線相機等特殊的裝置作為攝影機構,而可容易地進行潛影之檢查等。另外,例如於需求者等欲確認以潛影之形式印刷之製品資訊等圖像之情形時,或者欲確認製品之真偽等之情形時,可以低成本簡便地對製品進行識別。 According to the above configuration, a non-latent image region and a latent image region are provided on the surface of the edible object to be inspected, and the non-latent image region is a region where fluorescence is generated in the visible light region when the ultraviolet light is irradiated in the wavelength region. The aforementioned latent image region is a latent image formed by a latent image ink layer that absorbs ultraviolet rays in a wavelength range of 200 nm to 400 nm. Therefore, in the case of visual observation under the irradiation of ultraviolet rays, or when photographing is performed using a photographing mechanism with a light receiving wavelength in the visible light region (400nm to 760nm), fluorescence is generated in the non-latent image region, so it is a region with higher brightness Identified. On the other hand, in the latent image region, since ultraviolet rays are absorbed, fluorescence excitation is not performed. Therefore, no fluorescence is generated in the latent image area, and it is identified as a region having a lower brightness than the non-latent image area. Therefore, if the latent image area and the non-latent image area are irradiated with ultraviolet rays, the latent image of the latent image area can be developed with a good contrast (developing step), and a simple inspection can be realized in a subsequent inspection step. Here, the developing step is to develop the latent image by generating fluorescent light in a visible light region in the non-latent image region. Therefore, the latent image can be visually inspected in the inspection step. Alternatively, it can be performed using an imaging mechanism that receives light in a visible light region. Therefore, it is not necessary to use a special device such as an ultraviolet camera as a photographing mechanism, and a latent image inspection can be easily performed. In addition, for example, when a customer wants to confirm images such as product information printed in the form of a latent image, or when they want to confirm the authenticity of the product, the product can be easily and cheaply identified.
於上述構成中,較佳為上述顯影化步驟係僅使用波長區域為200nm以上且未達400nm之範圍之紫外線作為上述照射光之步驟。潛影墨層係吸收波長區域為200nm以上且未達400nm之範圍之紫外線之層,因此藉由將顯影化步驟中所使用之照射光設為僅有該波長區域之紫外線,可進一步提高潛影區域相對於非潛影區域之對比度,從而可實現 更良好的顯影化。 In the above configuration, it is preferable that the developing step is a step of using only ultraviolet rays having a wavelength range of 200 nm or more and less than 400 nm as the irradiation light. The latent image ink layer is a layer that absorbs ultraviolet rays in a wavelength range of 200 nm to 400 nm. Therefore, by setting the irradiation light used in the development step to only ultraviolet rays in the wavelength region, the latent image can be further improved. The contrast of the area with respect to the non-latent image area, so that better development can be achieved.
於上述構成中,較佳為上述可食用物之潛影墨層至少含有作為顏料之氧化鈦粒子及/或氧化鋅粒子。藉由使潛影墨層中至少含有作為顏料之氧化鈦粒子及/或氧化鋅粒子,可使該潛影墨層表現出對紫外線之良好的光吸收性。另外,氧化鈦及氧化鋅符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準,因此生物致害性低。結果,可使用由醫藥品或食品等錠劑等構成之固體製劑作為可食用物,可將於前述固體製劑直接印刷有潛影之固體製劑設為檢查對象。進而,與使用染料之墨層相比,亦可謀求提高耐光性。 In the said structure, it is preferable that the latent image ink layer of the said edible contains at least a titanium oxide particle and / or a zinc oxide particle as a pigment. By containing at least titanium oxide particles and / or zinc oxide particles as pigments in the latent image ink layer, the latent image ink layer can exhibit good light absorption to ultraviolet rays. In addition, titanium oxide and zinc oxide meet the standards of pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations stipulated in the Japanese Pharmacopoeia Law, and therefore have low biological hazards. As a result, a solid preparation composed of a tablet such as a pharmaceutical or food can be used as an edible substance, and a solid preparation directly printed with a latent image on the solid preparation can be used as an inspection object. Furthermore, compared with the ink layer using a dye, the light resistance can also be improved.
於上述構成中,較佳為上述可食用物之潛影墨層為由水性墨構成之乾燥前或乾燥後之塗膜。於潛影墨層為乾燥前之由水性墨構成之塗膜之情形時,可容易地確認該塗膜之印刷狀態之良否而進行判別。例如,於藉由噴墨方式使用水性墨進行印刷之情形時,可容易地檢查是否有於自噴墨頭噴出之水性墨之液滴之噴附位置產生誤差或於印刷位置產生偏差。另外,亦可容易地檢查是否因噴墨頭之噴嘴缺陷而產生印刷不良。結果,可提供良率較先前提高之可食用物的潛影印刷物。另外,於潛影墨層為乾燥後之由水性墨構成之塗膜之情形時,於使用時等可容易地確認以潛影之形式印刷之製品資訊等或製品之真偽等。 In the above configuration, it is preferable that the latent image ink layer of the edible material is a coating film made of water-based ink before or after drying. When the latent image ink layer is a coating film made of water-based ink before drying, it can be easily confirmed whether the printing state of the coating film is good or not. For example, in the case of printing using water-based ink by an inkjet method, it is possible to easily check whether there is an error in the spraying position of the droplets of the water-based ink ejected from the inkjet head or a deviation in the printing position. In addition, it is also possible to easily check whether a printing defect occurs due to a nozzle defect of the inkjet head. As a result, a latent image print of an edible which has a higher yield than before can be provided. In addition, in the case where the latent image ink layer is a coating film made of water-based ink after drying, the product information printed in the form of a latent image or the authenticity of the product can be easily confirmed at the time of use.
於上述構成中,較佳為上述可食用物之潛影墨層對可見光具有光透過性。藉由潛影墨層對可見光具有光透過性,可進一步降低可見光照射下之潛影之識別性。 In the above configuration, it is preferable that the latent image ink layer of the edible material has light transmittance to visible light. The latent image ink layer has light permeability to visible light, which can further reduce the visibility of the latent image under visible light.
於上述構成中,較佳為上述顯影化步驟之照射光中所包含之紫外線之波長與上述潛影墨層中所吸收之紫外線之波長至少一部分重疊。 In the above configuration, it is preferable that a wavelength of ultraviolet rays included in the irradiation light in the developing step and a wavelength of ultraviolet rays absorbed in the latent image ink layer overlap at least a part.
根據本發明之固體製劑的潛影印刷物,藉由潛影墨層而形成有潛影之潛影區域構成為:於對該潛影區域及非潛影區域照射可見光之情形時,潛影區域相對於非潛影區域之階度(gradation)值之差成為未達5。因此,本發明之潛影印刷物中,於可見光照射下難以視認(識別)潛影。另外,潛影區域係藉由吸收波長區域為200nm以上且未達400nm之範圍之紫外線之潛影墨層而形成有潛影之區域,非潛影區域係使該波長區域之紫外線反射及/或發出螢光之區域。並且,潛影區域構成為:於對該潛影區域及非潛影區域照射紫外線之情形時,該潛影區域相對於該非潛影區域之階度值之差成為5以上。因此,根據本發明,可提供一種具有潛影之固體製劑的潛影印刷物,前述潛影可藉由上述波長區域之紫外線照射而以良好的對比度顯影化。 According to the latent image printed matter of the solid preparation of the present invention, the latent image area formed with the latent image ink layer by the latent image ink layer is configured such that when the latent image area and the non-latent image area are irradiated with visible light, the latent image area is relatively The difference in the gradation value in the non-latent image area becomes less than 5. Therefore, in the latent image print of the present invention, it is difficult to visually recognize (identify) the latent image under visible light irradiation. In addition, the latent image region is a region in which a latent image is formed by absorbing a latent image ink layer in which the wavelength region is 200 nm or more and less than 400 nm. The non-latent image region is an ultraviolet reflection and / or in the wavelength region. Areas that emit fluorescence. In addition, the latent image area is configured such that, when the latent image area and the non-latent image area are irradiated with ultraviolet rays, the difference in the degree value of the latent image area with respect to the non-latent image area becomes 5 or more. Therefore, according to the present invention, a latent image printed matter having a solid preparation having a latent image can be provided, and the latent image can be developed with good contrast by irradiation with ultraviolet rays in the above-mentioned wavelength region.
另外,根據本發明之固體製劑的潛影印刷物之攝影方法,藉由對固體製劑之潛影區域及非潛影區域照射至少包含上述波長區域之紫外線之照射光而使潛影顯影化後,接收於非潛影區域所反射之反射光及/或於非潛影區域所產生之螢光,而對經顯影化之潛影區域及非潛影區域進行攝影。因此,例如對於以防止製造偽造製品等為目的而以潛影之形式印刷有製品資訊等之固體製劑的印刷物,可藉由照射上述波長區域之紫外線而容易地使潛影顯影化而進行攝影。結果,根據本發明,可提供一種固體製劑的潛影印刷物之攝影方法,可容易地進行設置於固體製劑之潛影之判別或檢查等。 In addition, according to the photographic method of the latent image printed matter of the solid preparation of the present invention, the latent image is developed by irradiating the latent image area and the non-latent image area of the solid preparation with at least the above-mentioned wavelength range of ultraviolet light, and receiving the developed image The reflected light reflected in the non-latent image area and / or the fluorescent light generated in the non-latent image area are photographed for the developed latent image area and the non-latent image area. Therefore, for example, a printed matter in which a solid preparation is printed with product information and the like in the form of a latent image for the purpose of preventing the manufacture of a fake product, can be easily developed by irradiating ultraviolet rays in the above-mentioned wavelength region and photographed. As a result, according to the present invention, a method for photographing a latent image printed matter of a solid preparation can be provided, and the latent image provided on the solid preparation can be easily identified or inspected.
另外,根據本發明之可食用物的檢查方法,成為檢查對象之可食用物係包括潛影區域及非潛影區域之潛影印刷物,前述潛影區域藉由吸收200nm以上且未達400nm之波長區域之紫外線之墨層而形成有潛影,前述非潛影區域藉由照射該紫外線而產生可見光區域之螢光。對於此種潛影印刷物,於本案發明中,於顯影化步驟中照射紫外線,藉此於非潛影區域產生可見光區域之螢光。藉此,非潛影區域作為亮度較高之區域被識別。另一方面,潛影區域吸收紫外線,結果未產生螢光,因此作為與非潛影區域相比亮度較低之區域被識別。結果,潛影區域之潛影藉由良好的對比度差而顯影化。藉此,可不使用紫外線相機等特殊的攝影機構而容易地進行潛影之檢查等。另外,例如於需求者 等欲確認以潛影之形式印刷之製品資訊等圖像之情形時,或者欲確認製品之真偽等之情形時,可以低成本簡便地識別潛影。 In addition, according to the edible matter inspection method of the present invention, the edible matter to be inspected includes a latent image printed matter of a latent image region and a non-latent image region, and the aforementioned latent image region absorbs a wavelength of 200 nm or more and less than 400 nm. A latent image is formed by the ultraviolet ink layer in the region, and the non-latent image region generates fluorescence in a visible light region by irradiating the ultraviolet light. For such a latent image print, in the present invention, ultraviolet rays are irradiated in the developing step, thereby generating fluorescent light in a visible light region in a non-latent image region. Thereby, the non-latent image region is recognized as a region with higher brightness. On the other hand, since the latent image region absorbs ultraviolet rays and no fluorescence is generated, it is recognized as a region having lower brightness than the non-latent image region. As a result, the latent image in the latent image area is developed with a good contrast. This makes it possible to easily perform latent image inspection and the like without using a special imaging mechanism such as an ultraviolet camera. In addition, for example, in the case of a demander and the like who want to confirm images of product information printed in the form of a latent image, or when they want to confirm the authenticity of a product, the latent image can be easily identified at low cost.
10、20‧‧‧固體製劑 10, 20‧‧‧ solid preparation
11‧‧‧潛影墨層 11‧‧‧ Latent Shadow Ink Layer
12‧‧‧可見墨層 12‧‧‧ visible ink layer
21‧‧‧光照射機構 21‧‧‧light irradiation mechanism
22‧‧‧攝影機構 22‧‧‧Photographic Agency
23‧‧‧第一光學濾波器 23‧‧‧The first optical filter
24‧‧‧第二光學濾波器 24‧‧‧Second Optical Filter
A‧‧‧潛影區域 A‧‧‧ Sub-Image Area
B、D‧‧‧非潛影區域 B, D‧‧‧ non-latent image area
C‧‧‧其他非潛影區域 C‧‧‧Other non-latent image areas
圖1係以示意方式表示本發明之之一實施形態之固體製劑的潛影印刷物之說明圖。 FIG. 1 is an explanatory view schematically showing a latent image printed matter of a solid preparation according to an embodiment of the present invention.
圖2係表示固體製劑的潛影印刷物之攝影方法中所使用之攝影裝置之概略之示意圖。 FIG. 2 is a schematic diagram showing an outline of a photographing device used in a method for photographing a latent image printed matter of a solid preparation.
圖3係以示意方式表示本發明之另一實施形態之固體製劑的潛影印刷物之說明圖。 FIG. 3 is an explanatory view schematically showing a latent image printed matter of a solid preparation according to another embodiment of the present invention.
圖4係以示意方式表示本發明之又一實施形態之固體製劑的潛影印刷物之說明圖。 FIG. 4 is an explanatory view schematically showing a latent image printed matter of a solid preparation according to still another embodiment of the present invention.
圖5係表示各實施例及各比較例中所使用之水性墨組成物之190nm至500nm之範圍內之吸收光譜之曲線圖。 FIG. 5 is a graph showing an absorption spectrum in a range of 190 nm to 500 nm of the water-based ink composition used in each of Examples and Comparative Examples.
圖6係表示各實施例中所使用之水性墨組成物之260nm至800nm之範圍內之吸收光譜之曲線圖。 FIG. 6 is a graph showing an absorption spectrum in the range of 260 nm to 800 nm of the water-based ink composition used in each Example.
(實施形態1) (Embodiment 1)
<固體製劑的潛影印刷物> <Latent image print of solid preparation>
以下,對實施形態1之固體製劑的潛影印刷物(以下,稱為『潛影印刷物』)進行說明。圖1係以示意方式表示本實施形態之固體製劑的潛影印刷物之說明圖。 Hereinafter, a latent image printed matter (hereinafter, referred to as a "latent image printed matter") of the solid preparation of the first embodiment will be described. FIG. 1 is an explanatory view schematically showing a latent image printed matter of the solid preparation of the present embodiment.
如圖1所示,本實施形態之潛影印刷物於固體製劑10的表面的至少一部分設置有潛影墨層11。潛影墨層11形成作為潛影之印刷圖像。並且,本實施形態之潛影印刷物至少具有:潛影區域A,潛影墨層11形成潛影;以及非潛影區域B,未形成潛影。 As shown in FIG. 1, the latent image print of the present embodiment is provided with a latent image ink layer 11 on at least a part of the surface of the solid preparation 10. The latent image ink layer 11 forms a printed image as a latent image. In addition, the latent image printed matter of this embodiment has at least: a latent image area A where the latent image ink layer 11 forms a latent image; and a non-latent image area B where no latent image is formed.
於本說明書中,『固體製劑』的含義包括食品製劑及醫藥製劑,作為該固體製劑的形態,例如可列舉:OD錠(oral dispersing tablet;口腔分散錠)、素錠、FC錠(film coating tablet;膜衣錠)、糖衣錠等錠劑或膠囊劑。固體製劑10可為醫藥品用途,亦可為食品用途。作為食品用途之錠劑之例子,可列舉錠狀點心或補充品(supplement)等保健食品。固體製劑10中,錠劑於常溫下為固體狀,例如較佳為藉由將包含有效成分之錠劑材料壓縮及/或成形成一定形狀而製造之錠劑。錠劑的形狀並無特別限定,可採用任意的形狀。另外,錠劑可為醫藥品用途之錠劑,亦可為食品用途之錠劑。作為食品用途之錠劑之例子,可列舉錠狀點心或補充品等保健食品。 In this specification, the meaning of "solid preparation" includes food preparations and pharmaceutical preparations. Examples of the solid preparation include OD tablets (oral dispersing tablets), plain tablets, and FC tablets (film coating tablets). Film-coated tablets), sugar-coated tablets and other lozenges or capsules. The solid preparation 10 may be used for medicine or food. Examples of lozenges for food use include health foods such as lozenges and supplements. In the solid preparation 10, the lozenge is solid at normal temperature, for example, it is preferably a lozenge manufactured by compressing and / or forming a lozenge material containing an active ingredient into a certain shape. The shape of the tablet is not particularly limited, and any shape can be adopted. In addition, the lozenge may be a lozenge for pharmaceutical use or a lozenge for food use. Examples of lozenges for food use include health foods such as lozenges and supplements.
另外,於本說明書中,所謂『潛影』,意指於照射可見光(波長區域400nm至760nm)之環境下難以識別,於特定之條件下顯影化之圖像。進而,本說明書中之『潛影印刷物』意指於固體製劑10印刷有潛影作為印刷圖像之印刷物。 此處,以潛影之形式印刷之圖像例如可使用後述之噴墨用水性墨藉由噴墨方式等而印刷。再者,所謂利用噴墨方式之印刷,意指將噴墨用水性墨液自微細之噴墨頭以液滴之形式噴出,使該液滴固定於固體製劑10,而形成圖像之方式。 In addition, in this specification, a "latent image" means an image that is difficult to recognize under an environment irradiated with visible light (wavelength region of 400 nm to 760 nm) and developed under specific conditions. Further, the “latent image print” in this specification means a printed product in which a latent image is printed on the solid preparation 10 as a printed image. Here, the image printed in the form of a latent image can be printed by, for example, an inkjet method using an inkjet aqueous ink described later. In addition, the so-called inkjet printing means a method in which an inkjet aqueous ink is ejected from a fine inkjet head in the form of droplets, and the droplets are fixed to the solid preparation 10 to form an image.
[潛影區域] [Latent image area]
潛影區域A係藉由潛影墨層11而形成有潛影之區域,前述潛影墨層11吸收波長區域為200nm以上且未達400nm之範圍之紫外線。上述波長區域更佳為260nm以上且380nm以下之範圍,尤佳為280nm以上且360nm以下之範圍。另外,潛影墨層11較佳為對可見光具有光透過性。進而,潛影墨層11亦可對可見光具有光反射性。該情形時,例如如後所述,若非潛影區域B為使可見光之至少一部分反射之區域,則可藉由潛影墨層11較佳地形成潛影。再者,本說明書中之『光透過性』意指使所入射之可見光等之至少一部分透過之性質。另外,光透過性的含義除包括潛影墨層11為無色之情形以外亦包括為有色之情形。進而,本說明書中之『光反射性』意指使所入射之可見光等之至少一部分反射之性質。 The latent image region A is a region in which a latent image is formed by the latent image ink layer 11. The latent image ink layer 11 absorbs ultraviolet rays in a wavelength range of 200 nm or more and less than 400 nm. The above-mentioned wavelength region is more preferably in a range of 260 nm to 380 nm, and particularly preferably in a range of 280 nm to 360 nm. The latent image ink layer 11 is preferably light-transmissive to visible light. Furthermore, the latent image ink layer 11 may have light reflectivity with respect to visible light. In this case, for example, as will be described later, if the non-latent image area B is an area that reflects at least a portion of visible light, the latent image can be preferably formed by the latent image ink layer 11. In addition, "light transmittance" in this specification means the property which transmits at least a part of incident visible light etc. In addition, the meaning of light transmittance includes a case where it is colored, in addition to a case where the latent image ink layer 11 is colorless. Furthermore, "light reflectivity" in this specification means a property which reflects at least a part of incident visible light and the like.
於潛影區域A,亦可設置形成於可見光下能夠視認之圖像之可見墨層或塗層。藉由使潛影墨層11對可見光具有光透過性,則即便於可見墨層設置於該潛影墨層11之下層 之情形時,亦可確保該可見墨層之視認性。再者,關於可見墨層之詳情,於後段之實施形態2中進行敘述。作為塗層,例如可列舉:用以被覆潛影墨層11而進行保護之外覆層或底塗層。 In the latent image region A, a visible ink layer or coating layer formed on an image that can be viewed under visible light may also be provided. By making the latent image ink layer 11 transparent to visible light, the visibility of the visible ink layer can be ensured even when the visible ink layer is disposed below the latent image ink layer 11. The details of the visible ink layer will be described in the second embodiment. Examples of the coating layer include an overcoat layer and an undercoat layer that cover the latent image ink layer 11 for protection.
作為潛影墨層11,較佳為由噴墨用水性墨(詳情將於後文進行敘述)之乾燥皮膜構成之層。乾燥皮膜可藉由下述方式而形成,亦即,使用噴墨用水性墨,利用例如噴墨方式等直接印刷於固體製劑10表面。另外,較佳為於潛影墨層11中至少含有對上述波長區域之範圍之紫外線具有光吸收性之成分(以下,有時稱為『紫外線吸收成分』)。進而,紫外線吸收成分較佳為均勻地含有於潛影墨層11中。作為紫外線吸收成分,例如可列舉作為顏料之氧化鈦(TiO2)粒子或氧化鋅粒子等。再者,作為潛影墨層11的厚度,並無特別限定,可適宜地根據需要進行設定。 The latent image ink layer 11 is preferably a layer composed of a dry film of an inkjet water-based ink (the details will be described later). The dry film can be formed by directly printing on the surface of the solid preparation 10 using, for example, an inkjet aqueous ink using an inkjet method or the like. In addition, it is preferable that the latent image ink layer 11 contains at least a component (hereinafter, sometimes referred to as an “ultraviolet absorbing component”) having a light absorptivity to ultraviolet rays in the above-mentioned wavelength range. Furthermore, it is preferable that the ultraviolet absorbing component is uniformly contained in the latent image ink layer 11. Examples of the ultraviolet absorbing component include titanium oxide (TiO 2 ) particles and zinc oxide particles as pigments. The thickness of the latent image ink layer 11 is not particularly limited, and can be appropriately set as needed.
[非潛影區域] [Non-latent image area]
非潛影區域B係於至少包含上述波長區域之紫外線之光(以下,稱為『照射光』)照射之情形時,使該紫外線反射之區域。或者,非潛影區域B係吸收紫外線作為激發光而發出螢光之區域。非潛影區域B中所產生之螢光中亦可包含上述波長區域之範圍之紫外線或可見光區域之光等。另外,亦可包括產生波長與所照射之紫外線不同之紫外線作為螢光之情形。再者,非潛影區域B亦可為同時使紫外 線反射及產生螢光之區域。 The non-latent image region B is a region that reflects the ultraviolet light when it is irradiated with at least ultraviolet light (hereinafter, referred to as "irradiation light") in the above-mentioned wavelength region. Alternatively, the non-latent image region B is a region that absorbs ultraviolet rays as excitation light and emits fluorescent light. The fluorescent light generated in the non-latent image region B may also include ultraviolet rays in the above-mentioned wavelength region or light in the visible region. In addition, it may include a case where ultraviolet rays having a wavelength different from that of the irradiated ultraviolet rays are generated as fluorescent light. Furthermore, the non-latent image area B may be an area that simultaneously reflects ultraviolet rays and generates fluorescence.
此處,本說明書中之『螢光』意指於200nm以上且未達400nm之波長區域之紫外線(激發光)照射之情形時,將該紫外線吸收並進行轉換波長,從而以螢光之形式發出不同波長之紫外線或可見光(380nm至760nm)。另外,其意義亦包含在紫外線之照射後仍發出之殘光中的衰減時間短之成分之螢光。另外,所謂衰減時間,意指自上述成分之發光開始至恢復為基底狀態(螢光消失)為止之躍遷所需要之時間。 Here, "fluorescence" in this specification means that when ultraviolet rays (excitation light) are irradiated in a wavelength range of 200 nm to 400 nm, the ultraviolet rays are absorbed and converted into wavelengths, so that they are emitted in the form of fluorescence. Different wavelengths of ultraviolet or visible light (380nm to 760nm). In addition, its significance also includes the fluorescence of components with short decay time in the residual light that is still emitted after the irradiation of ultraviolet rays. In addition, the decay time means the time required for the transition from the start of the emission of the above-mentioned components to the return to the ground state (the disappearance of fluorescence).
為了使非潛影區域B對200nm以上且未達400nm之波長區域之紫外線具備光反射性,例如較佳為於固體製劑10中含有用以使該波長區域之紫外線反射之成分。關於該方面,例如由於通常市售之白色性之錠劑或膠囊劑等具有使上述波長區域之紫外線反射之性質,故而可形成非潛影區域B。再者,即便於固體製劑10本身含有氧化鈦或氧化鋅等紫外線吸收成分之情形時,藉由將含有對上述波長區域之紫外線顯示光反射性之成分之紫外線反射層設置於固體製劑10表面,可形成非潛影區域B。或者,藉由控制潛影墨層11中所含之氧化鈦粒子或氧化鋅粒子等之粒徑,使潛影墨層11對紫外線之吸收波長與固體製劑10中所含之氧化鈦或氧化鋅等之吸收波長不同,亦可形成非潛影區域B。 In order for the non-latent image region B to have light reflectivity for ultraviolet rays in a wavelength range of 200 nm to 400 nm, for example, it is preferable that the solid preparation 10 contains a component for reflecting ultraviolet rays in the wavelength region. In this regard, for example, a commercially available white tablet or capsule has the property of reflecting ultraviolet rays in the above-mentioned wavelength region, so that a non-latent image region B can be formed. Furthermore, even when the solid preparation 10 itself contains ultraviolet absorbing components such as titanium oxide or zinc oxide, an ultraviolet reflecting layer containing a component that exhibits light reflectivity to ultraviolet rays in the above-mentioned wavelength region is provided on the surface of the solid preparation 10, Non-latent image area B can be formed. Alternatively, by controlling the particle size of the titanium oxide particles or zinc oxide particles contained in the latent image ink layer 11, the absorption wavelength of ultraviolet light by the latent image ink layer 11 and the titanium oxide or zinc oxide contained in the solid preparation 10 are controlled. Non-latent image regions B can also be formed with different absorption wavelengths.
另外,為了使非潛影區域B具備於照射上述波長區域之範圍之紫外線之情形時顯示螢光性之性質,例如較佳為於固體製劑10中含有吸收該波長區域之紫外線作為激發光而發出螢光之螢光成分。作為此種螢光成分,只要為具有可食用性之成分,則並無特別限定,具體而言,例如可列舉核黃素等。該等螢光成分可單獨使用1種或混合2種以上而使用。再者,即便於固體製劑10本身含有氧化鈦或氧化鋅等紫外線吸收成分之情形時,藉由針對上述波長區域之紫外線將含有螢光成分之螢光層設置於固體製劑10表面,亦可形成非潛影區域B。此處,本說明書中之『螢光性』意指發出螢光之性質。另外,於本說明書中,所謂『可食用性』,意指僅由作為醫藥品或醫藥品添加物確認可經口投予之物質、及/或確認為食品或食品添加物之物質構成。 In addition, in order to provide the non-latent image region B with the property of exhibiting fluorescence when irradiated with ultraviolet rays in the above-mentioned wavelength region, for example, it is preferable that the solid preparation 10 contains ultraviolet rays that absorb the wavelength region as excitation light to be emitted. Fluorescent component of fluorescence. Such a fluorescent component is not particularly limited as long as it is an edible component, and specific examples thereof include riboflavin and the like. These fluorescent components can be used individually by 1 type or in mixture of 2 or more types. Furthermore, even when the solid preparation 10 itself contains an ultraviolet absorbing component such as titanium oxide or zinc oxide, it can be formed by providing a fluorescent layer containing a fluorescent component on the surface of the solid preparation 10 with respect to the ultraviolet rays in the above-mentioned wavelength region. Non-latent image area B. Here, "fluorescence" in this specification means the property of emitting fluorescence. In addition, in this specification, "edible" means that it is comprised only of the substance confirmed as oral administration as a medicinal product or a medicinal additive, and / or the substance confirmed as a food or a food additive.
另外,非潛影區域B亦可包括於可見光之照射下使該可見光之至少一部分反射或吸收之情形。另外,於非潛影區域B亦可設置塗層等。 In addition, the non-latent image region B may include a case where at least a part of the visible light is reflected or absorbed under the irradiation of visible light. A coating or the like may be provided in the non-latent image region B.
[潛影區域及非潛影區域之階度值之差] [Difference between order values of latent image area and non-latent image area]
對潛影區域A及非潛影區域B同時照射可見光之情形時之潛影區域A相對於非潛影區域B之階度值之差較佳為未達5。藉由將階度值之差設為未達5,可使於可見光照射下視認(或識別)潛影(潛影墨層11)變得困難或減少。 In the case where the latent image area A and the non-latent image area B are simultaneously irradiated with visible light, the difference between the order values of the latent image area A and the non-latent image area B is preferably less than 5. By setting the difference between the gradation values to less than 5, it is possible to make it difficult to recognize (or identify) the latent image (latent image ink layer 11) under visible light irradiation.
於本說明書中,所謂『階度值』,係表示所攝影之圖像之濃淡之值,意指將圖像資料藉由簡單平均法、加權平均法或中間值法等轉換為灰度(gray scale)所獲得之8位元之階度值(0至255之256個階段之值)。另外,於本說明書中,所謂『階度值之差』,意指自潛影區域A之階度值之平均值減去非潛影區域B之階度值之平均值所得之值。進而,所謂階度值之平均值,意指潛影區域A或非潛影區域B之圖像資料中多個像素之階度值之平均值。 In this specification, the so-called "gradation value" refers to the value of the lightness or darkness of a photographed image, which means that the image data is converted into grayscale by a simple average method, a weighted average method, or a median method. scale) An 8-bit scale value (a value of 256 stages from 0 to 255). In the present specification, the "difference in gradation value" means a value obtained by subtracting the average value of the gradation value of the non-latent image area B from the average value of the gradation value of the latent image area A. Furthermore, the average value of the gradation value means the average value of the gradation values of a plurality of pixels in the image data of the latent image area A or the non-latent image area B.
對潛影區域A及非潛影區域B同時照射至少包含紫外線之照射光之情形時之潛影區域A相對於非潛影區域B之階度值之差為5以上,較佳為15以上,更佳為30以上。藉由將階度值之差設為5以上,於紫外線照射下可使潛影區域A顯影化而進行觀察。 When the latent image area A and the non-latent image area B are simultaneously irradiated with irradiation light containing at least ultraviolet rays, the difference in the degree value of the latent image area A with respect to the non-latent image area B is 5 or more, preferably 15 or more, More preferably, it is 30 or more. By setting the difference in the gradation value to 5 or more, the latent image region A can be developed and observed under ultraviolet irradiation.
照射照射光之情形時之潛影區域A及非潛影區域B中之階度值例如可藉由調節該照射光之光強度而控制。具體而言,藉由適當地控制照射光之光強度,可使潛影區域A與非潛影區域B之階度值之差最大化,從而實現更清晰的攝影。例如,於因照射光之光源之光強度過弱而潛影區域A與非潛影區域B之階度值均成為小值且階度值之差小之情形時,可藉由增大光源之光強度而增大階度值之差。另外,於光源之光強度過大而攝影過度曝光,潛影區域A與非潛影區域B之階度值均成為大值且階度值之差大之情形 時,可藉由減小光源之光強度而增大階度值之差。另外,潛影區域A相對於非潛影區域B之階度值之差除藉由照射光之光強度以外,亦可藉由與照射光中至少包含之紫外線之波長之最佳組合而控制。或者,亦可藉由調節潛影墨層11中所含之紫外線吸收成分之濃度,而使潛影區域A中之紫外線吸收能力提高或降低,從而控制潛影區域A相對於非潛影區域B之階度值之差。 The gradation values in the latent image area A and the non-latent image area B when the irradiation light is irradiated can be controlled by, for example, adjusting the light intensity of the irradiation light. Specifically, by appropriately controlling the light intensity of the irradiated light, the difference between the gradation values of the latent image area A and the non-latent image area B can be maximized, thereby achieving clearer photography. For example, when the light intensity of the light source irradiating the light is too weak, the order values of the latent image area A and the non-latent image area B both become small and the difference between the order values can be increased. Light intensity increases the difference in gradation values. In addition, when the light intensity of the light source is too large and the photography is overexposed, the order values of the latent image area A and the non-latent image area B both become large and the difference between the order values can be reduced. The intensity increases the difference in the order value. In addition, the difference in the gradation value of the latent image area A with respect to the non-latent image area B can be controlled by an optimal combination with the wavelength of at least ultraviolet rays included in the irradiated light, in addition to the light intensity of the irradiated light. Alternatively, by adjusting the concentration of the ultraviolet absorbing component contained in the latent image ink layer 11, the ultraviolet absorbing ability in the latent image area A can be increased or decreased, thereby controlling the latent image area A relative to the non-latent image area B. The difference in the degree value.
[潛影用水性墨] [Latent image water-based ink]
作為形成潛影區域A之潛影墨層11之構成材料,於本實施形態中,較佳為使用具有可食用性之潛影用水性墨。潛影用水性墨包含潛影用水性墨組成物,該潛影用水性墨組成物至少含有顏料組成物(詳情將於後文進行敘述)、及作為主溶媒之水。另外,本實施形態之潛影用水性墨組成物具有可食用性且適合用作噴墨記錄用。進而,潛影用水性墨組成物使用顏料作為有色材料,因此與使用染料之墨組成物相比,於顯色性或耐光性、耐水性等方面優異。 As a constituent material of the latent image ink layer 11 forming the latent image region A, in this embodiment, it is preferable to use an edible latent image water-based ink. The latent image water-based ink includes a latent image water-based ink composition. The latent image water-based ink composition contains at least a pigment composition (the details will be described later) and water as a main solvent. In addition, the latent image aqueous ink composition according to this embodiment is edible and is suitable for inkjet recording. Furthermore, since the latent image water-based ink composition uses a pigment as a colored material, it is superior in color development properties, light resistance, and water resistance compared to an ink composition using a dye.
顏料組成物的含量相對於潛影用水性墨組成物的總質量以顏料分換算計較佳為2質量%至40質量%之範圍,更佳為5質量%至30質量%之範圍內。藉由將顏料組成物的含量設為2質量%以上,可使著色力提高。另一方面,藉由將顏料組成物的含量設為40質量%以下,可使分散性提高。 The content of the pigment composition is preferably in a range of 2% to 40% by mass, and more preferably in a range of 5% to 30% by mass, based on the total mass of the latent image water-based ink composition. By setting the content of the pigment composition to 2% by mass or more, the coloring power can be improved. On the other hand, when the content of the pigment composition is 40% by mass or less, dispersibility can be improved.
本實施形態之潛影用水性墨組成物中,含有水(作為主溶媒之水)。作為水,較佳為使用離子交換水、超過濾水、逆滲透水、蒸餾水等純水、或超純水等去除了離子性雜質之水。尤其是,藉由照射紫外線或添加過氧化氫等而進行了殺菌處理之水可長期防止黴或菌之產生,故而較佳。另外,作為水的含量,並無特別限定,可適宜地根據需要進行設定。 The water-based ink composition of the latent image of this embodiment contains water (water as a main solvent). As the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, or distilled water, or water from which ionic impurities have been removed, such as ultra-pure water, is preferably used. In particular, water subjected to a sterilization treatment by irradiating ultraviolet rays or adding hydrogen peroxide is preferable because it can prevent the generation of mold or bacteria for a long period of time. The content of water is not particularly limited, and can be appropriately set as needed.
本實施形態之潛影用水性墨組成物中,亦可調配其他添加劑。但是,於用作針對醫藥品等錠劑之噴墨用墨之情形時,較佳為符合日本藥事法等基準之添加劑。 In the water-based ink composition of the latent image of this embodiment, other additives may be blended. However, when it is used as an inkjet ink for tablets such as pharmaceuticals, it is preferably an additive that complies with standards such as the Japanese Pharmaceutical Affairs Law.
作為添加劑,可列舉:表面張力調整劑、濕潤劑(抗乾燥劑)、抗褪色劑、乳化穩定劑、滲透促進劑、紫外線吸收劑、防腐劑、防黴劑、pH值調整劑、黏度調整劑、分散穩定劑、防鏽劑、螯合劑等公知的添加劑。該等各種添加劑的含量並無特別限定,可適宜地根據需要進行設定。 Examples of the additives include a surface tension adjuster, a wetting agent (anti-drying agent), an anti-fading agent, an emulsifying stabilizer, a penetration enhancer, an ultraviolet absorber, a preservative, a mold inhibitor, a pH adjuster, and a viscosity adjuster. , Well-known additives such as dispersion stabilizers, rust inhibitors, and chelating agents. The content of these various additives is not particularly limited, and can be appropriately set as needed.
作為表面張力調整劑,只要為符合日本藥事法等基準之化合物,則並無特別限定,具體而言,例如可列舉:甘油脂肪酸酯、聚甘油脂肪酸酯等。作為甘油脂肪酸酯,例如可列舉:辛酸十甘油酯、月桂酸十甘油酯等。 The surface tension adjusting agent is not particularly limited as long as it is a compound that complies with standards such as the Japanese Pharmaceutical Affairs Law. Specific examples include glycerin fatty acid esters and polyglycerol fatty acid esters. Examples of the glycerin fatty acid ester include deca glyceryl caprylate and deca glyceryl laurate.
表面張力調整劑之添加量較佳為可將潛影用水性墨組 成物的表面張力調整為25mN/m至40mN/m之範圍,更佳為可調整為27mN/m至36mN/m之範圍。若添加量為上述範圍內,則可謀求確保利用噴墨方式之印刷時之噴出穩定性等。 The addition amount of the surface tension adjusting agent is preferably such that the surface tension of the latent image water-based ink composition can be adjusted to a range of 25 mN / m to 40 mN / m, and more preferably can be adjusted to a range of 27 mN / m to 36 mN / m. When the addition amount is within the above range, it is possible to ensure the discharge stability and the like during printing by the inkjet method.
作為濕潤劑,只要為符合日本藥事法等基準之化合物,則並無特別限定,具體而言,例如可列舉:丙二醇、甘油等。 The wetting agent is not particularly limited as long as it is a compound that complies with standards such as the Japanese Pharmaceutical Affairs Law. Specific examples include propylene glycol, glycerin, and the like.
濕潤劑之添加量相對於潛影用水性墨組成物的總質量,較佳為3質量%至50質量%,更佳為10質量%至40質量%。 The added amount of the humectant is preferably 3% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass relative to the total mass of the latent image water-based ink composition.
關於本實施形態之潛影用水性墨組成物的黏度,若考慮自噴墨噴嘴之噴出穩定性,則於噴墨噴嘴噴出時,較佳為2mPa‧s至7mPa‧s,更佳為3mPa‧s至5mPa‧s。藉由將潛影用水性墨組成物的黏度設為上述數值範圍內,可抑制於噴墨噴嘴產生堵塞而謀求維持良好之噴出穩定性,抑制飛翔性之降低。再者,潛影用水性墨組成物的黏度例如藉由下述方式而獲得,亦即,使用黏度計(商品名:VISCOMATE MODEL VM-10A,Sekonic(股份公司)製造),於測定溫度25℃之條件下進行測定。 Regarding the viscosity of the water-based ink composition of the latent image according to this embodiment, if the discharge stability from the inkjet nozzle is considered, it is preferably 2mPa‧s to 7mPa‧s, and more preferably 3mPa‧ when spraying from the inkjet nozzle. s to 5mPa‧s. By setting the viscosity of the water-based ink composition of the latent image to be within the above-mentioned numerical range, clogging of the inkjet nozzle can be suppressed, and good ejection stability can be maintained, and reduction in flying properties can be suppressed. The viscosity of the latent image water-based ink composition is obtained, for example, by using a viscometer (trade name: VISCOMATE MODEL VM-10A, manufactured by Sekonic (Stock Corporation)) at a measurement temperature of 25 ° C. The measurement was performed under the conditions.
本實施形態之潛影用水性墨組成物可藉由將前述之各 成分利用適宜的方法混合而製造。亦即,例如於顏料組成物之分散液中另行加入添加劑等,進而利用水進行稀釋。其後,充分地進行攪拌,根據需要進行用以去除成為堵塞之原因之粗大粒子及異物之過濾。藉此,可獲得本實施形態之潛影用水性墨組成物。 The latent image water-based ink composition of this embodiment can be produced by mixing the aforementioned components by an appropriate method. That is, for example, an additive or the like is separately added to the dispersion liquid of the pigment composition, and then diluted with water. After that, the mixture is sufficiently stirred, and if necessary, filtration is performed to remove coarse particles and foreign matter that may cause clogging. Thereby, the latent image water-based ink composition of this embodiment can be obtained.
再者,作為各材料之混合方法,並無特別限定,例如於具備機械攪拌器、磁力攪拌器等攪拌裝置之容器中依序添加材料而進行攪拌混合。另外,作為過濾方法,並無特別限定,例如可採用離心過濾、過濾器過濾等。 The method of mixing the materials is not particularly limited. For example, materials are sequentially added to a container provided with a stirring device such as a mechanical stirrer or a magnetic stirrer, and the mixture is stirred and mixed. The filtration method is not particularly limited, and for example, centrifugal filtration or filter filtration can be used.
本實施形態之潛影用水性墨組成物由符合日本藥事法等基準之成分構成,故而具有可食用性,可直接印刷於醫藥品或補充品等錠劑的表面。另外,針對素錠或OD錠等表面的平滑性差之錠劑,亦可進行利用噴墨方式而行之非接觸印刷。進而,潛影用水性墨組成物由於耐光性亦優異,故而即便直接印刷於醫藥品或補充品等錠劑的表面,亦可防止滲出之產生。 The latent image water-based ink composition of this embodiment is composed of ingredients that conform to standards such as the Japanese Pharmaceutical Affairs Law, so it is edible and can be directly printed on the surface of tablets such as pharmaceuticals or supplements. In addition, for tablets with poor surface smoothness such as plain tablets or OD tablets, non-contact printing using inkjet methods can also be performed. Furthermore, since the latent image water-based ink composition is also excellent in light resistance, even if it is directly printed on the surface of a tablet such as a pharmaceutical or a supplement, the occurrence of bleeding can be prevented.
[顏料組成物] [Pigment composition]
潛影用水性墨組成物中所包含之顏料組成物係至少含有由氧化鈦(TiO2)粒子及/或氧化鋅粒子構成之顏料(紫外線吸收成分)、及作為顏料分散劑之聚丙烯酸鈉之顏料分散體之組成物。首先,對使用氧化鈦粒子作為具有作為紫外 線吸收成分之功能之顏料之情形進行說明。 The pigment composition contained in the latent image water-based ink composition contains at least a pigment (ultraviolet absorbing component) composed of titanium oxide (TiO 2 ) particles and / or zinc oxide particles, and sodium polyacrylate as a pigment dispersant. Composition of pigment dispersion. First, a case where titanium oxide particles are used as a pigment having a function as an ultraviolet absorbing component will be described.
由氧化鈦粒子構成之顏料為白色顏料,與其他公知的白色顏料相比,比重較小,折射率較大。另外,氧化鈦之顏料的化學性質及物理性質亦穩定。因此,由氧化鈦粒子構成之顏料的隱蔽性或著色性優異,且對酸或鹼、其他環境之耐久性亦優異。再者,本實施形態之顏料組成物中除顏料以外亦可含有公知的顏料。 The pigment composed of titanium oxide particles is a white pigment, which has a smaller specific gravity and a larger refractive index than other known white pigments. In addition, the chemical and physical properties of titanium oxide pigments are also stable. Therefore, a pigment composed of titanium oxide particles is excellent in concealability or colorability, and is also excellent in durability against acids, alkalis, and other environments. In addition, the pigment composition of this embodiment may contain a well-known pigment other than a pigment.
本實施形態中,作為氧化鈦粒子,可使用結晶結構為銳鈦礦(Anatase)型(正方晶)、金紅石(rutile)型(正方晶)或板鈦礦(brookite)型(斜方晶)之任一種氧化鈦粒子。但是,就印刷圖像的隱蔽性提高之觀點而言,較佳為金紅石型結晶結構之氧化鈦。藉此,可防止印刷圖像自該印刷圖像之被印刷(形成)面以目視被觀察到。再者,本發明中,所謂氧化鈦粒子,只要無特別說明,則意指結晶性之氧化鈦粒子。 In this embodiment, as the titanium oxide particles, an anatase (anatase), rutile (orthorhombic), or brookite (orthorhombic) crystal structure can be used. Any of titanium oxide particles. However, from the viewpoint of improving the concealment of a printed image, titanium oxide having a rutile crystal structure is preferred. This prevents the printed image from being visually observed from the printed (formed) surface of the printed image. In the present invention, the titanium oxide particles mean crystalline titanium oxide particles unless otherwise specified.
氧化鈦粒子的表面較佳為親水性。藉此,可使所分散之氧化鈦粒子的平均分散粒徑接近於該氧化鈦粒子的平均一次粒徑(詳情將於後文進行敘述)。於氧化鈦粒子的表面,通常存在羥基,藉此氧化鈦粒子的表面顯示親水性。再者,本發明中,所謂『親水性』,係指於氧化鈦粒子的表面存在具有對水之親和性之官能基等。 The surface of the titanium oxide particles is preferably hydrophilic. Thereby, the average dispersed particle diameter of the dispersed titanium oxide particles can be made close to the average primary particle diameter of the titanium oxide particles (the details will be described later). On the surface of the titanium oxide particles, a hydroxyl group usually exists, whereby the surface of the titanium oxide particles exhibits hydrophilicity. In the present invention, the term "hydrophilic" refers to the presence of a functional group having an affinity for water on the surface of the titanium oxide particles.
另外,本發明中,就使氧化鈦粒子的表面的親水性提高或維持之觀點而言,亦可進行親水化處理。於對氧化鈦粒子的表面進行親水化處理之情形時,例如可使用無機化合物及/或有機化合物之表面處理劑。 In addition, in the present invention, from the viewpoint of improving or maintaining the hydrophilicity of the surface of the titanium oxide particles, a hydrophilizing treatment may be performed. When hydrophilizing the surface of a titanium oxide particle, the surface treating agent of an inorganic compound and / or an organic compound can be used, for example.
作為無機化合物之表面處理劑,並無特別限定,例如可列舉:氫氧化鋁、氧化鋁、氧化鋯、氧化矽、氧化鈰等。另外,作為有機化合物之表面處理劑,並無特別限定,例如可列舉:二甲基聚矽氧烷、甲基氫聚矽氧烷、(二甲聚矽氧烷/甲聚矽氧烷)共聚物、甲基苯基矽酮、胺基改性矽酮、氫化二甲聚矽氧烷、三乙氧基矽烷基乙基聚二甲基矽烷氧基乙基二甲聚矽氧烷、三乙氧基矽烷基乙基聚二甲基矽烷氧基乙基己基二甲聚矽氧烷等矽酮油;硬脂酸、月桂酸等高級脂肪酸;三羥甲基乙烷、季戊四醇、三丙醇乙烷、二-三羥甲基丙烷、三羥甲基丙烷乙氧化物等多元醇;三乙醇胺、三丙醇胺等烷醇胺、或該等之鹽酸鹽或有機酸鹽等衍生物;辛基矽烷、癸基矽烷、全氟辛基矽烷等烷基矽烷、烷基鈦酸酯、烷基鋁酸酯、聚烯烴、聚酯、月桂醯基離胺酸等胺基酸;鈦系偶合劑、鋁系偶合劑、鋯系偶合劑等有機金屬化合物等。可利用選自該等有機化合物中之至少1種化合物進行表面處理。另外,亦可使無機化合物與有機化合物組合而進行親水化處理。 The surface treatment agent for the inorganic compound is not particularly limited, and examples thereof include aluminum hydroxide, aluminum oxide, zirconia, silicon oxide, and cerium oxide. In addition, the surface treatment agent for the organic compound is not particularly limited, and examples thereof include dimethyl polysiloxane, methyl hydrogen polysiloxane, and (dimethyl polysiloxane / methyl polysiloxane) copolymerization. Compounds, methylphenyl silicone, amine-modified silicone, hydrogenated dimethylpolysiloxane, triethoxysilylethylpolydimethylsiloxyethyldimethylsiloxane, triethyl Silicone oils such as oxysilylethyl polydimethylsilyloxyethylhexyldimethylpolysiloxane; higher fatty acids such as stearic acid and lauric acid; trimethylolethane, pentaerythritol, and tripropanol ethyl Polyols such as alkane, di-trimethylolpropane, trimethylolpropane ethoxylate; alkanolamines such as triethanolamine, tripropanolamine, or derivatives thereof such as hydrochloride or organic acid salt; octyl Alkyl silanes such as silanes, decyl silanes, perfluorooctyl silanes, alkyl titanates, alkyl aluminates, polyolefins, polyesters, lauryl lysines, etc. Organometallic compounds such as aluminum-based coupling agents and zirconium-based coupling agents. The surface treatment may be performed using at least one compound selected from the organic compounds. Alternatively, an inorganic compound and an organic compound may be combined to perform a hydrophilization treatment.
作為氧化鈦粒子,亦可使用市售品,作為此種市售品,例如可列舉:STR-100N(商品名,日商堺化學工業(股份公司)製造,金紅石型)、TTO-51A(商品名,日商石原產業(股份公司),金紅石型)、TTO-55A(商品名,日商石原產業(股份公司),金紅石型)、TTO-55A(商品名,日商石原產業(股份公司),金紅石型)、TTO-80A(商品名,日商石原產業(股份公司),金紅石型)、MPT-140(商品名,日商石原產業(股份公司),金紅石型)、MPT-141(商品名,日商石原產業(股份公司),金紅石型)、MKR-1(商品名,日商堺化學工業(股份公司),金紅石型)、KA-10(商品名,日商鈦工業(股份公司),銳鈦礦型)等。 Commercially available products can be used as the titanium oxide particles. Examples of such commercially available products include STR-100N (trade name, manufactured by Nissho Chemical Co., Ltd., rutile), TTO-51A ( Trade name, Nissho Ishihara Industry (stock company), rutile type), TTO-55A (trade name, Nissho Ishihara Industry (stock company), rutile type), TTO-55A (trade name, Nissho Ishihara industry ( Co., Ltd.), rutile type), TTO-80A (trade name, Nissho Ishihara Industries (stock company), rutile type), MPT-140 (trade name, Nissho Ishihara industry (stock company), rutile type) , MPT-141 (trade name, Nissho Ishihara Industries (stock company), rutile type), MKR-1 (trade name, Nissho chemical industry (stock company), rutile type), KA-10 (trade name , Nissho Titanium Industry (stock company), anatase type), etc.
其次,對使用氧化鋅粒子作為具有作為紫外線吸收成分之功能之顏料之情形進行說明。由氧化鋅粒子構成之顏料為白色顏料,為具有紫外線遮蔽性之無機顏料。 Next, a case where zinc oxide particles are used as a pigment having a function as an ultraviolet absorbing component will be described. The pigment composed of zinc oxide particles is a white pigment, and is an inorganic pigment having ultraviolet shielding properties.
氧化鋅粒子的表面亦可進行親水化處理。但是,較佳為氧化鋅粒子的表面未藉由二氧化矽之水合物(含水氧化矽)進行親水化處理之氧化鋅粒子。亦即,於將於表面形成由二氧化矽之水合物(含水氧化矽)構成之覆膜而進行了親水化處理之氧化鋅粒子,與後文作為顏料分散劑所敘述之聚丙烯酸鈉一起使用之情形時,會有該由氧化鋅粒子構成之顏料的平均分散粒徑變大,保存穩定性降低的情況。藉由使用氧化鋅粒子的表面未藉由二氧化矽之水合物進行親 水化處理之氧化鋅粒子作為氧化鋅粒子,可使所分散之氧化鋅粒子的平均分散粒徑接近於該氧化鋅粒子的平均一次粒徑。再者,本發明中,所謂氧化鋅粒子,只要無特別說明,則意指結晶性之氧化鋅粒子。另外,氧化鋅粒子可使用藉由二氧化矽之水合物以外之化合物被覆表面而進行了親水化處理之氧化鋅粒子。 The surface of the zinc oxide particles may be hydrophilized. However, the zinc oxide particles are preferably zinc oxide particles whose surface has not been hydrophilized with silicon dioxide hydrate (aqueous silicon oxide). That is, zinc oxide particles that have been hydrophilized by forming a film composed of silica hydrate (aqueous silica) on the surface are used together with sodium polyacrylate described later as a pigment dispersant. In such a case, the average dispersion particle diameter of the pigment composed of the zinc oxide particles may increase, and the storage stability may decrease. By using zinc oxide particles whose zinc oxide particles have not been hydrophilized with a silica hydrate surface as zinc oxide particles, the average dispersed particle diameter of the dispersed zinc oxide particles can be close to that of the zinc oxide particles. Average primary particle size. In the present invention, unless otherwise specified, zinc oxide particles mean crystalline zinc oxide particles. As the zinc oxide particles, zinc oxide particles that have been hydrophilized by coating the surface with a compound other than a hydrate of silicon dioxide can be used.
作為氧化鋅粒子,亦可使用市售品,作為此種市售品,例如可列舉:FINEX-50(商品名,日商堺化學工業(股份公司)製造)、FINEX-30(商品名,日商堺化學工業(股份公司)製造)、FINEX-25(商品名,日商堺化學工業(股份公司)製造)等。 Commercial products can also be used as the zinc oxide particles. Examples of such commercial products include FINEX-50 (trade name, manufactured by Nissho Chemical Industry Co., Ltd.), and FINEX-30 (trade name, Japan Shoji Chemical Industry Co., Ltd.), FINEX-25 (trade name, manufactured by Nisho Chemical Industry Co., Ltd.), etc.
關於氧化鈦粒子及/或氧化鋅粒子(以下,有時稱為『氧化鈦粒子等』)之顏料,於將本實施形態之顏料組成物用作對醫藥品或補充品等錠劑表面之印刷用之情形時,較佳為符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準(以下,稱為『日本藥事法等基準』)之顏料。 Regarding pigments of titanium oxide particles and / or zinc oxide particles (hereinafter sometimes referred to as "titanium oxide particles"), the pigment composition of this embodiment is used for printing on the surface of tablets such as pharmaceuticals or supplements. In this case, a pigment that meets the standards of the pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations (hereinafter referred to as the "Japanese Pharmaceutical Affairs Law and other standards") prescribed in the Japanese Pharmaceutical Affairs Law is preferred.
作為氧化鈦粒子等的平均一次粒徑(體積平均粒徑),較佳為20nm至400nm,更佳為30nm至200nm,尤佳為40nm至100nm。藉由將平均一次粒徑設為20nm以上,可抑制印刷圖像之耐光性之降低,並且可增大顏料之濃度,從而謀 求透明性之提高。另外,亦可確保充分的隱蔽性。另一方面,藉由將平均一次粒徑設為400nm以下,可謀求高色彩化,並且可防止氧化鈦粒子等之沈降或噴嘴之堵塞。另外,通常,於選擇平均一次粒徑大之顏料粒子之情形時,為了能夠實現對利用噴墨方式之印刷所要求之平均分散粒徑之水準下之顏料分散,而用以將顏料粒子充分磨碎之步驟時間變長。但是,如上所述,藉由將平均一次粒徑設為400nm以下,亦可抑制步驟時間之長期化。 The average primary particle diameter (volume average particle diameter) of titanium oxide particles and the like is preferably 20 nm to 400 nm, more preferably 30 nm to 200 nm, and even more preferably 40 nm to 100 nm. By setting the average primary particle diameter to be 20 nm or more, it is possible to suppress a decrease in light resistance of a printed image, and to increase the concentration of a pigment, thereby improving transparency. In addition, sufficient concealment can be ensured. On the other hand, by setting the average primary particle diameter to 400 nm or less, it is possible to achieve high colorization, and it is possible to prevent sedimentation of titanium oxide particles and the like and clogging of nozzles. In addition, when pigment particles with a large average primary particle size are selected, the pigment particles are sufficiently pulverized in order to achieve dispersion of the pigments at a level of the average dispersion particle size required for printing by the inkjet method. The step time becomes longer. However, as described above, by setting the average primary particle diameter to 400 nm or less, the prolongation of the step time can also be suppressed.
再者,本發明中,所謂『平均一次粒徑』,意指一次粒子之平均粒徑,所謂一次粒子,通常係指構成粉末之最小粒子,含義包括單晶或與單晶接近之微晶聚集而形成之粒子。 Moreover, in the present invention, the so-called "average primary particle size" means the average particle size of primary particles. The so-called primary particles generally refer to the smallest particles constituting a powder, and the meaning includes single crystals or agglomeration of microcrystals close to single crystals. And formed particles.
另外,平均一次粒徑係利用電子顯微鏡觀察氧化鈦粒子等而求出之算術平均粒徑。本實施形態中,雖使用具有單分散之粒徑分佈之氧化鈦粒子等,但本發明並不限定於此,亦可使用具有多分散之粒徑分佈之氧化鈦粒子。另外,亦可將具有單分散之粒徑分佈之顏料混合2種以上而使用。 The average primary particle diameter is an arithmetic average particle diameter determined by observing titanium oxide particles and the like with an electron microscope. Although titanium oxide particles and the like having a monodispersed particle size distribution are used in this embodiment, the present invention is not limited thereto, and titanium oxide particles having a polydispersed particle size distribution may be used. In addition, a pigment having a monodispersed particle size distribution may be used by mixing two or more kinds.
氧化鈦粒子等的形狀並無特別限定,可使用球狀、棒狀、針狀、紡錘狀、板狀等任意形狀之氧化鈦粒子。於本實施形態中,可使用同種形狀之氧化鈦粒子等,亦可將2 種以上之不同形狀之氧化鈦粒子等混合而使用。再者,為棒狀、針狀、紡錘狀粒子之情形時的平均一次粒徑係由長軸之長度(或高度)與短軸之長度(或寬度)之相乘平均值所規定。 The shape of the titanium oxide particles and the like is not particularly limited, and titanium oxide particles of any shape such as a spherical shape, a rod shape, a needle shape, a spindle shape, and a plate shape can be used. In this embodiment, titanium oxide particles and the like of the same shape may be used, and titanium oxide particles and the like of two or more different shapes may be mixed and used. In addition, the average primary particle diameter in the case of rod-shaped, needle-shaped, and spindle-shaped particles is defined by a multiplied average value of the length (or height) of the major axis and the length (or width) of the minor axis.
顏料的含量會直接影響圖像濃度,且會對潛影用水性墨組成物的保存性或黏度、pH值等造成影響,故而考慮該等方面而適宜設定即可。通常,顏料的含量相對於顏料組成物的總質量,較佳為2質量%至20質量%之範圍內,更佳為5質量%至15質量%之範圍內。藉由將由氧化鈦粒子等構成之顏料的含量設為2質量%以上,可抑制圖像濃度之降低。另一方面,藉由將由氧化鈦粒子等構成之顏料的含量設為20質量%以下,可防止光澤性之降低或噴嘴之堵塞、噴出穩定性之降低。 The content of the pigment directly affects the image density, and it also affects the storability, viscosity, and pH of the latent image water-based ink composition. Therefore, it may be appropriately set in consideration of these aspects. In general, the content of the pigment is preferably within a range of 2% to 20% by mass, and more preferably within a range of 5% to 15% by mass relative to the total mass of the pigment composition. By setting the content of the pigment composed of titanium oxide particles and the like to 2% by mass or more, it is possible to suppress a decrease in image density. On the other hand, by setting the content of the pigment composed of titanium oxide particles and the like to 20% by mass or less, it is possible to prevent a decrease in glossiness, a clogging of a nozzle, and a decrease in ejection stability.
聚丙烯酸鈉對於本實施形態之顏料作為顏料分散劑發揮功能。藉由調配聚丙烯酸鈉,可謀求顏料的分散性之提高。另外,藉由使用聚丙烯酸鈉,可抑制於顏料組成物及潛影用水性墨組成物產生氣泡。結果,可省略消泡劑之添加。進而,自噴墨頭使本實施形態之潛影用水性墨組成物噴出時,不會於該潛影用水性墨組成物中存在該氣泡,故而亦可抑制噴嘴逃逸或噴出不良、開放時間(open time)之降低。再者,聚丙烯酸鈉符合日本藥事法等中所規定之基準。因此,聚丙烯酸鈉可較佳地用於對醫藥品或食品等錠 劑等之印刷。 Sodium polyacrylate functions as a pigment dispersant for the pigment of this embodiment. By blending sodium polyacrylate, the dispersibility of a pigment can be improved. In addition, by using sodium polyacrylate, the generation of air bubbles in the pigment composition and the water-based ink composition of the latent image can be suppressed. As a result, the addition of a defoamer can be omitted. Furthermore, when the latent image aqueous ink composition is ejected from the inkjet head, the air bubbles are not present in the latent image aqueous ink composition, so it is possible to suppress nozzle escape or ejection failure, and open time ( open time). In addition, sodium polyacrylate meets the standards prescribed by the Japan Pharmaceutical Affairs Law and the like. Therefore, sodium polyacrylate can be preferably used for the printing of tablets such as pharmaceuticals or foods.
聚丙烯酸鈉的質量平均分子量為10000以下,較佳為1500至10000,更佳為2000至8000。藉由將聚丙烯酸鈉的質量平均分子量設為10000以下,而防止吸附於氧化鈦粒子等的表面之聚丙烯酸鈉的分子鏈變得過長。結果,可減少由氧化鈦粒子等構成之顏料彼此交聯而凝聚。再者,藉由將聚丙烯酸鈉的質量平均分子量設為1500以上,可使吸附於氧化鈦粒子等的表面之聚丙烯酸鈉充分地發揮因立體阻礙等所致之反彈力。結果,可抑制氧化鈦粒子等彼此再凝聚。再者,聚丙烯酸鈉的質量平均分子量例如係藉由後述之實施例中所記載之測定方法所獲得之值。 The mass average molecular weight of sodium polyacrylate is 10,000 or less, preferably 1500 to 10,000, and more preferably 2,000 to 8000. By setting the mass average molecular weight of sodium polyacrylate to 10,000 or less, the molecular chain of sodium polyacrylate adsorbed on the surface of titanium oxide particles or the like is prevented from becoming too long. As a result, it is possible to reduce the cross-linking and aggregation of pigments composed of titanium oxide particles and the like. In addition, by setting the mass average molecular weight of sodium polyacrylate to 1500 or more, the sodium polyacrylate adsorbed on the surface of titanium oxide particles and the like can sufficiently exhibit the repulsive force due to steric hindrance and the like. As a result, re-agglomeration of titanium oxide particles and the like can be suppressed. The mass average molecular weight of sodium polyacrylate is, for example, a value obtained by a measurement method described in Examples described later.
本實施形態之顏料與聚丙烯酸鈉之含有比以質量基準計較佳為1:0.05至1:1.5,更佳為1:0.1至1:1。藉由將含有比設為1:0.05以上,可防止氧化鈦粒子等顏料的分散性降低。另一方面,藉由將含有比設為1:1.5以下,例如於用於潛影用水性墨組成物之情形時,可防止起因於對噴嘴板之附著之噴出穩定性之降低。 The content ratio of the pigment and sodium polyacrylate in this embodiment is preferably 1: 0.05 to 1: 1.5 on a mass basis, and more preferably 1: 0.1 to 1: 1. By setting the content ratio to 1: 0.05 or more, it is possible to prevent a reduction in dispersibility of pigments such as titanium oxide particles. On the other hand, by setting the content ratio to 1: 1.5 or less, for example, in the case of a water-based ink composition for latent images, it is possible to prevent a decrease in ejection stability due to adhesion to the nozzle plate.
再者,聚丙烯酸鈉於例如添加至後述之分散介質時,與其他先前之顏料分散劑相比,相對較不易產生氣泡。因此,本實施形態之顏料組成物中,可省略消泡劑之添加。 In addition, when sodium polyacrylate is added to a dispersion medium described later, for example, it is relatively less likely to generate bubbles than other conventional pigment dispersants. Therefore, in the pigment composition of this embodiment, the addition of an antifoaming agent can be omitted.
本實施形態之顏料組成物中,含有用以使氧化鈦粒子及/或氧化鋅粒子之顏料分散之分散介質。作為分散介質,可列舉水,更詳細而言,可列舉:離子交換水、超過濾水、逆滲透水、蒸餾水等純水、或超純水等去除了離子性雜質之水。尤其是,藉由照射紫外線或添加過氧化氫等而進行了殺菌處理之水可長期防止黴或菌之產生,故而較佳。另外,作為分散介質的含量,並無特別限定,可適宜地根據需要進行設定。 The pigment composition of this embodiment contains a dispersion medium for dispersing pigments of titanium oxide particles and / or zinc oxide particles. Examples of the dispersion medium include water, and more specifically, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water, or water from which ionic impurities have been removed, such as ultrapure water. In particular, water subjected to a sterilization treatment by irradiating ultraviolet rays or adding hydrogen peroxide is preferable because it can prevent the generation of mold or bacteria for a long period of time. The content of the dispersion medium is not particularly limited, and can be appropriately set as required.
另外,作為分散介質,亦可使用水與水溶性有機溶劑之混合溶液。作為水溶性有機溶劑,只要為符合日本藥事法等基準之溶劑,則並無特別限定。具體而言,例如可列舉:乙醇、正丁醇、異丁醇、正丙醇、異丙醇、丙酮、丙二醇、聚乙二醇、甘油等。該等可單獨使用一種或混合兩種以上而使用。進而,作為分散介質使用水溶性有機溶劑之情形時之調配量,並無特別限定,可適宜地根據需要進行設定。 In addition, as the dispersion medium, a mixed solution of water and a water-soluble organic solvent may also be used. The water-soluble organic solvent is not particularly limited as long as it is a solvent that complies with standards such as the Japanese Pharmaceutical Affairs Law. Specific examples include ethanol, n-butanol, isobutanol, n-propanol, isopropanol, acetone, propylene glycol, polyethylene glycol, and glycerol. These can be used individually by 1 type or in mixture of 2 or more types. Furthermore, when the water-soluble organic solvent is used as a dispersion medium, the compounding amount is not particularly limited, and can be appropriately set as necessary.
處於分散狀態之氧化鈦粒子等的平均分散粒徑D50較佳為20nm至500nm之範圍內,更佳為40nm至100nm之範圍內。另外,顏料之分散粒徑D99(以體積累計粒度分佈中之累計粒度計為99%之粒徑)較佳為1000nm以下,更佳為500nm以下。藉由將D50設為20nm以上,可防止保存穩定性、耐光性及噴出穩定性之惡化,亦可防止印刷濃度之降 低。另一方面,藉由將D50設為500nm以下或將D99設為1000nm以下,可防止顏料之分離或沈降及凝聚,從而謀求保存穩定性之維持。再者,顏料的平均分散粒徑D50及D99係使用Microtrac UPA-EX150(商品名,日商日機裝(股份公司)製造)藉由動態光散射法所測定之值。 The average dispersed particle diameter D50 of the titanium oxide particles and the like in a dispersed state is preferably in a range of 20 nm to 500 nm, and more preferably in a range of 40 nm to 100 nm. In addition, the dispersed particle diameter D99 of the pigment (a particle diameter of 99% based on the cumulative particle size in the volume cumulative particle size distribution) is preferably 1000 nm or less, and more preferably 500 nm or less. By setting D50 to 20 nm or more, deterioration in storage stability, light resistance, and ejection stability can be prevented, and reduction in print density can be prevented. On the other hand, when D50 is set to 500 nm or less or D99 is set to 1000 nm or less, separation, sedimentation, and aggregation of pigments can be prevented, thereby maintaining preservation stability. The average dispersed particle diameters D50 and D99 of the pigments are values measured by a dynamic light scattering method using Microtrac UPA-EX150 (trade name, manufactured by Nissho Nikkiso Co., Ltd.).
另外,氧化鈦粒子等的平均一次粒徑與分散於分散介質中之氧化鈦粒子等的平均分散粒徑D50之比較佳為1:0.3至1:3之範圍內。於本實施形態中,藉由對氧化鈦粒子等顏料,使用質量平均分子量為10000以下之聚丙烯酸鈉作為顏料分散劑,可使氧化鈦粒子等的平均分散粒徑成為與氧化鈦粒子等的平均一次粒徑大致相同之水準。結果,例如於使用平均一次粒徑小之氧化鈦粒子等之情形時,可獲得平均分散粒徑D50小之顏料組成物,防止顏料之分離或沈降及凝聚,從而謀求保存穩定性之維持。再者,氧化鈦粒子等的平均一次粒徑與氧化鈦粒子等的平均分散粒徑D50之比更佳為1:0.5至1:2.5,尤佳為1:0.8至1:2。 The average primary particle diameter of the titanium oxide particles and the like and the average dispersed particle diameter D50 of the titanium oxide particles and the like dispersed in the dispersion medium are preferably within a range of 1: 0.3 to 1: 3. In this embodiment, by using a sodium polyacrylate having a mass average molecular weight of 10,000 or less as a pigment dispersant for pigments such as titanium oxide particles, the average dispersed particle diameter of the titanium oxide particles and the like can be made the same as that of the titanium oxide particles. The primary particle size is about the same level. As a result, for example, when titanium oxide particles having a small average primary particle diameter are used, a pigment composition having a small average dispersed particle diameter D50 can be obtained to prevent separation, sedimentation, and aggregation of the pigment, thereby maintaining preservation stability. The ratio of the average primary particle diameter of the titanium oxide particles and the like to the average dispersed particle diameter D50 of the titanium oxide particles and the like is more preferably 1: 0.5 to 1: 2.5, and even more preferably 1: 0.8 to 1: 2.
本實施形態之顏料組成物之製造方法中,由氧化鈦粒子等構成之顏料、聚丙烯酸鈉、分散介質及根據需要調配之其他添加劑之混合方法或添加順序並無特別限定。例如,亦可將氧化鈦粒子等顏料、聚丙烯酸鈉及作為分散介質之水等一次性混合,並對該混合液使用通常之分散機實施分散處理。 In the method for producing a pigment composition according to this embodiment, the mixing method or the order of adding a pigment composed of titanium oxide particles and the like, sodium polyacrylate, a dispersion medium, and other additives formulated as required are not particularly limited. For example, pigments such as titanium oxide particles, sodium polyacrylate, and water as a dispersion medium may be mixed at one time, and the mixed solution may be subjected to a dispersion treatment using a general disperser.
但是,於本實施形態中,藉由使用作為顏料分散劑之聚丙烯酸鈉,可抑制於顏料組成物及包含該顏料組成物之潛影用水性墨組成物中產生氣泡。因此,可省略用以使該氣泡減少或消失之消泡步驟,從而可謀求製造效率之提高。另外,由於亦可省略消泡劑之含有,故而符合日本藥事法等基準之顏料組成物及潛影用水性墨組成物之製造變得更容易。 However, in this embodiment, by using sodium polyacrylate as a pigment dispersant, it is possible to suppress the generation of bubbles in the pigment composition and the water-based ink composition of the latent image containing the pigment composition. Therefore, a defoaming step for reducing or disappearing the bubbles can be omitted, and an improvement in manufacturing efficiency can be achieved. In addition, since the content of the defoaming agent can be omitted, it is easier to manufacture a pigment composition and a latent image water-based ink composition that meet the standards of the Japanese Pharmaceutical Affairs Law.
分散處理中之分散時間並無特別限定,可適宜地根據需要進行設定。作為顏料之分散處理時所使用之分散機,只要為通常所使用之分散機,則並無特別限定。具體而言,例如可列舉:球磨機、輥磨機、砂磨機、珠磨機、塗料振盪機、奈米均質機(Nanomizer)等。 The dispersion time in the dispersion treatment is not particularly limited, and can be appropriately set as required. The dispersing machine used for dispersing the pigment is not particularly limited as long as it is a dispersing machine generally used. Specific examples thereof include a ball mill, a roll mill, a sand mill, a bead mill, a paint shaker, a nanonomizer, and the like.
再者,本實施形態之顏料組成物除作為最終製品之潛影用水性墨組成物之形態以外,亦包含用以製備該潛影用水性墨組成物之顏料分散液之形態。 In addition, the pigment composition of the present embodiment includes the form of a pigment dispersion liquid for preparing the latent image water-based ink composition in addition to the form of the latent image water-based ink composition as a final product.
顏料的含量會直接影響圖像濃度,且會對潛影用水性墨組成物的保存性或黏度、pH值等造成影響,故而考慮該等方面適宜設定即可。通常,顏料的含量相對於顏料組成物的總質量,較佳為2質量%至20質量%之範圍內,更佳為5質量%至15質量%之範圍內。藉由將由氧化鈦粒子及/或 氧化鋅粒子構成之顏料的含量設為2質量%以上,可抑制圖像濃度之降低。另一方面,藉由將由氧化鈦粒子及/或氧化鋅粒子構成之顏料的含量設為20質量%以下,可防止光澤性之降低或噴嘴之堵塞、噴出穩定性之降低。 The content of the pigment directly affects the image density, and it also affects the storability, viscosity, and pH of the water-based ink composition of the latent image. Therefore, it may be appropriately set in consideration of these aspects. In general, the content of the pigment is preferably within a range of 2% to 20% by mass, and more preferably within a range of 5% to 15% by mass relative to the total mass of the pigment composition. By setting the content of the pigment composed of titanium oxide particles and / or zinc oxide particles to 2% by mass or more, a reduction in image density can be suppressed. On the other hand, by setting the content of the pigment composed of titanium oxide particles and / or zinc oxide particles to 20% by mass or less, it is possible to prevent a decrease in glossiness, a clogging of a nozzle, and a decrease in ejection stability.
<固體製劑的潛影印刷物之印刷方法> <Printing method of latent image printed matter of solid preparation>
本實施形態之固體製劑的潛影印刷物之印刷方法至少包括潛影印刷步驟,該潛影印刷步驟係於固體製劑的表面上印刷潛影。 The method for printing a latent image printed matter of the solid preparation of this embodiment includes at least a latent image printing step, and the latent image printing step is to print a latent image on the surface of the solid preparation.
作為於固體製劑10的表面印刷潛影(潛影墨層11)之方法,例如可列舉使用由潛影用水性墨組成物構成之潛影用水性墨之噴墨記錄方法。如上所述,本實施形態之潛影用水性墨組成物由於耐光性優異,亦不會產生滲出,故而可印刷為可使固體製劑10之製品資訊等顯影化之潛影。 As a method of printing a latent image (latent image ink layer 11) on the surface of the solid preparation 10, for example, an inkjet recording method using a latent image water-based ink composed of a latent image water-based ink composition is mentioned. As described above, the latent image water-based ink composition of this embodiment is excellent in light resistance and does not bleed out, so it can be printed as a latent image capable of developing the product information of the solid preparation 10 and the like.
關於對錠劑表面之噴墨記錄方法,並無特別限定。具體而言,例如可藉由下述方式而進行,亦即,自微細噴嘴將潛影用水性墨組成物以液滴之形式噴出,使該液滴附著於錠劑表面。作為噴出方法,並無特別限定,例如可採用連續噴射型(帶電控制型、噴霧型等)、即需即噴(on-demand)型(壓電方式、溫控(thermal)方式、靜電抽吸方式等)等公知的方法。 The inkjet recording method on the surface of the tablet is not particularly limited. Specifically, it can be performed, for example, by spraying a latent image water-based ink composition from a fine nozzle as a droplet, and making this droplet adhere to the surface of a tablet. The ejection method is not particularly limited. For example, continuous ejection type (charge control type, spray type, etc.), on-demand type (piezo method, thermal method, electrostatic suction) can be used. Methods, etc.) and other well-known methods.
另外,潛影印刷步驟中可包括乾燥步驟,該乾燥步驟係使附著於固體製劑10的表面而形成之由潛影用水性墨之液滴構成之塗膜(覆膜)乾燥。作為乾燥方法,並無特別限定,除熱風乾燥以外,亦可進行自然乾燥等。另外,關於乾燥時間或乾燥溫度等乾燥條件,亦無特別限定,可根據液滴之噴出量或潛影用水性墨組成物的種類等而適宜設定。 In addition, the latent image printing step may include a drying step of drying a coating film (coated film) composed of droplets of the latent image water-based ink formed on the surface of the solid preparation 10. The drying method is not particularly limited, and in addition to hot air drying, natural drying may be performed. In addition, the drying conditions such as the drying time and the drying temperature are not particularly limited, and can be appropriately set depending on the ejection amount of droplets, the type of the water-based ink composition of the latent image, and the like.
<固體製劑的潛影印刷物之攝影方法> <Photographing method of latent image printed matter of solid preparation>
其次,以下對本實施形態之固體製劑的潛影印刷物之攝影方法進行說明。 Next, a photographing method of a latent image printed matter of the solid preparation of the present embodiment will be described below.
本實施形態之攝影方法包括:顯影化步驟,使潛影顯影化;以及攝影步驟,對該顯影化步驟中經顯影化之潛影進行攝影。 The photographing method of this embodiment includes: a developing step to develop a latent image; and a photographing step to photograph the developed latent image in the developing step.
顯影化步驟可藉由下述方式而進行,亦即,對潛影區域A及非潛影區域B照射至少包含紫外線之照射光。藉由照射光之照射,於潛影區域A之潛影墨層11中吸收紫外線。另一方面,於非潛影區域B中,使紫外線反射及/或發出螢光。藉此,潛影區域A相對於非潛影區域B之階度值之差成為5以上,可使潛影墨層11所形成之潛影顯影化。 The development step can be performed by irradiating the latent image region A and the non-latent image region B with irradiation light including at least ultraviolet rays. The latent image ink layer 11 of the latent image area A absorbs ultraviolet rays by the irradiation of the irradiation light. On the other hand, in the non-latent image region B, ultraviolet rays are reflected and / or fluorescent light is emitted. Thereby, the difference of the order value of the latent image area A with respect to the non-latent image area B becomes 5 or more, and the latent image formed by the latent image ink layer 11 can be developed.
紫外線之波長區域為200nm以上且未達400nm之範圍內,可根據潛影墨層11中所含之紫外線吸收成分的種類適 宜設定。另外,照射光之出射時之光強度(μW/cm2)可根據紫外線吸收成分的種類或潛影墨層11中的含量、紫外線的光吸收性之程度等適宜設定。例如,於使用氧化鈦或氧化鋅作為紫外線吸收成分之情形時,光強度為4000μW/cm2至35000μW/cm2之範圍,更佳為5000μW/cm2至30000μW/cm2,尤佳為10000μW/cm2至20000μW/cm2。進而,照射光對固體製劑10之照射角度並無特別限定,可適宜設定。再者,所謂『照射角度』,意指對固體製劑10所照射之照射光之照射方向、與載置該固體製劑10之水平面所成之角度。 The wavelength range of the ultraviolet rays is in a range of 200 nm or more and less than 400 nm, and can be appropriately set according to the type of the ultraviolet absorption component contained in the latent image ink layer 11. In addition, the light intensity (μW / cm 2 ) when the irradiated light is emitted can be appropriately set according to the type of the ultraviolet absorbing component, the content in the latent image ink layer 11, the degree of ultraviolet light absorption, and the like. For example, in the case where titanium oxide or zinc oxide is used as an ultraviolet absorbing component, the light intensity is in the range of 4000 μW / cm 2 to 35000 μW / cm 2 , more preferably 5000 μW / cm 2 to 30,000 μW / cm 2 , and most preferably 10000 μW / cm 2 to 20000 μW / cm 2 . Furthermore, the irradiation angle of the solid preparation 10 by the irradiation light is not particularly limited, and can be appropriately set. In addition, the "irradiation angle" means the angle which the irradiation direction of the irradiation light which irradiates the solid preparation 10 and the horizontal plane on which the solid preparation 10 is mounted.
攝影步驟可藉由下述方式而進行,亦即,接收照射光於非潛影區域B所反射之反射光及/或於非潛影區域B所產生之螢光(以下,稱為『反射光等』),而對顯影化步驟中經顯影化之潛影區域及非潛影區域進行攝影。受光條件較佳為以對照射光之波長區域顯示最大感度之方式進行設定。具體而言,較佳為以使可接收之光之波長區域與照射光之波長區域至少一部分一致之方式設定受光條件,更佳為將可接收之光之波長區域設定為未達400nm。藉此,可謀求受光量之增大,從而可對潛影區域A及非潛影區域B以良好的對比度進行攝影。於對反射光等之波長區域之受光感度低或者無受光感度之情形時,則有難以對經顯影化之潛影區域A及非潛影區域B進行攝影的情形。 The photographing step can be performed by receiving reflected light reflected from the non-latent image area B and / or fluorescent light generated from the non-latent image area B (hereinafter, referred to as "reflected light"). Etc. ", and photographed the developed latent image area and non-latent image area in the developing step. The light receiving conditions are preferably set so that the maximum sensitivity is displayed in the wavelength region of the irradiated light. Specifically, it is preferable to set the light receiving conditions so that at least a part of the wavelength region of the receivable light coincides with the wavelength region of the irradiated light, and it is more preferable to set the wavelength region of the receivable light to less than 400 nm. Thereby, the amount of received light can be increased, and the latent image area A and the non-latent image area B can be photographed with good contrast. When the light receiving sensitivity is low or there is no light receiving sensitivity in a wavelength region such as reflected light, it may be difficult to photograph the developed latent image region A and the non-latent image region B.
接收反射光等時之受光角度並無特別限定,以反射光等之受光量成為最大之方式適宜設定即可。再者,所謂『受光角度』,意指非潛影區域B中之反射光等之光量成為最大之光線、與相對於水平面之法線間所成之角度。 The light receiving angle when receiving reflected light and the like is not particularly limited, and may be appropriately set so that the amount of light received by the reflected light or the like becomes maximum. In addition, the "light receiving angle" means the angle between the light with the maximum amount of reflected light in the non-latent image area B and the normal to the horizontal plane.
再者,本實施形態之潛影印刷物之攝影方法中,亦可於攝影步驟之後,進而進行檢查步驟,該檢查步驟係確認潛影墨層11有無印刷不良。該情形時,作為確認有無印刷不良之檢查方法,並無特別限定,可採用先前公知的方法。 In addition, in the photographing method of the latent image printed matter according to this embodiment, an inspection step may be performed after the photographing step, and the inspection step is to confirm whether the latent image ink layer 11 is defective in printing. In this case, the inspection method for confirming the presence or absence of printing defects is not particularly limited, and a conventionally known method can be adopted.
<固體製劑的潛影印刷物之攝影裝置> <Photographic device for latent image printed matter of solid preparation>
其次,以下基於圖2對潛影印刷物之攝影方法中所使用之攝影裝置進行說明。圖2係表示攝影方法中所使用之攝影裝置之概略之示意圖。 Next, a photographing device used in a photographing method of a latent image print will be described below based on FIG. 2. FIG. 2 is a schematic diagram showing an outline of a photographing device used in a photographing method.
如圖2所示,本實施形態之攝影裝置至少具備:光照射機構21,用以對固體製劑10照射照射光;以及攝影機構22,用以對該固體製劑10進行攝影。 As shown in FIG. 2, the photographing device of this embodiment includes at least: a light irradiation mechanism 21 for irradiating the solid preparation 10 with irradiation light; and an imaging mechanism 22 for photographing the solid preparation 10.
作為光照射機構21,只要為可照射包含波長區域為200nm以上且未達400nm之波長區域之紫外線之光之機構,則並無特別限定。例如可列舉:黑光燈、水銀燈、金屬鹵化物燈、氙氣燈、LED(Light Emitting Diode;發光二極 體)等各種公知的光照射機構。 The light irradiation means 21 is not particularly limited as long as it can irradiate light including ultraviolet rays in a wavelength range of 200 nm to 400 nm. Examples thereof include various known light irradiation mechanisms such as a black light lamp, a mercury lamp, a metal halide lamp, a xenon lamp, and an LED (Light Emitting Diode).
另外,於光照射機構21為照射包含可見光等之光之機構,且欲對固體製劑10僅照射上述波長區域之紫外線之情形時,亦可經由將該波長區域以外之波長區域之光(例如,可見光或紅外光等)遮斷或衰減之第一光學濾波器23進行照射。或者,亦可使用內建有此種第一光學濾波器23之光照射機構作為光照射機構21。 In addition, when the light irradiation mechanism 21 is a mechanism that irradiates light including visible light and the like, and it is intended to irradiate the solid preparation 10 only with ultraviolet rays in the above-mentioned wavelength region, light in a wavelength region other than the wavelength region (for example, Visible light, infrared light, etc.) is irradiated by the first optical filter 23 that is cut off or attenuated. Alternatively, a light irradiation mechanism having such a first optical filter 23 built in may be used as the light irradiation mechanism 21.
攝影機構22係接收藉由照射光之照射而於非潛影區域B所反射之反射光或螢光,對潛影區域A及非潛影區域B之圖像進行攝影之機構。更具體而言,可列舉先前公知的紫外線相機等作為攝影機構22。 The photographing mechanism 22 is a mechanism that receives the reflected light or fluorescent light reflected by the non-latent image area B by the irradiation of the irradiation light, and photographs the images of the latent image area A and the non-latent image area B. More specifically, a conventionally known ultraviolet camera or the like can be cited as the imaging mechanism 22.
另外,於欲控制攝影機構22中所接收之光之波長之情形時,亦可經由波長濾波器等第二光學濾波器24於攝影機構22中進行受光。藉此,例如可使所接收之光之波長區域與照射光之波長區域一致。作為第二光學濾波器24,並無特別限定,例如可列舉可將可見光或紅外光等遮斷或衰減之先前公知的波長濾波器等。另外,亦可使用內建有此種第二光學濾波器24之攝影機構作為攝影機構22。 In addition, when it is desired to control the wavelength of the light received by the imaging mechanism 22, light can also be received by the imaging mechanism 22 through a second optical filter 24 such as a wavelength filter. This makes it possible, for example, to make the wavelength region of the received light coincide with the wavelength region of the irradiated light. The second optical filter 24 is not particularly limited, and examples thereof include a conventionally known wavelength filter that can block or attenuate visible light, infrared light, and the like. Alternatively, a photographing mechanism having the second optical filter 24 built in may be used as the photographing mechanism 22.
(實施形態2) (Embodiment 2)
<固體製劑的潛影印刷物> <Latent image print of solid preparation>
以下對實施形態2之固體製劑的潛影印刷物進行說明。圖3係以示意方式表示本實施形態之固體製劑的潛影印刷物之說明圖。再者,以下,對與實施形態1相同之構成標附相同的符號並省略該構成之說明。 The latent image printed matter of the solid preparation of the second embodiment will be described below. FIG. 3 is an explanatory view schematically showing a latent image printed matter of the solid preparation of the present embodiment. In the following, the same components as those in the first embodiment are denoted by the same reference numerals, and descriptions of the components are omitted.
如圖3所示,本實施形態之潛影印刷物與實施形態1之潛影印刷物相比,在進一步設置有其他非潛影區域C之方面不同,該其他非潛影區域C藉由可見墨層12而形成有可見圖像。可見墨層12設置於固體製劑10的表面上,潛影墨層11以一部分重疊之狀態積層而設置於可見墨層12上。 As shown in FIG. 3, the latent image printed matter of this embodiment is different from the latent image printed matter of Embodiment 1 in that another non-latent image area C is further provided, and the other non-latent image area C is provided with a visible ink layer. 12 and a visible image is formed. The visible ink layer 12 is provided on the surface of the solid preparation 10, and the latent image ink layer 11 is laminated on the visible ink layer 12 in a state of being partially overlapped.
此處,於本說明書中,所謂『可見圖像』,意指於照射可見光(波長區域400nm至760nm)之環境下能夠識別之圖像。進而,可見圖像中亦可包含於照射波長區域為200nm以上且未達400nm之紫外線之環境下潛影化而難以識別之圖像。以可見圖像之形式印刷之圖像例如可使用後述之噴墨用水性墨藉由噴墨方式進行印刷。 Here, in the present specification, the "visible image" means an image that can be recognized under an environment in which visible light (wavelength region of 400 nm to 760 nm) is irradiated. Furthermore, the visible image may include an image that is latently imaged and difficult to recognize in an environment irradiated with ultraviolet rays having a wavelength range of 200 nm or more and less than 400 nm. An image printed as a visible image can be printed by an inkjet method using, for example, an inkjet aqueous ink described later.
[其他非潛影區域] [Other non-latent image areas]
其他非潛影區域C係藉由至少吸收可見光(波長區域400nm至760nm)之可見墨層12而形成有可見圖像之區域。 The other non-latent image region C is a region where a visible image is formed by the visible ink layer 12 that absorbs at least visible light (wavelength region 400 nm to 760 nm).
於如本實施形態般,將潛影墨層11與可見墨層12以至少一部分重疊之狀態進行積層之情形時,潛影墨層11較佳 為積層於可見墨層12上。藉此,於潛影墨層11對可見光具有光透過性之情形時,可見光透過潛影墨層11,因此可不受該潛影墨層11阻礙而識別可見圖像。結果,即便於可印刷之區域的面積小之情形時,亦可將更多的資訊記錄於固體製劑10表面。另外,於潛影之顯影化時,可對潛影墨層11之整個區域照射紫外線。結果,可使潛影以良好的狀態顯影化。 In the case where the latent image ink layer 11 and the visible ink layer 12 are laminated in a state where at least a portion is overlapped as in this embodiment, the latent image ink layer 11 is preferably laminated on the visible ink layer 12. Thereby, when the latent image ink layer 11 is light-transmissive to visible light, visible light passes through the latent image ink layer 11, and thus a visible image can be identified without being hindered by the latent image ink layer 11. As a result, even when the area of the printable area is small, more information can be recorded on the surface of the solid preparation 10. When developing the latent image, the entire area of the latent image ink layer 11 may be irradiated with ultraviolet rays. As a result, the latent image can be developed in a good state.
可見墨層12亦可為將波長區域為200nm以上且未達400nm之範圍之紫外線吸收之層,但較佳為使上述紫外線透過或反射之層。藉此,由於非潛影區域B為使紫外線反射及/或發出螢光之區域,故藉由紫外線之照射,可使於照射紫外線時藉由可見墨層12所形成之可見圖像潛影化。結果,於使潛影區域A之潛影顯影化時,可避免與可見圖像重疊地視認,從而可謀求經顯影化之潛影之視認性之提高。 It can be seen that the ink layer 12 may be a layer that absorbs ultraviolet rays in a wavelength range of 200 nm to 400 nm, but is preferably a layer that transmits or reflects the ultraviolet rays. Therefore, since the non-latent image area B is an area that reflects ultraviolet light and / or emits fluorescence, the visible image formed by the visible ink layer 12 when the ultraviolet light is irradiated can be converted into a latent image by the ultraviolet light. . As a result, when the latent image of the latent image area A is developed, it is possible to avoid the superimposed recognition with the visible image, so that the visibility of the developed latent image can be improved.
作為可見墨層12,較佳為由後述之可見圖像用水性墨之乾燥皮膜構成之層。乾燥皮膜可藉由下述方式而形成,亦即,使用可見圖像用水性墨,例如藉由噴墨方式等,直接印刷於固體製劑10表面。另外,較佳為於可見墨層12中至少含有對可見光具有光吸收性之成分(以下,有時稱為『可見光吸收成分』)。進而,可見光吸收成分較佳為均勻地含有於可見墨層12中。作為可見光吸收成分,可列舉染料 或顏料(關於詳情,將於後文進行敘述)。再者,作為可見墨層12的厚度,並無特別限定,可適宜地根據需要進行設定。 The visible ink layer 12 is preferably a layer composed of a dry film of an aqueous ink for visible images described later. The dried film can be formed by directly printing on the surface of the solid preparation 10 using an aqueous ink for visible images, for example, by an inkjet method or the like. In addition, it is preferable that the visible ink layer 12 contains at least a component having a light absorption property with respect to visible light (hereinafter, sometimes referred to as a "visible light absorption component"). Furthermore, the visible light absorbing component is preferably contained uniformly in the visible ink layer 12. Examples of visible light absorbing components include dyes and pigments (for details, they will be described later). The thickness of the visible ink layer 12 is not particularly limited, and can be appropriately set as needed.
再者,本實施形態並不限定於將潛影墨層11積層於可見墨層12上之情形。例如,潛影墨層11與可見墨層12亦可分別設置於固體製劑10的表面上的不同區域。藉此,即便於可見墨層12為吸收上述波長區域之紫外線之層,於該紫外線照射下未潛影化之情形時,亦可防止與經顯影化之潛影重疊而被視認,可防止經顯影化之潛影與可見圖像之兩者之視認性降低。另外,亦可於潛影墨層11上積層可見墨層11。 Moreover, this embodiment is not limited to the case where the latent image ink layer 11 is laminated on the visible ink layer 12. For example, the latent image ink layer 11 and the visible ink layer 12 may be respectively disposed in different regions on the surface of the solid preparation 10. Thereby, even when the visible ink layer 12 is a layer that absorbs the ultraviolet rays in the above-mentioned wavelength region, and when the latent image is not irradiated under the ultraviolet light irradiation, it can be prevented from being recognized by overlapping with the developed latent image, which can prevent the The visibility of both the developed latent image and the visible image is reduced. In addition, the visible ink layer 11 may be laminated on the latent image ink layer 11.
[非潛影區域及其他非潛影區域之階度值之差] [Difference between order values of non-latent image area and other non-latent image areas]
對非潛影區域B及其他非潛影區域C同時照射可見光之情形時之其他非潛影區域C相對於非潛影區域B之階度值之差為5以上,較佳為15以上,更佳為30以上。藉由將階度值之差設為5以上,可實現可見光照射下之可見圖像(可見墨層12)之良好的視認(或識別)。 When the non-latent image area B and other non-latent image areas C are simultaneously irradiated with visible light, the difference between the order values of the other non-latent image areas C relative to the non-latent image area B is 5 or more, preferably 15 or more, more Preferably it is 30 or more. By setting the difference in the gradation value to 5 or more, a good visual recognition (or recognition) of a visible image (visible ink layer 12) under visible light irradiation can be achieved.
再者,本實施形態中所謂之『階度值』與實施形態1中所說明之階度值相同。另外,本實施形態中所謂之『階度值之差』意指自其他非潛影區域C之階度值之平均值減去非潛影區域B之階度值之平均值所得之值。進而,所謂 階度值之平均值,意指其他非潛影區域C或非潛影區域B之圖像資料中多個像素之階度值之平均值。 The so-called "gradation value" in this embodiment is the same as that described in the first embodiment. In addition, the "difference in the gradation value" in this embodiment means a value obtained by subtracting the average value of the gradation values of the non-latent image area B from the average value of the gradation values of the other non-latent image area C. Furthermore, the average value of the gradation value means the average value of the gradation values of a plurality of pixels in the image data of the other non-latent image area C or the non-latent image area B.
可見光之照射下之可見圖像之較佳的視認性可藉由可見墨層12中所含之可見光吸收成分吸收最多該可見光之峰值波長與所照射之可見光之波長之組合進行控制。或者,亦可藉由調節可見墨層12中所含之可見光吸收成分之濃度,而提高可見墨層12之可見光吸收能力,以其他非潛影區域C相對於非潛影區域B之階度值之差最大化之方式進行控制。 The better visibility of the visible image under visible light irradiation can be controlled by the combination of the peak wavelength of the visible light absorbed by the visible light absorbing component contained in the visible ink layer 12 and the wavelength of the visible light irradiated. Alternatively, the visible light absorbing ability of the visible ink layer 12 can be improved by adjusting the concentration of the visible light absorbing component contained in the visible ink layer 12, and the order values of other non-latent image regions C relative to the non-latent image regions B can be increased. The way to maximize the difference is controlled.
對非潛影區域B及其他非潛影區域C同時照射至少包含紫外線之照射光之情形時之其他非潛影區域C相對於非潛影區域B之階度值之差較佳為未達5。藉由將階度值之差設為未達5,使於紫外線照射下視認(或識別)可見圖像(可見墨層12)變得困難或減少。亦即,藉此於包含上述波長區域之紫外線之光之照射下,可使可見圖像潛影化。為了可使可見圖像潛影化,可藉由將可見墨層12設為使紫外線透過或反射之層而實現。 When the non-latent image area B and other non-latent image areas C are simultaneously irradiated with at least ultraviolet light, the difference between the order values of the other non-latent image areas C relative to the non-latent image area B is preferably less than 5 . By setting the difference between the gradation values to less than 5, it becomes difficult or reduced to visually recognize (or recognize) a visible image (visible ink layer 12) under ultraviolet irradiation. That is, a visible image can be latently imaged under the irradiation of light including ultraviolet rays in the above-mentioned wavelength region. In order to make a visible image latent image, it can be achieved by setting the visible ink layer 12 as a layer that transmits or reflects ultraviolet rays.
[可見圖像用水性墨] [Visible image with water-based ink]
作為形成其他非潛影區域C之可見墨層12之構成材料,於本實施形態中,較佳為使用具有可食用性之可見圖像用水性墨。可見圖像用水性墨包含可見圖像用水性墨組成 物。 As a constituent material of the visible ink layer 12 forming other non-latent image regions C, in this embodiment, it is preferable to use a water-based ink for visible images having edible properties. The visible image water-based ink contains a visible image water-based ink composition.
可見圖像用水性墨組成物中,於使用染料作為著色劑(可見光吸收成分)之情形時,可見圖像用水性墨組成物至少含有至少1種染料、及作為主溶媒之水。 In the case of using a dye as a colorant (visible light absorbing component) in the aqueous ink composition for visible images, the aqueous ink composition for visible images contains at least one dye and water as a main solvent.
作為染料,並無特別限定,可列舉先前公知的食用合成色素(合成焦油色素)或食用天然色素等。 The dye is not particularly limited, and examples thereof include conventionally known edible synthetic pigments (synthetic tar pigments) and edible natural pigments.
作為食用合成色素,可列舉選自由偶氮系染料、三苯基甲烷系染料、二苯駢吡喃(xanthene)系染料及靛藍系染料所組成之群組中的至少1種。進而,作為偶氮系染料,並無特別限定,例如可列舉選自由紅色2號、紅色102號、紅色40號、黃色4號及黃色5號所組成之群組中的至少1種。作為三苯基甲烷系染料,並無特別限定,例如可列舉藍色1號或綠色3號之至少任一者。作為二苯駢吡喃系染料,並無特別限定,例如可列舉選自由紅色3號、紅色104號、紅色105號及紅色106號所組成之群組中的至少1種。作為靛藍系染料,可列舉藍色2號。 Examples of the edible synthetic pigment include at least one selected from the group consisting of an azo dye, a triphenylmethane dye, a xanthene dye, and an indigo dye. Furthermore, the azo dye is not particularly limited, and examples thereof include at least one selected from the group consisting of Red No. 2, Red No. 102, Red No. 40, Yellow No. 4, and Yellow No. 5. The triphenylmethane-based dye is not particularly limited, and examples thereof include at least one of Blue No. 1 and Green No. 3. The diphenylpyranopyran dye is not particularly limited, and examples thereof include at least one selected from the group consisting of Red No. 3, Red No. 104, Red No. 105, and Red No. 106. Examples of the indigo dye include Blue No. 2.
另外,作為食用天然色素,可列舉選自由胭脂蟲紅色素、葉綠素銅鈉、可可色素及焦糖色素所組成之群組中的至少1種。 The edible natural pigment includes at least one selected from the group consisting of cochineal red pigment, sodium copper chlorophyll, cocoa pigment, and caramel pigment.
進而,於本實施形態中,亦可使用將上述例示之染料藉由公知的色澱化劑進行色澱化而成之色澱顏料。 Furthermore, in the present embodiment, a lake pigment obtained by subjecting the dyes exemplified above to lake formation using a known lake formation agent may be used.
該等染料等可適宜根據需要單獨使用或混合兩種以上而使用。另外,該等染料等符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準。 These dyes, etc. can be used individually or in mixture of 2 or more types as needed suitably. In addition, these dyes and the like comply with the standards for pharmaceutical additives, the Japanese Pharmacopoeia, and the Japanese Food Additives Regulations as specified in the Japanese Pharmaceutical Affairs Law.
上述例示之染料等對可見光顯示光吸收性。另外,該等染料對200nm以上且未達400nm之波長區域之紫外線顯示光透過性。因此,於將該等染料用於可見墨層12之構成材料之情形時,可形成如下可見墨層12,該可見墨層12於可見光照射下能夠視認,而於上述波長區域之紫外線照射下,則由於非潛影區域B為使該紫外線反射及/或發出螢光之區域,故而藉由潛影化而使視認變得困難。再者,上述例示之各染料可單獨使用或併用2種以上。另外,該等染料較佳為均符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準。 The dyes and the like exemplified above show light absorption to visible light. In addition, these dyes show light transmittance to ultraviolet rays in a wavelength range of 200 nm to 400 nm. Therefore, when these dyes are used as a constituent material of the visible ink layer 12, a visible ink layer 12 can be formed, which can be visually recognized under visible light irradiation, and under ultraviolet radiation in the above-mentioned wavelength region, Since the non-latent image region B is a region that reflects the ultraviolet light and / or emits fluorescence, it becomes difficult to visually recognize the latent image. The dyes exemplified above can be used alone or in combination of two or more. In addition, it is preferable that these dyes conform to the standards of the pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations as stipulated in the Japanese Pharmaceutical Affairs Law.
染料的含量並無特別限定,通常相對於可見圖像用水性墨組成物的總質量,為0.2質量%至20質量%之範圍內,較佳為1質量%至10質量%。 The content of the dye is not particularly limited, but it is usually within a range of 0.2% to 20% by mass, and preferably 1% to 10% by mass, relative to the total mass of the aqueous ink composition for visible images.
本實施形態之可見圖像用水性墨組成物中,亦可含有表面張力調整劑。表面張力調整劑只要為符合日本藥事法 等基準之化合物,則並無特別限定,具體而言,例如可列舉:聚甘油脂肪酸酯、辛酸十甘油酯、月桂酸六甘油酯、油酸六甘油酯等。該等可單獨使用一種或混合兩種以上而使用。表面張力調整劑的含量並無特別限定,通常相對於可見圖像用水性墨組成物的總質量,為0.5質量%至5質量%之範圍內。 The water-based ink composition for visible images of this embodiment may further contain a surface tension adjuster. The surface tension adjusting agent is not particularly limited as long as it is a compound that complies with standards such as the Japanese Pharmaceutical Affairs Law. Specific examples include polyglycerol fatty acid esters, decaglyceryl caprylate, hexaglyceryl laurate, and hexaoleate Glycerides, etc. These can be used individually by 1 type or in mixture of 2 or more types. The content of the surface tension adjuster is not particularly limited, and it is usually within a range of 0.5% by mass to 5% by mass based on the total mass of the aqueous ink composition for visible images.
另外,本實施形態之可見圖像用水性墨組成物中,亦可含有濕潤劑。濕潤劑只要為符合日本藥事法等基準之化合物,則並無特別限定,具體而言,例如可列舉丙二醇、甘油等。濕潤劑的添加量並無特別限定,通常相對於水性墨組成物的總質量,為20質量%至50質量%之範圍內。 Moreover, the water-based ink composition for visible images of this embodiment may contain a wetting agent. The humectant is not particularly limited as long as it is a compound that complies with standards such as the Japanese Pharmaceutical Affairs Law, and specific examples thereof include propylene glycol and glycerin. The amount of the humectant to be added is not particularly limited, and it is usually within a range of 20% by mass to 50% by mass based on the total mass of the aqueous ink composition.
本實施形態之可見圖像用水性墨組成物中,亦可調配其他添加劑。但是,於用作針對醫藥品等固體製劑之噴墨用墨之情形時,較佳為符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準之添加劑。作為添加劑,可列舉:水溶性樹脂、有機胺、界面活性劑、pH值調整劑、螯合化劑、防腐劑、黏度調整劑、消泡劑等。該等添加劑的含量並無特別限定,可適宜地根據需要進行設定。 In the aqueous ink composition for visible images of this embodiment, other additives may be blended. However, when used as inkjet inks for solid preparations such as pharmaceuticals, it is preferred that the additives comply with the standards of pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations as specified in the Japanese Pharmaceutical Affairs Law. . Examples of the additives include water-soluble resins, organic amines, surfactants, pH adjusters, chelating agents, preservatives, viscosity adjusters, and antifoaming agents. The content of these additives is not particularly limited, and can be appropriately set as needed.
另外,本實施形態之可見圖像用水性墨組成物中,亦可使用顏料作為著色劑(可見光吸收成分)。該情形時,作 為可見圖像用水性墨組成物,至少含有顏料組成物、及作為主溶媒之水。 In the aqueous ink composition for visible images of this embodiment, a pigment may be used as a colorant (visible light absorbing component). In this case, the water-based ink composition for visible images contains at least a pigment composition and water as a main solvent.
顏料組成物係至少含有顏料及顏料分散劑之組成物。顏料組成物的含量並無特別限定,通常相對於可見圖像用水性墨組成物的總質量以顏料分換算計為0.5質量%至20質量%之範圍。 The pigment composition is a composition containing at least a pigment and a pigment dispersant. The content of the pigment composition is not particularly limited, and is usually in the range of 0.5% by mass to 20% by mass in terms of pigment fraction based on the total mass of the aqueous ink composition for visible images.
作為顏料,例如可列舉:碳黑或黑色氧化鐵等。該等顏料對可見光具有光吸收性。因此,於非潛影區域B使可見光反射之情形時,藉由將該等顏料用於可見墨層12之構成材料,可增大其他非潛影區域C相對於非潛影區域B之階度值之差。再者,該等顏料對波長區域為200nm以上且未達400nm之紫外線亦具有光吸收性。因此,於照射紫外線而使由潛影墨層11構成之潛影顯影化之情形時,由可見墨層12構成之可見圖像亦與該經顯影化之潛影一起於固體製劑10表面被視認。因此,於使用該等顏料之情形時,較佳為可充分地視認(判別)經顯影化之潛影。具體而言,可將可見墨層12印刷於與潛影墨層11不同之區域,或者於可充分地確保可見光照射時之視認性之範圍內減少顏料之濃度。再者,上述例示之各顏料可單獨使用或併用2種以上。另外,該等顏料較佳為均符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準。 Examples of the pigment include carbon black and black iron oxide. These pigments are light absorbing to visible light. Therefore, in the case where the non-latent image area B reflects visible light, by using these pigments as the constituent material of the visible ink layer 12, the order of the other non-latent image area C with respect to the non-latent image area B can be increased. The difference in values. Furthermore, these pigments are also light-absorptive to ultraviolet rays in a wavelength range of 200 nm to 400 nm. Therefore, when the latent image composed of the latent image ink layer 11 is developed by irradiating ultraviolet rays, the visible image composed of the visible ink layer 12 is also visually recognized on the surface of the solid preparation 10 together with the developed latent image. . Therefore, in the case of using these pigments, it is preferable that the developed latent image can be sufficiently recognized (discriminated). Specifically, the visible ink layer 12 can be printed on a region different from the latent image ink layer 11, or the concentration of the pigment can be reduced within a range that can sufficiently ensure the visibility during irradiation with visible light. The pigments exemplified above may be used alone or in combination of two or more. In addition, these pigments are preferably in accordance with the standards of the pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations as stipulated in the Japanese Pharmaceutical Affairs Law.
顏料的含量並無特別限定,可考慮可見圖像用水性墨組成物的保存性或黏度、圖像濃度而適宜設定。通常,顏料的含量相對於顏料組成物的總質量為0.5質量%至40質量%之範圍。 The content of the pigment is not particularly limited, and it may be appropriately set in consideration of the preservation property, viscosity, and image density of the aqueous ink composition for visible images. Generally, the content of the pigment is in a range of 0.5% to 40% by mass based on the total mass of the pigment composition.
作為顏料分散劑,可使用噴墨用之水性墨組成物中通常使用之顏料分散劑。具體而言,例如可列舉非離子系界面活性劑、陰離子系界面活性劑等。作為非離子系界面活性劑,例如可列舉:聚氧乙烯氫化蓖麻油、聚氧乙烯月桂醚、聚氧乙烯鯨蠟醚、聚氧乙烯油醚、聚氧乙烯硬脂醚、聚氧乙烯山箭醚等聚氧乙烯烷基醚、聚山梨醇酯、油酸十甘油酯等。作為陰離子系界面活性劑,例如可列舉聚丙烯酸鈉等。該等可單獨使用或混合兩種以上而使用。但是,於將本實施形態之顏料組成物用作對醫藥品或食品等錠劑表面之印刷用之情形時,較佳為使用符合日本藥事法中所規定之醫藥添加物、日本藥典或日本食品添加物公定書之基準之化合物。 As the pigment dispersant, a pigment dispersant generally used in an aqueous ink composition for inkjet can be used. Specific examples include nonionic surfactants and anionic surfactants. Examples of the nonionic surfactant include polyoxyethylene hydrogenated castor oil, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, and polyoxyethylene mountain arrow. Polyoxyethylene alkyl ethers such as ethers, polysorbates, deca glyceryl oleate, and the like. Examples of the anionic surfactant include sodium polyacrylate. These can be used individually or in mixture of 2 or more types. However, when the pigment composition of this embodiment is used for printing on the surface of tablets such as pharmaceuticals or foods, it is preferable to use pharmaceutical additives, Japanese Pharmacopoeia, or Japanese foods that comply with the provisions of the Japanese Pharmaceutical Affairs Law. A compound that is the basis of the Addendum.
另外,顏料組成物中,含有用以使顏料分散之分散介質,作為該分散介質,可採用與實施形態1之潛影用水性墨組成物中之顏料組成物中所使用之分散介質相同之分散介質。因此,關於該分散介質之詳情省略說明。 The pigment composition contains a dispersion medium for dispersing the pigment. As the dispersion medium, the same dispersion medium as that used for the pigment composition in the latent image water-based ink composition of Embodiment 1 can be used. medium. Therefore, the details of the dispersion medium are omitted.
本實施形態之可見圖像用水性墨組成物中,含有水( 作為主溶媒之水)。作為水,較佳為使用離子交換水、超過濾水、逆滲透水、蒸餾水等純水、或超純水等去除了離子性雜質之水。作為水的含量,並無特別限定,可適宜地根據需要進行設定。 The water-based ink composition for visible images of this embodiment contains water (water as a main solvent). As the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, or distilled water, or water from which ionic impurities have been removed, such as ultra-pure water, is preferably used. The content of water is not particularly limited, and can be appropriately set as needed.
本實施形態之可見圖像用水性墨組成物中,亦可調配表面張力調整劑、濕潤劑(抗乾燥劑)、抗褪色劑、乳化穩定劑、滲透促進劑、紫外線吸收劑、防腐劑、防黴劑、pH值調整劑、黏度調整劑、分散穩定劑、防鏽劑、螯合劑等添加劑。但是,於用作針對醫藥品等錠劑之噴墨用墨之情形時,較佳為符合日本藥事法等基準之添加劑。 In the aqueous ink composition for visible images of this embodiment, a surface tension adjusting agent, a wetting agent (anti-drying agent), an anti-fading agent, an emulsifying stabilizer, a penetration enhancer, an ultraviolet absorber, a preservative, and Additives such as mold agents, pH adjusters, viscosity adjusters, dispersion stabilizers, rust inhibitors, and chelating agents. However, when it is used as an inkjet ink for tablets such as pharmaceuticals, it is preferably an additive that complies with standards such as the Japanese Pharmaceutical Affairs Law.
作為表面張力調整劑,只要為符合日本藥事法等基準之化合物,則並無特別限定,具體而言,例如可列舉:甘油脂肪酸酯、聚甘油脂肪酸酯等。作為甘油脂肪酸酯,例如可列舉:辛酸十甘油酯、月桂酸十甘油酯等。表面張力調整劑之添加量並無特別限定,通常以可將潛影用水性墨組成物的表面張力調整為25mN/m至40mN/m之範圍之方式設定。 The surface tension adjusting agent is not particularly limited as long as it is a compound that complies with standards such as the Japanese Pharmaceutical Affairs Law. Specific examples include glycerin fatty acid esters and polyglycerol fatty acid esters. Examples of the glycerin fatty acid ester include deca glyceryl caprylate and deca glyceryl laurate. The amount of the surface tension adjusting agent to be added is not particularly limited, and is usually set so that the surface tension of the latent image water-based ink composition can be adjusted to a range of 25 mN / m to 40 mN / m.
作為濕潤劑,只要為符合日本藥事法等基準之化合物,則並無特別限定,具體而言,例如可列舉丙二醇、甘油等。濕潤劑之添加量並無特別限定,通常相對於可見圖像用水性墨組成物的總質量為3質量%至50質量%之範圍。 The wetting agent is not particularly limited as long as it is a compound that complies with standards such as the Japanese Pharmaceutical Affairs Law, and specific examples thereof include propylene glycol and glycerin. The amount of the humectant added is not particularly limited, and it is usually in the range of 3% by mass to 50% by mass based on the total mass of the aqueous ink composition for visible images.
關於顏料組成物及可見圖像用水性墨組成物之製造方法,並無特別限定,可採用先前公知的方法。 The manufacturing method of a pigment composition and an aqueous ink composition for visible images is not specifically limited, A conventionally well-known method can be used.
<固體製劑的潛影印刷物之印刷方法> <Printing method of latent image printed matter of solid preparation>
本實施形態之固體製劑的潛影印刷物之印刷方法至少包括:可見圖像印刷步驟,於固體製劑的表面上印刷可見圖像;以及潛影印刷步驟,於固體製劑的表面上印刷潛影。 The method for printing the latent image printed matter of the solid preparation of this embodiment at least includes a visible image printing step of printing a visible image on the surface of the solid preparation; and a latent image printing step of printing a latent image on the surface of the solid preparation.
可見圖像印刷步驟係藉由於固體製劑10的表面,使用可見圖像用水性墨,印刷可見墨層12,而形成可見圖像之步驟。作為形成可見墨層12之方法,並無特別限定,較佳為利用噴墨方式之印刷。更具體而言,利用噴墨方式之可見墨層12之印刷係藉由下述方式而進行,亦即,自微細噴嘴將可見圖像用水性墨以液滴之形式噴出,使該液滴附著於固體製劑10上。作為可見圖像用水性墨之噴出方法,並無特別限定,例如可採用連續噴射型(帶電控制型、噴霧型等)、即需即噴型(壓電方式、溫控方式、靜電抽吸方式等)等公知的方法。墨滴之噴出量、印刷速度等印刷條件並無特別限定,可適宜地根據需要進行設定。 The visible image printing step is a step of forming a visible image by printing the visible ink layer 12 on the surface of the solid preparation 10 using an aqueous ink for visible images. The method for forming the visible ink layer 12 is not particularly limited, but printing using an inkjet method is preferred. More specifically, the printing of the visible ink layer 12 using the inkjet method is performed by a method in which a water-based ink of a visible image is ejected as droplets from a fine nozzle to make the droplets adhere On the solid preparation 10. The method of ejecting water-based ink for visible images is not particularly limited. For example, continuous ejection type (charge control type, spray type, etc.), and on-demand type (piezoelectric method, temperature control method, electrostatic suction method) can be used. Etc.) and other well-known methods. Printing conditions such as the amount of ink droplets to be discharged and the printing speed are not particularly limited, and can be appropriately set as needed.
另外,可見圖像印刷步驟中可包括乾燥步驟,該乾燥步驟係使附著於固體製劑10的表面之可見圖像用水性墨之 液滴乾燥。作為乾燥方法,並無特別限定,除熱風乾燥以外,亦可進行自然乾燥等。另外,關於乾燥時間或乾燥溫度等乾燥條件,亦無特別限定,可根據液滴的噴出量或可見圖像用水性墨組成物的種類等適宜設定。 In addition, the visible image printing step may include a drying step of drying the visible image adhered to the surface of the solid preparation 10 by droplets of water-based ink. The drying method is not particularly limited, and in addition to hot air drying, natural drying may be performed. In addition, the drying conditions such as the drying time and the drying temperature are not particularly limited, and can be appropriately set in accordance with the amount of droplets ejected, the type of the aqueous ink composition for visible images, and the like.
潛影印刷步驟係藉由於固體製劑10的表面,使用潛影用水性墨,印刷潛影墨層11,而形成潛影之步驟。作為形成潛影墨層11之方法,並無特別限定,與可見圖像印刷步驟之情形同樣地,較佳為利用噴墨方式之印刷。利用噴墨方式之潛影墨層11之印刷除使用潛影用水性墨以外,與可見圖像印刷步驟之情形相同。另外,潛影印刷步驟中可包括乾燥步驟,該乾燥步驟係使附著於固體製劑10的表面之潛影用水性墨之液滴乾燥。乾燥方法或乾燥條件與可見圖像印刷步驟之情形相同。 The latent image printing step is a step of forming a latent image by printing a latent image ink layer 11 by using the latent image aqueous ink on the surface of the solid preparation 10. The method for forming the latent image ink layer 11 is not particularly limited, and, as in the case of the visible image printing step, printing by an inkjet method is preferred. The printing of the latent image ink layer 11 by the inkjet method is the same as that in the visible image printing step except that the latent image water-based ink is used. In addition, the latent image printing step may include a drying step of drying the latent image attached to the surface of the solid preparation 10 with droplets of an aqueous ink. The drying method or drying conditions are the same as those in the visible image printing step.
此處,於使可見圖像之印刷區域(其他非潛影區域C)與潛影之印刷區域(潛影區域A),於固體製劑10的表面上相互不同之情形時,可見圖像印刷步驟與潛影印刷步驟之順序並無特別限定。例如,於較可見圖像印刷步驟先進行潛影印刷步驟之情形時,於與可見圖像之印刷預定區域不同之區域印刷潛影即可。另一方面,於使可見圖像之印刷區域與潛影之印刷區域,如本實施形態般於固體製劑10的表面上至少一部分重疊之情形時,較佳為首先於可見圖像印刷步驟中印刷可見圖像後,於潛影印刷步驟中印刷潛影。 藉此,於可見圖像與潛影重疊之區域中,可於可見墨層12上積層潛影墨層11,於該潛影墨層11之顯影化時,可使紫外線照射至潛影墨層11之整個區域。 Here, when the printed area of the visible image (other non-latent image area C) and the printed area of the latent image (latent image area A) are different from each other on the surface of the solid preparation 10, the visible image printing step The sequence with the latent image printing step is not particularly limited. For example, in the case where the latent image printing step is performed first than the visible image printing step, the latent image may be printed in a region different from a predetermined area for printing the visible image. On the other hand, when the printed area of the visible image and the printed area of the latent image overlap at least partly on the surface of the solid preparation 10 as in this embodiment, it is preferable to first print in the visible image printing step. After the image is visible, the latent image is printed in the latent image printing step. Thereby, in the area where the visible image and the latent image overlap, the latent image ink layer 11 can be laminated on the visible ink layer 12, and when the latent image ink layer 11 is developed, ultraviolet rays can be irradiated to the latent image ink layer. 11 of the entire area.
<固體製劑的潛影印刷物之攝影方法及攝影裝置> <Photographic method and device for latent image printed matter of solid preparation>
其次,以下對本實施形態之固體製劑的潛影印刷物之攝影方法進行說明。 Next, a photographing method of a latent image printed matter of the solid preparation of the present embodiment will be described below.
本實施形態之固體製劑的潛影印刷物之攝影方法與實施形態1之情形同樣地,至少包括:顯影化步驟,使潛影顯影化;以及攝影步驟,對該顯影化步驟中經顯影化之潛影進行攝影。 The method of photographing the latent image printed matter of the solid preparation of this embodiment is the same as the case of Embodiment 1, and includes at least a developing step to develop the latent image, and a photographing step to develop the latent image in the developing step. Film for photography.
顯影化步驟係藉由下述方式而進行,亦即,對潛影區域A、非潛影區域B及其他非潛影區域C照射至少包含紫外線之照射光。藉由照射光之照射,於潛影區域A之潛影墨層11中吸收紫外線,於非潛影區域B中使紫外線反射及/或發出螢光。另一方面,於可見墨層12為使紫外線透過或反射之層之情形時,其他非潛影區域C相對於非潛影區域B之階度值之差成為未達5,而可使可見墨層12所形成之可見圖像潛影化。但是,於可見墨層12與潛影墨層11同樣地為吸收紫外線之層之情形時,其他非潛影區域C相對於非潛影區域B之階度值之差成為5以上,可見墨層12於紫外線之照射下亦可識別。 The developing step is performed by irradiating the latent image region A, the non-latent image region B, and other non-latent image regions C with irradiation light including at least ultraviolet rays. By the irradiation of the irradiation light, ultraviolet rays are absorbed in the latent image ink layer 11 of the latent image region A, and ultraviolet rays are reflected and / or fluorescent light is emitted in the non-latent image region B. On the other hand, when the visible ink layer 12 is a layer that transmits or reflects ultraviolet rays, the difference between the order values of the other non-latent image regions C and the non-latent image regions B becomes less than 5, so that the visible ink can be made. The visible image formed by the layer 12 is latent imaged. However, when the visible ink layer 12 is the same as the latent image ink layer 11 as a layer that absorbs ultraviolet rays, the difference between the order values of the other non-latent image regions C with respect to the non-latent image region B becomes 5 or more, and the visible ink layer 12 It can also be identified under ultraviolet radiation.
再者,紫外線之照射條件與實施形態1中所述之照射條件相同。因此,關於該照射條件之詳情省略說明。 The irradiation conditions of ultraviolet rays are the same as the irradiation conditions described in the first embodiment. Therefore, the detailed description of the irradiation conditions is omitted.
攝影步驟係藉由下述方式而進行,亦即,接收照射光於非潛影區域B所反射之反射光及/或於非潛影區域B所產生之螢光(以下,稱為『反射光等』),而對顯影化步驟中經顯影化之潛影區域A、非潛影區域B及其他非潛影區域C進行攝影。此處,於可見墨層12由使紫外線反射之層構成之情形時,亦可接收於該可見墨層12所反射之反射光。再者,受光條件與實施形態1中所述之受光條件相同。因此,關於該受光條件之詳情省略說明。 The photographing step is performed by receiving reflected light reflected from the non-latent image area B and / or fluorescent light generated from the non-latent image area B (hereinafter, referred to as "reflected light"). Etc. ", and photographed the developed latent image area A, non-latent image area B, and other non-latent image areas C in the developing step. Here, when the visible ink layer 12 is composed of a layer that reflects ultraviolet rays, the reflected light reflected by the visible ink layer 12 may also be received. The light receiving conditions are the same as the light receiving conditions described in the first embodiment. Therefore, detailed descriptions of the light receiving conditions are omitted.
另外,本實施形態之潛影印刷物之攝影方法中,可於攝影步驟之後,進行檢查步驟,該檢查步驟係除潛影墨層11以外,亦確認可見墨層12有無印刷不良。 In addition, in the photographing method of the latent image printed matter of this embodiment, an inspection step may be performed after the photographing step. This inspection step is performed in addition to the latent image ink layer 11 and also confirms whether or not the ink layer 12 is defective in printing.
再者,本實施形態之潛影印刷物之攝影方法中所使用之攝影裝置可採用與實施形態1中所使用之攝影裝置相同之構成。因此,關於該攝影裝置之詳情省略說明。 In addition, the photographing apparatus used in the photographing method of the latent image printed matter of the present embodiment may have the same configuration as the photographing apparatus used in the first embodiment. Therefore, the detailed description of the photographing device is omitted.
(實施形態3) (Embodiment 3)
本實施形態之可食用物的檢查方法係不使用紫外線相機等特殊的攝影裝置,於螢光燈等照射可見光之通常之環境下,簡便地識別設置於該可食用物的表面的至少一部分 之潛影而進行檢查。 The inspection method of the edible matter according to this embodiment does not use a special photographic device such as an ultraviolet camera, and easily recognizes the potential of at least a part of the surface of the edible matter in a normal environment in which visible light such as a fluorescent lamp is irradiated. Shadow and check.
本說明書中,所謂『可食用物』,意指具有可食用性之固形物,具體而言,例如除固體狀之食品以外,可列舉可食用性膜、可食用性片等。進而,可食用物中亦包括固體製劑。 In the present specification, the "edible substance" means an edible solid substance. Specifically, for example, in addition to solid foods, edible films, edible tablets, and the like are listed. Furthermore, solid preparations are also included in edible materials.
以下,對作為可食用物之固體製劑的潛影印刷物進行說明。圖4係以示意方式表示本實施形態之固體製劑的潛影印刷物之說明圖。 Hereinafter, a latent image printed matter as a solid preparation of an edible substance will be described. FIG. 4 is an explanatory view schematically showing a latent image printed matter of the solid preparation of the present embodiment.
如圖4所示,本實施形態之潛影印刷物於固體製劑20的表面的至少一部分設置有潛影墨層11。潛影墨層11形成作為潛影之印刷圖像。並且,本實施形態之潛影印刷物至少具有:潛影區域A,潛影墨層11形成潛影;以及非潛影區域D,未形成潛影。 As shown in FIG. 4, the latent image print of the present embodiment is provided with a latent image ink layer 11 on at least a part of the surface of the solid preparation 20. The latent image ink layer 11 forms a printed image as a latent image. In addition, the latent image printed matter of this embodiment has at least: a latent image area A where the latent image ink layer 11 forms a latent image; and a non-latent image area D where no latent image is formed.
此處,以潛影之形式印刷之圖像與實施形態1及實施形態2之情形同樣地,例如可使用噴墨用水性墨藉由噴墨方式等進行印刷。另外,對於固體製劑以外之可食用物,除噴墨方式以外,亦可採用凹版印刷或軟版印刷等。 Here, the image printed as a latent image is the same as in the case of the first and second embodiments, and for example, the ink can be printed by an inkjet method using an aqueous inkjet ink. In addition, for edibles other than solid preparations, in addition to the inkjet method, gravure printing or flexographic printing can also be used.
[潛影區域] [Latent image area]
潛影區域A係藉由潛影墨層11而形成有潛影之區域, 該潛影墨層11吸收波長區域為200nm以上且未達400nm之範圍之紫外線。上述波長區域更佳為260nm以上且380nm以下之範圍,尤佳為280nm以上且360nm以下之範圍。另外,潛影墨層11較佳為對可見光具有光透過性。再者,本說明書中之『光透過性』意指使所入射之可見光之至少一部分透過之性質。另外,光透過性之含義除潛影墨層11為無色之情形以外,亦包括為有色之情形。 The latent image region A is a region where a latent image is formed by the latent image ink layer 11, and the latent image ink layer 11 absorbs ultraviolet rays in a wavelength range of 200 nm or more and less than 400 nm. The above-mentioned wavelength region is more preferably in a range of 260 nm to 380 nm, and particularly preferably in a range of 280 nm to 360 nm. The latent image ink layer 11 is preferably light-transmissive to visible light. In addition, "light transmittance" in this specification means the property which transmits at least a part of incident visible light. In addition, the meaning of light transmittance includes a case where the latent image ink layer 11 is colored, and a case where the latent image ink layer 11 is colored.
於潛影區域A,亦可設置形成於可見光下能夠視認之圖像之其他墨層或塗層。藉由潛影墨層11對可見光具有光透過性,即便於將其他墨層設置於該潛影墨層11之下層之情形時,亦可確保該其他墨層之視認性。作為塗層,例如可列舉用以被覆潛影墨層11而進行保護之外覆層或底塗層。 In the latent image region A, other ink layers or coatings formed on an image that can be viewed under visible light may also be provided. Since the latent image ink layer 11 has light permeability to visible light, the visibility of the other ink layers can be ensured even when other ink layers are disposed under the latent image ink layer 11. Examples of the coating layer include an overcoat layer and an undercoat layer for covering the latent image ink layer 11 for protection.
作為潛影墨層11,較佳為由噴墨用水性墨(詳情將於後文進行敘述)之乾燥覆膜(乾燥後之塗膜)構成之層。乾燥覆膜可藉由下述方式而形成,亦即,使用噴墨用水性墨,例如藉由噴墨方式等直接印刷於固體製劑20表面。另外,較佳為於潛影墨層11中至少含有對上述波長區域之範圍之紫外線具有光吸收性之成分(以下,有時稱為『紫外線吸收成分』)。進而,紫外線吸收成分較佳為均勻地含有於潛影墨層11中。作為紫外線吸收成分,例如可列舉作為顏料之氧化鈦(TiO2)粒子或氧化鋅粒子等。再者,作為潛影墨層11 的厚度,並無特別限定,可適宜地根據需要進行設定。 The latent image ink layer 11 is preferably a layer composed of a dry coating film (dried coating film) of an aqueous inkjet ink (the details will be described later). The dry film can be formed by printing directly on the surface of the solid preparation 20 using an inkjet water-based ink, for example, by an inkjet method or the like. In addition, it is preferable that the latent image ink layer 11 contains at least a component (hereinafter, sometimes referred to as an “ultraviolet absorbing component”) having a light absorptivity to ultraviolet rays in the above-mentioned wavelength range. Furthermore, it is preferable that the ultraviolet absorbing component is uniformly contained in the latent image ink layer 11. Examples of the ultraviolet absorbing component include titanium oxide (TiO 2 ) particles and zinc oxide particles as pigments. The thickness of the latent image ink layer 11 is not particularly limited, and can be appropriately set as needed.
[非潛影區域] [Non-latent image area]
非潛影區域D係於照射至少包含上述波長區域之紫外線之光(以下,稱為『照射光』)之情形時,吸收紫外線作為激發光而發出可見光區域之螢光之區域。 The non-latent image region D is a region where ultraviolet light (hereinafter, referred to as "irradiated light") including at least the above-mentioned wavelength region is irradiated, and ultraviolet rays are emitted as visible light in the visible light region.
為了使非潛影區域D具備於照射上述波長區域之範圍之紫外線之情形時顯示螢光性之性質,較佳為於固體製劑20中含有吸收該波長區域之紫外線作為激發光而發出可見光區域之螢光之螢光成分。作為此種螢光成分,只要為具有可食用性之螢光成分,則並無特別限定,具體而言,例如可列舉:NAD(P)H(Nicotinamide adenine dinucleotide phosphate;菸草醯胺腺嘌呤二核苷酸磷酸鹽)(激發光波長340nm、螢光波長450nm)、葉綠素(激發光波長465nm或665nm、螢光波長673nm或726nm)、膠原蛋白(激發光波長區域270nm至370nm、螢光波長區域305nm至450nm)、二酪胺酸(激發光波長325nm、螢光波長400nm)、醣化加成物(激發光波長370nm、螢光波長450nm)、黃素(激發光波長區域380nm至490nm、螢光波長區域520nm至560nm)、黑色素(激發光波長區域340nm至400nm、螢光波長區域360至560)、彈力蛋白(激發光波長360nm、螢光波長410nm)等自體螢光成分。該等自體螢光成分係含有於源自動物或植物之原料(具體而言,澱粉、糖、蛋白質類等)中,該原料通常用 於市售之錠劑等。再者,上述例示之螢光成分可單獨使用1種或混合2種以上而使用。 In order for the non-latent image region D to exhibit a fluorescent property when it is irradiated with ultraviolet rays in the above-mentioned wavelength region, it is preferable that the solid preparation 20 contains a visible light region that absorbs ultraviolet rays in the wavelength region as excitation light. Fluorescent component of fluorescence. Such a fluorescent component is not particularly limited as long as it is an edible fluorescent component, and specific examples thereof include: NAD (P) H (Nicotinamide adenine dinucleotide phosphate; tobacco nicotine adenine dinucleotide phosphate) Glycosyl phosphate) (excitation wavelength 340nm, fluorescence wavelength 450nm), chlorophyll (excitation wavelength 465nm or 665nm, fluorescence wavelength 673nm or 726nm), collagen (excitation wavelength range 270nm to 370nm, fluorescence wavelength range 305nm To 450nm), bistyrosine (excitation light wavelength 325nm, fluorescence wavelength 400nm), saccharification adduct (excitation light wavelength 370nm, fluorescence wavelength 450nm), flavin (excitation light wavelength range 380nm to 490nm, fluorescence wavelength Autofluorescence components such as 520nm to 560nm), melanin (excitation light wavelength range 340nm to 400nm, fluorescence wavelength range 360 to 560), elastin (excitation light wavelength 360nm, fluorescence wavelength 410nm) and the like. These autofluorescent components are contained in animal or plant-derived raw materials (specifically, starch, sugar, protein, etc.), and the raw materials are generally used in commercially available tablets and the like. The fluorescent components exemplified above may be used alone or in combination of two or more.
再者,即便於固體製劑20本身含有氧化鈦等紫外線吸收成分之情形時,藉由針對上述波長區域之紫外線將包含螢光成分之螢光層設置於固體製劑20表面,亦可形成非潛影區域D。 Furthermore, even when the solid preparation 20 itself contains ultraviolet absorbing components such as titanium oxide, a non-latent image can be formed by providing a fluorescent layer containing a fluorescent component on the surface of the solid preparation 20 for ultraviolet rays in the above-mentioned wavelength region. Area D.
另外,非潛影區域D亦可包括於可見光之照射下將該可見光之至少一部分反射或吸收之情形。另外,於非潛影區域D,亦可設置塗層等。 In addition, the non-latent image region D may include a case where at least a part of the visible light is reflected or absorbed under the irradiation of visible light. A coating or the like may be provided in the non-latent image region D.
[潛影用水性墨] [Latent image water-based ink]
作為形成潛影區域A之潛影墨層11之構成材料,可使用實施形態1及實施形態2之潛影用水性墨。進而,關於潛影用水性墨中所含之潛影用水性墨組成物等、或該潛影用水性墨組成物中所含之顏料組成物等,亦可使用與實施形態1及實施形態2相同之組成物等。因此,關於該等組成物之詳情省略說明。 As a constituent material of the latent image ink layer 11 forming the latent image region A, the latent image water-based ink according to the first and second embodiments can be used. Furthermore, the latent image water-based ink composition and the like contained in the latent image water-based ink and the pigment composition and the like contained in the latent image water-based ink composition can also be used in the same manner as in Embodiment 1 and Embodiment 2. Same composition, etc. Therefore, detailed descriptions of these compositions are omitted.
[顏料組成物] [Pigment composition]
潛影用水性墨組成物中所含之顏料組成物與實施形態1及實施形態2之情形同樣地,為至少含有由氧化鈦(TiO2)粒子及/或氧化鋅(ZnO)粒子構成之顏料(紫外線吸收成分 )、及作為顏料分散劑之聚丙烯酸鈉之顏料分散體之組成物。另外,關於本實施形態之顏料組成物之製造方法,亦與實施形態1及實施形態2之情形相同。因此,省略該等之詳細說明。 The pigment composition contained in the latent image water-based ink composition is a pigment containing at least titanium oxide (TiO 2 ) particles and / or zinc oxide (ZnO) particles, as in the case of Embodiment 1 and Embodiment 2. (Ultraviolet absorbing component), and a composition of a pigment dispersion of sodium polyacrylate as a pigment dispersant. In addition, the manufacturing method of the pigment composition of this embodiment is also the same as that of Embodiment 1 and Embodiment 2. Therefore, detailed descriptions of these are omitted.
<固體製劑的潛影印刷物之印刷方法> <Printing method of latent image printed matter of solid preparation>
本實施形態之固體製劑的潛影印刷物之印刷方法與實施形態1之情形同樣地,至少包括潛影印刷步驟,該潛影印刷步驟係於固體製劑20的表面上印刷潛影。因此,省略該印刷方法之詳細說明。 The method for printing the latent image printed matter of the solid preparation of the present embodiment is the same as that of the first embodiment, and includes at least a latent image printing step. The latent image printing step is to print a latent image on the surface of the solid preparation 20. Therefore, a detailed description of this printing method is omitted.
<固體製劑的潛影印刷物的檢查方法> <Inspection method of latent image printed matter of solid preparation>
其次,以下對本實施形態之固體製劑的潛影印刷物的檢查方法進行說明。 Next, a method for inspecting a latent image print of the solid preparation of the present embodiment will be described below.
本實施形態的檢查方法至少包括:顯影化步驟,使潛影顯影化;以及檢查步驟,對該顯影化步驟中經顯影化之潛影進行檢查。 The inspection method of this embodiment includes at least a development step to develop a latent image, and an inspection step to inspect the developed latent image in the development step.
顯影化步驟係藉由下述方式而進行,亦即,對潛影區域A及非潛影區域D照射至少包含紫外線之照射光。藉由照射光之照射,於潛影區域A之潛影墨層11中吸收紫外線。另一方面,於非潛影區域D中,以紫外線作為激發光而發出可見光區域之螢光。藉此,於潛影區域A中,相對於發出螢光之非潛影區域D,可使潛影作為亮度較低之區域被 視認出,從而可使潛影墨層11所形成之潛影顯影化。 The developing step is performed by irradiating the latent image region A and the non-latent image region D with irradiation light including at least ultraviolet rays. The latent image ink layer 11 of the latent image area A absorbs ultraviolet rays by the irradiation of the irradiation light. On the other hand, in the non-latent image region D, ultraviolet rays are used as excitation light to emit fluorescent light in a visible region. As a result, in the latent image area A, the latent image can be visually recognized as a region with a lower brightness than the non-latent image area D that emits fluorescence, so that the latent image formed by the latent image ink layer 11 can be developed. Into.
紫外線之波長區域為200nm以上且未達400nm之範圍內,可根據潛影墨層11中所含之紫外線吸收成分的種類而適宜設定。另外,照射光之出射時之光強度(μW/cm2)可根據紫外線吸收成分的種類或潛影墨層11中的含量、紫外線的光吸收性之程度等而適宜設定。例如,於使用氧化鈦或氧化鋅作為紫外線吸收成分之情形時,光強度為4000μW/cm2至35000μW/cm2之範圍,更佳為5000μW/cm2至30000μW/cm2,尤佳為10000μW/cm2至20000μW/cm2。進而,照射光對固體製劑20之照射角度並無特別限定,可適宜設定。再者,所謂『照射角度』,意指對固體製劑20所照射之照射光之照射方向、與載置該固體製劑20之水平面所成之角度。 The wavelength range of the ultraviolet rays is in a range of 200 nm or more and less than 400 nm, and can be appropriately set according to the type of the ultraviolet absorbing component contained in the latent image ink layer 11. In addition, the light intensity (μW / cm 2 ) at the time of emission of the irradiated light can be appropriately set depending on the type of the ultraviolet absorbing component, the content in the latent image ink layer 11, the degree of ultraviolet light absorption, and the like. For example, in the case where titanium oxide or zinc oxide is used as an ultraviolet absorbing component, the light intensity is in the range of 4000 μW / cm 2 to 35000 μW / cm 2 , more preferably 5000 μW / cm 2 to 30,000 μW / cm 2 , and most preferably 10000 μW / cm 2 to 20000 μW / cm 2 . Furthermore, the irradiation angle of the solid preparation 20 by the irradiation light is not particularly limited, and can be appropriately set. In addition, the "irradiation angle" means the angle which the irradiation direction of the irradiation light which irradiates the solid preparation 20 and the horizontal plane on which the solid preparation 20 is mounted.
檢查步驟係藉由下述方式而進行,亦即,以目視或使用受光波長為可見光區域之攝影機構,對顯影化步驟中經顯影化之潛影進行攝影。本實施形態中可利用目視進行檢查之原因在於,於非潛影區域D中發出可見光區域之螢光,另一方面,於潛影區域A中,潛影墨層11吸收紫外線,而作為亮度較非潛影區域D低之區域被視認出。 The inspection step is performed by photographing the developed latent image in the developing step visually or by using an imaging mechanism whose receiving wavelength is a visible light region. The reason for visual inspection in this embodiment is that in the non-latent image area D, fluorescent light in the visible light region is emitted. On the other hand, in the latent image area A, the latent image ink layer 11 absorbs ultraviolet rays, and the brightness is relatively high. A region where the non-latent image region D is low is recognized.
另外,於使用攝影機構之情形時,藉由下述方式而進行,亦即,接收非潛影區域D中所產生之螢光,對顯影化 步驟中經顯影化之潛影區域A及非潛影區域D進行攝影。受光條件較佳為以對非潛影區域D中所產生之螢光之波長區域(400nm至760nm)顯示最大感度之方式進行設定。藉此,可謀求受光量之增大,從而可對潛影區域A及非潛影區域D以良好的對比度進行攝影。於對螢光之波長區域之受光感度低或無受光感度之情形時,有時難以對經顯影化之潛影區域A及非潛影區域D進行攝影。 In addition, in the case of using a photographing mechanism, it is performed by receiving fluorescence generated in the non-latent image area D, and comparing the developed latent image area A and the non-latent image in the developing step. The shadow area D is photographed. The light receiving condition is preferably set so as to display the maximum sensitivity in a wavelength region (400 nm to 760 nm) of the fluorescent light generated in the non-latent image region D. Thereby, the amount of received light can be increased, and the latent image area A and the non-latent image area D can be photographed with good contrast. When the light receiving wavelength sensitivity is low or there is no light receiving sensitivity, it is sometimes difficult to photograph the developed latent image area A and the non-latent image area D.
接收螢光時之受光角度並無特別限定,以螢光之受光量成為最大之方式適宜設定即可。再者,所謂『受光角度』,意指非潛影區域D中之螢光之光量成為最大之光線、與相對於水平面之法線間所成之角度。 The light receiving angle when receiving fluorescent light is not particularly limited, and it may be appropriately set so that the light receiving amount of the fluorescent light becomes the maximum. In addition, the "light receiving angle" means the angle between the light with the maximum amount of fluorescent light in the non-latent image region D and the normal to the horizontal plane.
另外,於檢查步驟中,確認潛影墨層11有無印刷不良之情形時,可採用先前公知的檢查方法。例如,對無印刷不良之墨層照射紫外線,對吸收紫外線之墨層、及發出螢光之非潛影區域D預先進行攝影而設為基準墨層。然後,針對作為檢查對象之墨層(以下,稱為『被檢查墨層』),亦於與基準墨層相同之照射條件下照射紫外線,且於與基準墨層相同之攝影條件下進行攝影。其後,將基準墨層與被檢查墨層之攝影資料進行對比,判別是否於被檢查墨層存在印刷不良。藉此,可檢查潛影墨層11有無印刷不良。 In addition, in the inspection step, when it is confirmed whether the latent image ink layer 11 is defective in printing, a conventionally known inspection method can be adopted. For example, an ink layer having no printing defects is irradiated with ultraviolet rays, an ink layer that absorbs ultraviolet rays, and a non-latent image region D that emits fluorescence are photographed in advance to be a reference ink layer. Then, the ink layer to be inspected (hereinafter referred to as "inspected ink layer") was also irradiated with ultraviolet rays under the same irradiation conditions as the reference ink layer, and photographed under the same imaging conditions as the reference ink layer. After that, the photographic data of the reference ink layer and the ink layer to be inspected are compared to determine whether there is a printing failure in the ink layer to be inspected. With this, it is possible to check whether the latent image ink layer 11 is defective in printing.
照射照射光之情形時之潛影區域A及非潛影區域D中 之對比度例如可藉由調節該照射光之光強度而進行控制。具體而言,藉由適當地控制照射光之光強度,可使潛影區域A與非潛影區域D之對比度之差最大化,從而可良好地進行潛影之識別等。例如,於因照射光之光源之光強度過弱而潛影區域A與非潛影區域D之對比度之差小之情形時,可藉由增大光源之光強度而增大對比度之差。另外,於使用攝影機構之情形時,光源之光強度過大而攝影過度曝光,無法識別潛影區域A與非潛影區域D之對比度之情形時,可藉由減小光源之光強度而增大對比度之差。另外,潛影區域A與非潛影區域D之對比度之差除照射光之光強度以外,亦可藉由與照射光中所至少包含之紫外線之波長之最佳組合而控制。具體而言,較佳為以使紫外線之波長與潛影墨層11中所吸收之紫外線之波長至少一部分重疊之方式進行設定。或者,亦可藉由調節潛影墨層11中所含之紫外線吸收成分之濃度,而使潛影區域A中之紫外線吸收能力提高或降低,從而控制潛影區域A與非潛影區域D之對比度之差。 The contrast in the latent image area A and the non-latent image area D when the irradiation light is irradiated can be controlled by, for example, adjusting the light intensity of the irradiation light. Specifically, by appropriately controlling the light intensity of the irradiated light, the difference in contrast between the latent image area A and the non-latent image area D can be maximized, so that the identification of the latent image can be performed well. For example, when the difference in contrast between the latent image area A and the non-latent image area D is small because the light intensity of the light source irradiating the light is too weak, the difference in contrast can be increased by increasing the light intensity of the light source. In addition, in the case of using a photography mechanism, when the light intensity of the light source is too large and the photography is overexposed, and the contrast between the latent image area A and the non-latent image area D cannot be identified, it can be increased by reducing the light intensity of the light source. The difference in contrast. In addition, the difference in contrast between the latent image area A and the non-latent image area D can be controlled by an optimal combination with the wavelength of at least ultraviolet rays included in the irradiated light, in addition to the light intensity of the irradiated light. Specifically, it is preferable to set it so that the wavelength of ultraviolet rays and the wavelength of ultraviolet rays absorbed in the latent image ink layer 11 at least partially overlap. Alternatively, the ultraviolet absorption capacity in the latent image area A can be increased or decreased by adjusting the concentration of the ultraviolet absorbing component contained in the latent image ink layer 11, so as to control the latent image area A and the non-latent image area D. The difference in contrast.
[實施例] [Example]
以下,以例示方式詳細地說明本發明之較佳的實施例。但是,下述之實施例中所記載之材料或含量等只要無特別限定性之記載,則並非將本發明之範圍僅限定於該等。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of illustration. However, the materials and contents described in the following examples are not limited to the scope of the present invention as long as they are not particularly limited.
(潛影用水性墨組成物A之製備) (Preparation of latent image water-based ink composition A)
首先,進行顏料組成物之製作。亦即,將作為顏料之氧化鈦奈米粒子、作為顏料分散劑之聚丙烯酸鈉及作為分散介質之純水加入至容器中,利用分散機(塗料振盪機,日商淺田鐵工股份有限公司製造),於常溫下分散24小時(分散時間)。另外,分散時,混合氧化鋯珠而進行。藉此,製作顏料組成物。再者,作為氧化鈦奈米粒子,使用日商石原產業(股份公司)製造之TTO-55A(型號,結晶結構:金紅石型、平均一次粒徑40nm)。進而,氧化鈦奈米粒子的形狀為大致球狀。另外,作為聚丙烯酸鈉,使用Evonik公司製造之TEGO Dispers 715W(質量平均分子量3000)。 First, a pigment composition is produced. That is, titanium oxide nano particles as a pigment, sodium polyacrylate as a pigment dispersant, and pure water as a dispersion medium are added to a container, and a disperser (paint shaker, manufactured by Nissho Asada Iron Works Co., Ltd.) is used. ), Disperse at normal temperature for 24 hours (dispersion time). In addition, during the dispersion, zirconia beads were mixed. Thereby, a pigment composition is produced. In addition, as the titanium oxide nano particles, TTO-55A (type, crystal structure: rutile type, average primary particle size: 40 nm) manufactured by Nissho Ishihara Industry Co., Ltd. was used. Furthermore, the shape of the titanium oxide nanoparticle is substantially spherical. As sodium polyacrylate, TEGO Dispers 715W (mass average molecular weight 3000) manufactured by Evonik was used.
其次,於顏料組成物中,添加作為表面張力調整劑之聚甘油脂肪酸酯(商品名:SY Glister,日商阪本藥品工業(股份公司)製造)、作為濕潤劑之丙二醇及純水,以成為下述表1所示之調配比率之方式製備,利用分散機進行攪拌。藉此,製作潛影用水性墨組成物A。 Next, a polyglyceryl fatty acid ester (trade name: SY Glister, manufactured by Nissho Sakamoto Pharmaceutical Co., Ltd.) as a surface tension adjuster, propylene glycol and pure water as a wetting agent are added to the pigment composition so as to become It was prepared as a mixing ratio shown in Table 1 below, and stirred with a disperser. Thereby, a latent image water-based ink composition A was produced.
再者,顏料組成物及潛影用水性墨組成物A之製作過程中,均未產生氣泡,故而未進行利用添加消泡劑而行之消泡步驟。另外,下述表1中之數值只要無特別說明,則以相對於潛影用水性墨組成物A的總質量之質量%表示。另外,各材料均符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準。 In addition, during the production of the pigment composition and the latent image water-based ink composition A, no air bubbles were generated, so the defoaming step performed by adding an antifoaming agent was not performed. In addition, the numerical values in the following Table 1 are expressed as mass% relative to the total mass of the latent image water-based ink composition A unless otherwise specified. In addition, each material complies with the standards for pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations as specified in the Japanese Pharmaceutical Affairs Law.
(表中之數值只要無特別說明則係表示質量%。) (The values in the table are expressed as mass% unless otherwise specified.)
(潛影用水性墨組成物B之製備) (Preparation of latent image water-based ink composition B)
首先,進行顏料組成物之製作。亦即,將作為顏料之氧化鋅奈米粒子、作為顏料分散劑之聚丙烯酸鈉及作為分散介質之純水加入至容器中,利用分散機(塗料振盪機,日商淺田鐵工股份有限公司製造),於常溫下分散24小時(分散時間)。另外,分散時,混合氧化鋯珠而進行。藉此,製作顏料組成物。再者,作為氧化鋅奈米粒子,使用日商堺化學工業(股份公司)製造之FINEX-30(型號,平均一次粒徑35nm,表面未藉由二氧化矽之水合物(含水氧化矽)進行親水化處理)。進而,氧化鋅奈米粒子的形狀為大致球狀。另外,作為聚丙烯酸鈉,使用Evonik公司製造之TEGO Dispers 715W(質量平均分子量3000)。 First, a pigment composition is produced. That is, zinc oxide nano particles as a pigment, sodium polyacrylate as a pigment dispersant, and pure water as a dispersion medium are added to a container, and a disperser (paint shaker, manufactured by Nissho Asada Iron Works Co., Ltd.) is used. ), Disperse at normal temperature for 24 hours (dispersion time). In addition, during the dispersion, zirconia beads were mixed. Thereby, a pigment composition is produced. In addition, as zinc oxide nano particles, FINEX-30 (model, with an average primary particle size of 35 nm, manufactured by Nissho Chemical Co., Ltd.) was used, and the surface was not subjected to silica hydrate (aqueous silica). Hydrophilization treatment). Furthermore, the shape of the zinc oxide nanoparticle is substantially spherical. As sodium polyacrylate, TEGO Dispers 715W (mass average molecular weight 3000) manufactured by Evonik was used.
其次,於顏料組成物中,添加作為表面張力調整劑之 聚甘油脂肪酸酯(商品名:SY Glister,日商阪本藥品工業(股份公司)製造)、作為濕潤劑之丙二醇及純水,以成為下述表2所示之調配比率之方式製備,利用分散機進行攪拌。藉此,製作潛影用水性墨組成物B。 Next, a polyglyceryl fatty acid ester (trade name: SY Glister, manufactured by Nissho Sakamoto Pharmaceutical Co., Ltd.) as a surface tension adjuster, propylene glycol and pure water as a wetting agent are added to the pigment composition so as to become It was prepared as a mixing ratio shown in Table 2 below, and stirred with a disperser. Thereby, a latent image water-based ink composition B was produced.
再者,顏料組成物及潛影用水性墨組成物B之製作過程中,均未產生氣泡,故而未進行利用添加消泡劑而行之消泡步驟。另外,下述表2中之數值只要無特別說明,則以相對於潛影用水性墨組成物B的總質量之質量%表示。另外,各材料均符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準。 In addition, during the production of the pigment composition and the latent image water-based ink composition B, no air bubbles were generated, so the defoaming step by adding an antifoaming agent was not performed. In addition, the numerical values in the following Table 2 are expressed as mass% relative to the total mass of the latent image water-based ink composition B unless otherwise specified. In addition, each material complies with the standards for pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations as specified in the Japanese Pharmaceutical Affairs Law.
(表中之數值只要無特別說明則係表示質量%。) (The values in the table are expressed as mass% unless otherwise specified.)
(可見圖像用水性墨組成物A之製備) (Preparation of water-based ink composition A for visible images)
首先,進行顏料組成物之製作。亦即,將作為顏料之 碳黑、作為顏料分散劑之聚氧乙烯烷基醚及作為分散介質之純水加入至容器中,利用分散機(塗料振盪機,日商淺田鐵工股份有限公司製造),於常溫下分散24小時(分散時間)。另外,分散時,混合氧化鋯珠而進行。藉此,製作顏料組成物。 First, a pigment composition is produced. That is, carbon black as a pigment, polyoxyethylene alkyl ether as a pigment dispersant, and pure water as a dispersion medium are added to a container, and a disperser (paint shaker, manufactured by Nissho Asada Iron Works Co., Ltd.) is used. ), Disperse at normal temperature for 24 hours (dispersion time). In addition, during the dispersion, zirconia beads were mixed. Thereby, a pigment composition is produced.
其次,於顏料組成物中,添加作為表面張力調整劑之聚甘油脂肪酸酯(商品名:SY Glister,日商阪本藥品工業(股份公司)製造)、作為濕潤劑之丙二醇及純水,以成為下述表3所示之調配比率之方式製備,利用分散機進行攪拌。藉此,製作可見圖像用水性墨組成物A。 Next, a polyglyceryl fatty acid ester (trade name: SY Glister, manufactured by Nissho Sakamoto Pharmaceutical Co., Ltd.) as a surface tension adjuster, propylene glycol and pure water as a wetting agent are added to the pigment composition so as to become It was prepared as a mixing ratio shown in Table 3 below, and was stirred with a disperser. Thereby, a water-based ink composition A for visible images was produced.
再者,下述表3中之數值只要無特別說明,則以相對於可見圖像用水性墨組成物A的總質量之質量%表示。另外,各材料均符合日本藥事法中所規定之醫藥品添加物、日本藥典或日本食品添加物公定書之基準。 In addition, the numerical value in the following Table 3 is shown as mass% with respect to the total mass of the water-based ink composition A for a visible image, unless there is particular notice. In addition, each material complies with the standards for pharmaceutical additives, the Japanese Pharmacopoeia, or the Japanese Food Additives Regulations as specified in the Japanese Pharmaceutical Affairs Law.
(可見圖像用水性墨組成物B之製備) (Preparation of water-based ink composition B for visible images)
添加作為染料之食用綠色3號、作為表面張力調整劑之聚甘油脂肪酸酯(商品名:SY Glister,日商阪本藥品工業(股份公司)製造)、作為濕潤劑之丙二醇及純水,以成為下述表4所示之調配比率之方式製備,利用分散機進行攪拌。藉此,製作可見圖像用水性墨組成物B。 Edible Green No. 3 as a dye, polyglycerin fatty acid ester (trade name: SY Glister, manufactured by Nissho Sakamoto Pharmaceutical Co., Ltd.) as a surface tension adjuster, propylene glycol and pure water as a wetting agent are added to become It was prepared as a mixing ratio shown in Table 4 below, and stirred with a disperser. Thereby, a visible image water-based ink composition B was produced.
(潛影用水性墨組成物A及潛影用水性墨組成物B之光吸收光譜) (Light absorption spectrum of latent image water-based ink composition A and latent image water-based ink composition B)
針對潛影用水性墨組成物A及潛影用水性墨組成物B,使用分光光度計(商品名:UVmini-1240,日商島津製作所(股份公司)製造)確認紫外-可見光區域(190nm至500nm)中之吸收光譜。再者,將所製備之潛影用水性墨組成物A以原液之狀態進行測定時,濃度過高,因此以利用純水稀釋4000倍之溶液進行測定。另外,測定中使用光程長度1cm之石英池。結果示於圖5。 For the latent image water-based ink composition A and the latent image water-based ink composition B, the ultraviolet-visible light region (190 nm to 500 nm) was confirmed using a spectrophotometer (trade name: UVmini-1240, manufactured by Nissho Shimadzu Corporation). ) In the absorption spectrum. Furthermore, when the prepared latent image water-based ink composition A was measured in the state of a stock solution, the concentration was too high. Therefore, the solution was measured by diluting 4000 times with pure water. In addition, a quartz cell having an optical path length of 1 cm was used for the measurement. The results are shown in Fig. 5.
(可見圖像用水性墨組成物A及可見圖像用水性墨組成物B之光吸收光譜) (Light absorption spectrum of water-based ink composition A for visible images and water-based ink composition B for visible images)
針對可見圖像用水性墨組成物A及可見圖像用水性墨 組成物B之各者,使用分光光度計(商品名:UVmini-1240,日商島津製作所(股份公司)製造)確認紫外-可見光區域(260nm至800nm)內之吸收光譜。再者,將所製備之可見圖像用水性墨組成物A及可見圖像用水性墨組成物B分別以原液之狀態進行測定時,濃度過高,因此以利用純水稀釋4000倍之溶液進行測定。另外,測定中使用光程長度1cm之石英池。結果示於圖6。 For each of the visible image water-based ink composition A and the visible image water-based ink composition B, a UV-visible light was confirmed using a spectrophotometer (trade name: UVmini-1240, manufactured by Nissho Shimadzu Manufacturing Co., Ltd.). Absorption spectrum in the region (260nm to 800nm). Furthermore, when the prepared water-based ink composition A for visible images and water-based ink composition B for visible images were respectively measured in the state of the original solution, the concentration was too high, so the solution was diluted by 4000 times with pure water. Determination. In addition, a quartz cell having an optical path length of 1 cm was used for the measurement. The results are shown in Fig. 6.
(聚丙烯酸鈉的質量平均分子量之測定) (Measurement of mass average molecular weight of sodium polyacrylate)
聚丙烯酸鈉的質量平均分子量係以聚環氧乙烷(PEO;polyethylene oxide)/聚乙二醇(PEG;polyethylene glycol)作為標準品,藉由凝膠滲透層析法(GPC;gel permeation chromatography)所求出之值。 The mass average molecular weight of sodium polyacrylate is based on polyethylene oxide (PEO; polyethylene oxide) / polyethylene glycol (PEG; polyethylene glycol) as a standard, and gel permeation chromatography (GPC) The value found.
(氧化鈦奈米粒子及氧化鋅奈米粒子的平均一次粒徑及平均分散粒徑之測定) (Measurement of average primary particle diameter and average dispersed particle diameter of titanium oxide nano particles and zinc oxide nano particles)
氧化鈦奈米粒子氧化鋅奈米粒子的平均一次粒徑、以及平均分散粒徑D50及D99係使用Microtrac UPA-EX150(商品名,日商日機裝(股份公司)製造)藉由動態光散射法而測定。 The average primary particle diameters and average dispersed particle diameters of the titanium oxide nano particles and zinc oxide nano particles are D50 and D99. Microtrac UPA-EX150 (trade name, manufactured by Nissho Nikkiso Co., Ltd.) is used for dynamic light scattering. And measured.
(實施例1-1至實施例1-7) (Examples 1-1 to 1-7)
使用由前述之潛影用水性墨組成物A構成之潛影用水性墨,藉由噴墨記錄方法,對素錠進行潛影之印刷。印刷 係僅對素錠之一面進行,且使用噴墨印表機(KC 600dpi搭載有列印頭之印字治具),以單程(one pass)方式進行。印刷條件係將液滴每1滴之質量設為7ng,將液滴量設為7pl。另外,印刷後,使印刷圖像面藉由24小時之自然乾燥而乾燥。 The latent image water-based ink composed of the aforementioned latent image water-based ink composition A was used to print a latent image on the plain ingot by an inkjet recording method. Printing is performed only on one side of the ingot, and it is performed in a one-pass method using an inkjet printer (KC 600dpi printing fixture equipped with a print head). The printing conditions were such that the mass of each droplet was 7 ng, and the amount of droplets was 7 pl. After printing, the printed image surface was dried by natural drying for 24 hours.
其次,針對印刷有潛影之素錠,求出可見光(室內燈)下的經該潛影用水性墨組成物A印刷之區域(潛影區域A)相對於未經潛影用水性墨組成物A印刷之區域(非潛影區域B)之階度值之差。素錠中之印刷有潛影之面之攝影係使用智慧型手機內建相機(商品名:iPhone6(註冊商標),美商Apple Inc.製造)。 Next, for the plain tablets printed with latent images, the area (latent image area A) printed by the latent image water-based ink composition A in visible light (interior light) is determined relative to the non-latent image water-based ink composition. Difference in the degree value of the area printed by A (non-latent image area B). The photograph with the latent image printed on the plain tablet uses a built-in camera (brand name: iPhone6 (registered trademark), manufactured by Apple Inc.) in a smartphone.
階度值之差係以下述方式而求出。亦即,將利用數位相機進行攝影所獲取之圖像資料使用市售之軟體而圖像轉換為8位元灰度,求出多個像素中之0至255之256個階段之階度值。進而,算出所獲得之階度值之平均值,自潛影區域A之階度值之平均值減去非潛影區域B之階度值之平均值而算出階度值之差。 The difference in the gradation values is obtained in the following manner. That is, the image data obtained by photographing with a digital camera is converted into 8-bit grayscale using commercially available software, and the gradation values of 256 stages from 0 to 255 in a plurality of pixels are obtained. Furthermore, the average value of the obtained gradation values is calculated, and the difference of the gradation values is calculated from the average value of the gradation values of the latent image area A minus the average value of the gradation values of the non-latent image area B.
其次,針對印刷有潛影之素錠,於每個實施例一面改變波長,一面照射紫外線(顯影化步驟),使該潛影顯影化而進行攝影(攝影步驟)。如下述表5所示,使用日商朝日分光(股份公司)製造之氙光源(商品名:MAX-303)作為照射機 構。所照射之紫外線之波長之變更係藉由併用氙光源所附帶之鏡模組(mirror module)與各種UV(ultra violet,紫外線)帶通濾波器(第一光學濾波器)而進行。如下述表7所示,紫外線之波長設為260nm、280nm、300nm、320nm、340nm、360nm、380nm。另外,氙光源之光強度設為約5000μW/cm2。 Next, the latent image printed with a latent image was irradiated with ultraviolet rays (developing step) while changing the wavelength in each of the examples to develop the latent image for photographing (photographing step). As shown in Table 5 below, a xenon light source (trade name: MAX-303) manufactured by Nissho Asahi Kogyo Co., Ltd. was used as the irradiation mechanism. The wavelength of the irradiated ultraviolet rays was changed by using a mirror module attached to the xenon light source and various UV (ultra violet) band-pass filters (first optical filters) in combination. As shown in Table 7 below, the wavelengths of the ultraviolet rays are 260 nm, 280 nm, 300 nm, 320 nm, 340 nm, 360 nm, and 380 nm. The light intensity of the xenon light source was set to about 5000 μW / cm 2 .
另外,作為攝影步驟中所使用之攝影機構,使用下述表6所示之紫外線相機。另外,攝影係於氙光源以外之外界光未侵入之暗室中進行。 In addition, as a photographing mechanism used in the photographing step, an ultraviolet camera shown in Table 6 below was used. In addition, photography was performed in a dark room where outside light outside the xenon light source did not enter.
繼而,算出各波長之紫外線照射下的經該潛影用水性墨組成物A印刷之區域(潛影區域A)相對於未經潛影用水性墨組成物A印刷之區域(非潛影區域B)之階度值之差。該階度值之差係以與可見光照射下之情形相同之方式求出。結果示於下述表7。 Then, the area printed by the latent image water-based ink composition A (latent image area A) under the irradiation of ultraviolet light of each wavelength is calculated with respect to the area (non-latent image area B) not printed by the latent image water-based ink composition A. ). The difference in the gradation values is obtained in the same manner as in the case of irradiation with visible light. The results are shown in Table 7 below.
(實施例1-8至實施例1-12) (Examples 1-8 to 1-12)
實施例1-8至實施例1-12中,將顯影化步驟中所照射之紫外線之波長設為260nm,且將氙光源之光強度分別變更為下述表7所示之值。除此以外,以與實施例1-1相同之方式,使各潛影顯影化後,利用紫外線相機進行攝影。另外,以與實施例1-1相同之方式,算出波長260nm之紫外線照射下之潛影區域A相對於非潛影區域B之階度值之差。結果示於下述表8。 In Examples 1-8 to 1-12, the wavelength of the ultraviolet light irradiated in the developing step was set to 260 nm, and the light intensity of the xenon light source was changed to the values shown in Table 7 below. Other than that, after developing each latent image in the same manner as in Example 1-1, photography was performed using an ultraviolet camera. In addition, in the same manner as in Example 1-1, the difference in the degree value of the latent image area A with respect to the non-latent image area B under the irradiation of ultraviolet rays with a wavelength of 260 nm was calculated. The results are shown in Table 8 below.
(比較例1-1至比較例1-3) (Comparative Example 1-1 to Comparative Example 1-3)
比較例1-1至比較例1-3中,將顯影化步驟中所照射之紫外線之波長設為260nm,且將氙光源之光強度分別變更為下述表7所示之值。除此以外,以與實施例1-1相同之方式,使各潛影顯影化後,利用紫外線相機進行攝影。另外,以與實施例1-1相同之方式,算出波長260nm之紫外線照射下之潛影區域A相對於非潛影區域B之階度值之差。結果示於下述表8。 In Comparative Examples 1-1 to 1-3, the wavelength of ultraviolet rays irradiated in the developing step was set to 260 nm, and the light intensity of the xenon light source was changed to the values shown in Table 7 below. Other than that, after developing each latent image in the same manner as in Example 1-1, photography was performed using an ultraviolet camera. In addition, in the same manner as in Example 1-1, the difference in the degree value of the latent image area A with respect to the non-latent image area B under the irradiation of ultraviolet rays with a wavelength of 260 nm was calculated. The results are shown in Table 8 below.
(實施例1-13) (Example 1-13)
使用由前述之可見圖像用水性墨組成物A構成之可見圖像用水性墨,藉由噴墨記錄方法對素錠進行可見圖像之印刷。印刷係僅對素錠之一面進行,且使用噴墨印表機(KC 600dpi搭載有列印頭之印字治具),以單程(one pass)方式進行。印刷條件係將液滴每1滴之質量設為7ng,將液滴量設為7pl。另外,印刷後,使印刷圖像面藉由24小時之自然乾燥而乾燥。 The visible image water-based ink composed of the visible image water-based ink composition A described above was used to print a visible image on the plain ingot by an inkjet recording method. Printing is performed on only one side of the plain ingot, and is performed in one pass using an inkjet printer (KC 600dpi printing fixture equipped with a print head). The printing conditions were such that the mass of each droplet was 7 ng, and the amount of droplets was 7 pl. After printing, the printed image surface was dried by natural drying for 24 hours.
其次,使用由前述之潛影用水性墨組成物A構成之潛影用水性墨,藉由噴墨記錄方法對素錠進行潛影之印刷。潛影之印刷係於可見圖像之印刷面進行。另外,作為潛影,印刷GS1QR編碼。進而,印刷方法及印刷條件係設為與實施例1-1相同。 Next, a latent image was printed on the plain ingot by an inkjet recording method using the latent image water-based ink composed of the aforementioned latent image water-based ink composition A. The latent image is printed on the printed side of the visible image. In addition, as a latent image, a GS1QR code is printed. Furthermore, the printing method and printing conditions were the same as those in Example 1-1.
其次,針對印刷有可見圖像及潛影之素錠,求出可見光(室內燈)下的經該潛影用水性墨組成物A印刷之區域(潛影區域A)相對於未經可見圖像用水性墨組成物A及潛影用水性墨組成物A印刷之區域(非潛影區域B)之階度值之差。進而,亦求出經可見圖像用水性墨組成物A印刷之區域(其他非潛影區域C)相對於非潛影區域B之階度值之差。素錠中之印刷有可見圖像及潛影之面之攝影係使用數位相機(商品名:PIASTM-II,QEA公司製造)。 Secondly, for the ingots printed with visible images and latent images, the area (latent image area A) printed by the latent image water-based ink composition A under visible light (interior lamp) is compared with the unvisible image. The difference in the order value of the area (non-latent image area B) printed with the water-based ink composition A and the latent image water-based ink composition A. Furthermore, the difference in the degree value of the area (other non-latent image area C) printed with the water-based ink composition A of the visible image with respect to the non-latent image area B was also calculated. Digital cameras (trade name: PIAS TM -II, manufactured by QEA) are used for photography in which the visible image and the latent image are printed on the plain tablets.
階度值之差係以下述方式而求出。亦即,針對利用數位相機進行攝影所獲取之圖像資料,求出以利用中間值法算出之8位元灰度換算之階度值。進而,自所獲得之潛影區域A之階度值減去非潛影區域B之階度值而算出階度值之差。 The difference in the gradation values is obtained in the following manner. That is, for the image data obtained by photographing with a digital camera, a gradation value of 8-bit gray scale conversion calculated by the median method is obtained. Furthermore, the difference between the gradation values is calculated by subtracting the gradation value of the non-latent image area B from the obtained gradation value of the latent image area A.
其次,針對印刷有可見圖像及潛影之素錠,照射波長為320nm之紫外線(顯影化步驟),使該潛影顯影化,並且使可見圖像潛影化而進行攝影(攝影步驟)。照射機構、除紫外線之波長區域以外之照射條件、及攝影裝置係設為與實施例1-1相同。 Next, a plain ingot printed with a visible image and a latent image is irradiated with ultraviolet rays having a wavelength of 320 nm (developing step), the latent image is developed, and the visible image is latent imaged to perform photography (photographing step). The irradiation mechanism, irradiation conditions other than the wavelength range of ultraviolet rays, and the imaging device were set to be the same as those in Example 1-1.
繼而,算出各波長之紫外線照射下的經該潛影用水性墨組成物A印刷之區域(潛影區域A)相對於未經可見圖像用水性墨組成物A及潛影用水性墨組成物A印刷之區域(非潛影區域B)之階度值之差。進而,亦求出經可見圖像用水性墨組成物A印刷之區域(其他非潛影區域C)相對於非潛影區域B之階度值之差。該等階度值之差係以與實施例1-1中之紫外線照射之情形相同之方式求出。結果示於下述表9。再者,求出潛影區域A相對於非潛影區域B之階度值之差時,亦可藉由對其他非潛影區域C進行亮度、色彩、對比度之調整、二值化等圖像處理而使該其他非潛影區域C不可見化,從而以潛影區域A相對於潛影區域A以外之區域之 階度值之差之形式求出。 Then, the area printed by the latent image water-based ink composition A (latent image area A) under ultraviolet light irradiation of each wavelength is calculated with respect to the water-based ink composition A and latent image water-based ink composition without visible images. Difference in the degree value of the area printed by A (non-latent image area B). Furthermore, the difference in the degree value of the area (other non-latent image area C) printed with the water-based ink composition A of the visible image with respect to the non-latent image area B was also calculated. The difference between these gradation values was determined in the same manner as in the case of the ultraviolet irradiation in Example 1-1. The results are shown in Table 9 below. Furthermore, when the difference in the degree value of the latent image area A with respect to the non-latent image area B is obtained, the brightness, color, contrast, and binarization of other non-latent image areas C can also be used. The processing makes the other non-latent image area C invisible, and is obtained as the difference in the degree value of the latent image area A with respect to areas other than the latent image area A.
(實施例1-14) (Examples 1-14)
實施例1-14中,與實施例1-13相比,使用可見圖像用水性墨組成物B代替可見圖像用水性墨組成物A。除此以外,以與實施例1-13相同之方式,使各潛影顯影化後,利用紫外線相機進行攝影。另外,以與實施例1-13相同之方式,分別算出波長320nm之紫外線照射下潛影區域A相對於非潛影區域B之階度值、及其他非潛影區域C相對於非潛影區域B之階度值之差。結果示於下述表9。 In Example 1-14, compared with Example 1-13, the visible image water-based ink composition B was used instead of the visible image water-based ink composition A. Other than that, after developing each latent image in the same manner as in Example 1-13, photography was performed with an ultraviolet camera. In addition, in the same manner as in Example 1-13, the degree values of the latent image area A with respect to the non-latent image area B and the other non-latent image areas C with respect to the non-latent image area were respectively calculated under ultraviolet irradiation at a wavelength of 320 nm. The difference in the order of B. The results are shown in Table 9 below.
(經顯影化之潛影之視認性及讀取性1) (Visibility and readability of developed latent image 1)
實施例1-1至實施例1-11及比較例1-1至比較例1-3中,進行經顯影化之潛影之紫外線照射下之視認性之評價。另外,針對紫外線照射前之素錠,亦進行可見光下之視認性之評價。評價基準係設為如下所述。結果示於表7及表8。 In Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-3, the visibility of the developed latent images under ultraviolet irradiation was evaluated. In addition, the plain ingots before ultraviolet irradiation were also evaluated for visibility under visible light. The evaluation criteria are as follows. The results are shown in Tables 7 and 8.
○:潛影區域A相對於非潛影區域B之階度值之差為5以上,能夠視認潛影。 (Circle): The difference of the order value of the latent image area A with respect to the non-latent image area B is 5 or more, and a latent image can be recognized.
×:潛影區域A相對於非潛影區域B之階度值之差未達5,難以視認潛影。 ×: The difference in the order value between the latent image area A and the non-latent image area B is less than 5, making it difficult to recognize the latent image.
另外,實施例1-13及實施例1-14中,分別進行可見圖像及經顯影化之潛影之紫外線照射下之視認性之評價。另外,針對紫外線照射前之素錠,亦進行可見光下之可見圖像之視認性之評價。評價基準除上述基準以外,設為如下所述。結果示於表9。 In Examples 1-13 and 1-14, the visibility of the visible image and the developed latent image under ultraviolet irradiation was evaluated, respectively. In addition, the plain ingots before ultraviolet irradiation were also evaluated for the visibility of visible images under visible light. The evaluation criteria are set as follows in addition to the above criteria. The results are shown in Table 9.
○:其他非潛影區域C相對於非潛影區域B之階度值之差為5以上,能夠視認可見圖像。 (Circle): The difference of the order value of the other non-latent image area C with respect to the non-latent image area B is 5 or more, and an image can be visually recognized.
×:其他非潛影區域C相對於非潛影區域B之階度值之差未達5,難以視認可見圖像。 ×: The difference between the order values of the other non-latent image regions C and the non-latent image regions B is less than 5, making it difficult to visually recognize the image.
進而,實施例1-13及實施例1-14中,亦進行以潛影之形式印刷之GS1QR編碼(以下,稱為『潛影GS1QR編碼』)之讀取性之評價。評價係藉由下述方式而進行,亦即,針 對上述之視認性評價中所攝影之圖像,舉起智慧型手機內建相機(商品名:iPhone6(商標註冊),美商Apple Inc.製造),使用GS1QR編碼讀取應用程式(應用程式名:GS1QR scodt,Leontec製造),讀取潛影GS1QR編碼。評價基準係設為如下所述。結果示於表9。 Furthermore, in Examples 1-13 and 1-14, the readability of the GS1QR code (hereinafter, referred to as "latent image GS1QR code") printed as a latent image was also evaluated. The evaluation was performed by raising the built-in camera of the smartphone (trade name: iPhone6 (trademark registration), manufactured by American Inc.) for the image taken in the above-mentioned visibility evaluation. ), Use the GS1QR code reading application (application name: GS1QR scodt, manufactured by Leontec), and read the latent image GS1QR code. The evaluation criteria are as follows. The results are shown in Table 9.
○:能夠讀取潛影GS1QR編碼,且所表示之內建資訊亦正確。 ○: The latent image GS1QR code can be read, and the built-in information indicated is also correct.
△:能夠讀取潛影GS1QR編碼,但所表示之內建資訊不正確。 △: The latent image GS1QR code can be read, but the built-in information indicated is incorrect.
×:無法讀取潛影GS1QR編碼。 ×: Unable to read the latent image GS1QR code.
(結果1) (Result 1)
如表7所示,印刷有潛影之素錠之可見光照射下潛影區域A相對於非潛影區域B之階度值之差為1,無法藉由目視確認該潛影。藉此,確認到潛影用水性墨組成物A藉由使用氧化鈦奈米粒子作為顏料,可印刷良好的潛影。 As shown in Table 7, the difference in the order value of the latent image area A with respect to the non-latent image area B under the visible light of the plain ingot printed with the latent image is 1, and the latent image cannot be confirmed visually. Thus, it was confirmed that the latent image water-based ink composition A can print a good latent image by using titanium oxide nano particles as a pigment.
其次,如表7所示,若對實施例1-1至實施例1-7之素錠,於260nm至380nm之範圍內分別照射預定之波長之紫外線,則於藉由潛影用水性墨組成物A所印刷之潛影區域A中,所照射之紫外線被吸收,結果,於紫外線相機中攝影為黑色。另一方面,未藉由潛影用水性墨組成物A印刷之非潛影區域B中,所照射之紫外線被反射,結果,於紫外線相機中攝影為白色。進而,於各實施例1-1至實施例1-7中, 可使潛影區域A相對於非潛影區域B之階度值之差成為5以上,可使潛影區域A與非潛影區域B之間產生可充分地視認潛影之程度之對比度。藉此,確認到於使用顏料中包含氧化鈦奈米粒子之潛影用水性墨組成物A之印刷中,可使潛影於紫外線照射下顯影化,可充分地識別印刷圖像。 Secondly, as shown in Table 7, if the ingots of Examples 1-1 to 1-7 were irradiated with ultraviolet rays of a predetermined wavelength in the range of 260nm to 380nm, the water-based inks composed of latent images were used. In the latent image area A printed by the object A, the irradiated ultraviolet rays are absorbed, and as a result, the photography is black in the ultraviolet camera. On the other hand, in the non-latent image area B which is not printed with the latent image water-based ink composition A, the irradiated ultraviolet rays are reflected, and as a result, the photography is white in an ultraviolet camera. Furthermore, in each of Examples 1-1 to 1-7, the difference between the order value of the latent image area A and the non-latent image area B can be made 5 or more, and the latent image area A and the non-latent image can be made. The contrast between the regions B is such that the latent image is sufficiently recognized. Accordingly, it was confirmed that in the printing using the water-based ink composition A of the latent image containing titanium oxide nano particles in the pigment, the latent image can be developed under ultraviolet irradiation, and the printed image can be fully recognized.
另外,如表8所示,確認到若對實施例1-8至實施例1-12之素錠,於約5000μW/cm2至30000μW/cm2之範圍內分別照射預定之光強度之紫外線,則可將潛影區域A相對於非潛影區域B之階度值之差控制為5以上。尤其是,可知於如實施例1-10般紫外線之波長區域為260nm之情形時,將光強度設為約20000μW/cm2時,可使潛影區域A相對於非潛影區域B之階度值之差成為極大值。 In addition, as shown in Table 8, it was confirmed that if the ingots of Examples 1-8 to 1-12 were irradiated with ultraviolet light of a predetermined light intensity within a range of about 5000 μW / cm 2 to 30,000 μW / cm 2 , Then, the difference between the order values of the latent image area A and the non-latent image area B can be controlled to be 5 or more. In particular, it can be seen that when the wavelength region of ultraviolet light is 260 nm as in Example 1-10, when the light intensity is set to about 20,000 μW / cm 2 , the order of the latent image region A relative to the non-latent image region B can be made. The difference in values becomes a maximum.
另一方面,於如比較例1-1般紫外線之光強度為約3000μW/cm2之情形或如比較例1-2及比較例1-3般光強度為約40000μW/cm2以上之情形時,難以使潛影區域A相對於非潛影區域B之階度值之差成為5以上,無法以良好的對比度使潛影充分地顯影化。 On the other hand, as in Comparative Example 1-1 as the ultraviolet light intensity of about 3000μW / cm 2 of the case or, as Comparative Example 1-2 and Comparative Examples 1-3 as a light intensity of about 40000μW / cm 2 or more of the case It is difficult to make the difference in the gradation value of the latent image area A with respect to the non-latent image area B be 5 or more, and it is impossible to sufficiently develop the latent image with good contrast.
另外,如表9所示,實施例1-13及實施例1-14中,素錠之可見光照射下之潛影區域A相對於非潛影區域B之階度值之差分別為3.5及1,無法藉由目視確認該潛影。進而,於潛影GS1QR編碼之讀取性評價中,亦無法讀取潛影 GS1QR編碼。藉此,確認到潛影用水性墨組成物A藉由使用氧化鈦奈米粒子作為顏料,可印刷良好的潛影。另一方面,素錠之可見光照射下之其他非潛影區域C相對於非潛影區域B之階度值之差分別為81.5及139.5,可藉由目視充分地識別該可見圖像。 In addition, as shown in Table 9, in Examples 1-13 and 1-14, the difference between the order values of the latent image area A and the non-latent image area B under the visible light irradiation of the plain ingot was 3.5 and 1 respectively. , The latent image cannot be confirmed visually. Furthermore, in the readability evaluation of the latent image GS1QR code, the latent image GS1QR code cannot be read. Thus, it was confirmed that the latent image water-based ink composition A can print a good latent image by using titanium oxide nano particles as a pigment. On the other hand, the difference between the order values of the other non-latent image regions C and the non-latent image regions B under the visible light irradiation of the plain ingot is 81.5 and 139.5, respectively, and the visible image can be fully identified by visual observation.
其次,如表9所示,於對實施例1-13及實施例1-14之素錠,分別照射波長為320nm之紫外線之情形時,於藉由潛影用水性墨組成物A所印刷之潛影區域A中所照射之紫外線被吸收,結果,於紫外線相機中攝影為黑色。另一方面,未藉由潛影用水性墨組成物A印刷之非潛影區域B中所照射之紫外線被反射,結果,於紫外線相機中攝影為白色。但是,實施例1-13中,藉由使用綠色3號之可見圖像用水性墨組成物B所印刷之其他非潛影區域C中,可見圖像潛影化,結果,於紫外線相機中攝影為白色,無法識別該可見圖像。另一方面,實施例1-14中,藉由使用碳黑之可見圖像用水性墨組成物A所印刷之其他非潛影區域C中所照射之紫外線被吸收,結果,於紫外線相機中攝影為黑色。另外,潛影GS1QR編碼之讀取性評價中,實施例1-13及實施例1-14中,均可讀取潛影GS1QR編碼。尤其是,實施例1-14中,潛影GS1QR編碼及可見圖像均可視認到,但潛影GS1QR編碼中所內建之資訊亦正確地表示。藉此,亦可知於實施例1-13及實施例1-14之兩者中,可正確地讀取潛影GS1QR編碼。 Next, as shown in Table 9, in the case where the ingots of Examples 1-13 and 1-14 were irradiated with ultraviolet rays having a wavelength of 320 nm, the printed materials were printed with the latent image water-based ink composition A. The ultraviolet rays irradiated in the latent image region A are absorbed, and as a result, the image is black in the ultraviolet camera. On the other hand, the ultraviolet rays irradiated in the non-latent image area B that was not printed with the latent image water-based ink composition A were reflected, and as a result, the photography was white in the ultraviolet camera. However, in Example 1-13, in the other non-latent image area C printed by using the water-based ink composition B of the visible image No. 3 in green, the visible image was latent imaged, and as a result, it was photographed in an ultraviolet camera. Is white and the visible image cannot be recognized. On the other hand, in Example 1-14, the ultraviolet rays irradiated in the other non-latent image area C printed by the aqueous ink composition A for visible images using carbon black were absorbed, and as a result, photographed in an ultraviolet camera It's black. In addition, in the readability evaluation of the latent image GS1QR code, the latent image GS1QR code can be read in both Examples 1-13 and 1-14. In particular, in Example 1-14, the latent image GS1QR code and the visible image were both visually recognized, but the information built into the latent image GS1QR code was also correctly represented. This also shows that in both of Examples 1-13 and 1-14, the latent image GS1QR code can be read correctly.
(實施例2-1至實施例2-7) (Examples 2-1 to 2-7)
實施例2-1至實施例2-7中,作為潛影用水性墨,使用由前述之潛影用水性墨組成物B構成之墨。除此以外,以與實施例1-1相同之方式,使各潛影顯影化後,利用紫外線相機進行攝影。另外,於每個實施例將紫外線之波長變更為下述表10所示之值,除此以外,以與實施例1-1相同之方式,算出各波長之紫外線照射下之潛影區域A相對於非潛影區域B之階度值之差。結果示於下述表10。 In Examples 2-1 to 2-7, as the latent image water-based ink, an ink composed of the aforementioned latent image water-based ink composition B was used. Other than that, after developing each latent image in the same manner as in Example 1-1, photography was performed using an ultraviolet camera. In addition, in each example, the wavelength of ultraviolet rays was changed to the values shown in Table 10 below, and the latent image area A under each wavelength of ultraviolet rays was calculated in the same manner as in Example 1-1. Difference in order value between non-latent image regions B. The results are shown in Table 10 below.
(實施例2-8) (Example 2-8)
實施例2-8中,與實施例1-13相比,使用潛影用水性墨組成物B代替潛影用水性墨組成物A。除此以外,以與實施例1-13相同之方式,使各潛影顯影化後,利用紫外線相機進行攝影。另外,以與實施例1-13相同之方式,分別算出波長320nm之紫外線照射下之潛影區域A相對於非潛影區域B之階度值、及其他非潛影區域C相對於非潛影區域B之階度值之差。結果示於下述表11。 In Example 2-8, compared with Example 1-13, the latent image water-based ink composition B was used instead of the latent image water-based ink composition A. Other than that, after developing each latent image in the same manner as in Example 1-13, photography was performed with an ultraviolet camera. In addition, in the same manner as in Example 1-13, the degree values of the latent image area A with respect to the non-latent image area B under the irradiation of ultraviolet rays with a wavelength of 320 nm were calculated, and other non-latent image areas C with respect to the non-latent image were calculated. The difference in the degree value of the region B. The results are shown in Table 11 below.
(實施例2-9) (Example 2-9)
實施例2-9中,與實施例2-8相比,使用可見圖像用水性墨組成物B代替可見圖像用水性墨組成物A。除此以外,以與實施例2-8相同之方式,使各潛影顯影化後,利用紫外線相機進行攝影。另外,以與實施例2-8相同之方式,分別算出波長320nm之紫外線照射下之潛影區域A相對於非潛影區域B之階度值、及其他非潛影區域C相對於非潛影區域B之階度值之差。結果示於下述表11。 In Example 2-9, compared with Example 2-8, the visible image water-based ink composition B was used instead of the visible image water-based ink composition A. Other than that, each latent image was developed in the same manner as in Example 2-8, and then photographed with an ultraviolet camera. In addition, in the same manner as in Example 2-8, the degree values of the latent image area A with respect to the non-latent image area B under the irradiation of ultraviolet rays with a wavelength of 320 nm and the other non-latent image areas C with respect to the non-latent image were calculated respectively. The difference in the degree value of the region B. The results are shown in Table 11 below.
(經顯影化之潛影之視認性及讀取性2) (Visualization and readability of the developed latent image 2)
實施例2-1至實施例2-7中,以與實施例1-1之情形相同之方式,進行經顯影化之潛影之紫外線照射下之視認性之評價。另外,針對紫外線照射前之素錠,亦以與實施例1-1之情形相同之方式,進行可見光下之視認性之評價。結果示於表10。 In Examples 2-1 to 2-7, the visibility of the developed latent image under ultraviolet irradiation was evaluated in the same manner as in the case of Example 1-1. In addition, the plain ingots before ultraviolet irradiation were also evaluated for visibility under visible light in the same manner as in the case of Example 1-1. The results are shown in Table 10.
另外,實施例2-8及實施例2-9中,以與實施例1-1之情形相同之方式,分別進行可見圖像及經顯影化之潛影之紫外線照射下之視認性之評價。另外,針對紫外線照射前之素錠,亦以與實施例1-1之情形相同之方式,進行可見光下之可見圖像之視認性之評價。結果示於表11。 In addition, in Examples 2-8 and 2-9, the visibility of a visible image and a developed latent image under ultraviolet irradiation was evaluated in the same manner as in the case of Example 1-1, respectively. In addition, with respect to the plain ingots before ultraviolet irradiation, the visibility of visible images under visible light was also evaluated in the same manner as in the case of Example 1-1. The results are shown in Table 11.
進而,實施例2-8及實施例2-9中,以與實施例1-1之情形相同之方式,亦進行潛影GS1QR編碼之讀取性之評價。結果示於表11。 Furthermore, in Examples 2-8 and 2-9, the readability of the latent image GS1 QR code was also evaluated in the same manner as in the case of Example 1-1. The results are shown in Table 11.
(結果2) (Result 2)
如表10所示,印刷有潛影之素錠之可見光照射下之潛影區域A相對於非潛影區域B之階度值之差為1,無法藉由目視確認該潛影。藉此,確認到潛影用水性墨組成物B藉由使用氧化鋅奈米粒子作為顏料,可印刷良好的潛影。 As shown in Table 10, the difference between the order value of the latent image area A and the non-latent image area B under the visible light irradiation of the plain ingot printed with the latent image is 1, and the latent image cannot be confirmed visually. From this, it was confirmed that the latent image aqueous ink composition B can print a good latent image by using zinc oxide nano particles as a pigment.
其次,如表10所示,若對實施例2-1至實施例2-7之素錠,於260nm至380nm之範圍內分別照射預定之波長之紫外線,則藉由潛影用水性墨組成物B所印刷之潛影區域A中所照射之紫外線被吸收,結果,於紫外線相機中攝影為黑色。另一方面,非藉由潛影用水性墨組成物B印刷之非潛影區域B中所照射之紫外線被反射,結果,於紫外線相機中攝影為白色。進而,各實施例2-1至實施例2-7中,可使潛影區域A相對於非潛影區域B之階度值之差成為5以上,可使潛影區域A與非潛影區域B之間產生可充分地視認潛影之程度之對比度。藉此,確認到於使用顏料中包含氧化鋅奈米粒子之潛影用水性墨組成物B之印刷中,可使潛影於紫外線照射下顯影化,可充分地識別印刷圖像。 Next, as shown in Table 10, if the ingots of Examples 2-1 to 2-7 were irradiated with ultraviolet rays of a predetermined wavelength in the range of 260nm to 380nm, the water-based ink composition of the latent image was used. The ultraviolet rays irradiated in the latent image region A printed by B are absorbed, and as a result, the photograph is black in the ultraviolet camera. On the other hand, the ultraviolet light irradiated in the non-latent image area B printed without the latent image water-based ink composition B was reflected, and as a result, the photography was white in the ultraviolet camera. Furthermore, in each of Examples 2-1 to 2-7, the difference between the order value of the latent image area A and the non-latent image area B can be made 5 or more, and the latent image area A and the non-latent image area can be made. The contrast between B is sufficient to recognize the latent image. Accordingly, it was confirmed that in the printing using the water-based ink composition B of the latent image containing zinc oxide nano particles in the pigment, the latent image can be developed under ultraviolet irradiation, and the printed image can be fully recognized.
另外,如表11所示,實施例2-8及實施例2-9中,素錠之可見光照射下之潛影區域A相對於非潛影區域B之階度值之差分別為0.5及4,無法藉由目視確認該潛影。進而,潛影GS1QR編碼之讀取性評價中,無法讀取潛影GS1QR編碼。藉此,確認到潛影用水性墨組成物B藉由使用氧化鋅奈米粒子作為顏料,可印刷良好的潛影。另一方面,素錠之可見光照射下之其他非潛影區域C相對於非潛影區域B之階度值之差分別為81.5及133,可藉由目視充分地識別該可見圖像。 In addition, as shown in Table 11, in Examples 2-8 and 2-9, the difference between the order values of the latent image area A and the non-latent image area B under the visible light irradiation of the ingot was 0.5 and 4 respectively. , The latent image cannot be confirmed visually. Furthermore, in the readability evaluation of the latent image GS1QR code, the latent image GS1QR code cannot be read. From this, it was confirmed that the latent image aqueous ink composition B can print a good latent image by using zinc oxide nano particles as a pigment. On the other hand, the difference between the order values of the other non-latent image areas C and the non-latent image areas B under the visible light irradiation of the plain ingots is 81.5 and 133, respectively, and the visible images can be fully identified by visual observation.
其次,如表11所示,於對實施例2-8及實施例2-9之素 錠,分別照射波長為320nm之紫外線之情形時,藉由於潛影用水性墨組成物B所印刷之潛影區域A中所照射之紫外線被吸收,結果,於紫外線相機中攝影為黑色。另一方面,於未藉由潛影用水性墨組成物B印刷之非潛影區域B中所照射之紫外線被反射,結果,於紫外線相機中攝影為白色。但是,實施例2-8中,藉由使用綠色3號之可見圖像用水性墨組成物B所印刷之其他非潛影區域C中,可見圖像潛影化,結果,於紫外線相機中攝影為白色,無法識別該可見圖像。另一方面,實施例2-9中,藉由使用碳黑之可見圖像用水性墨組成物A所印刷之其他非潛影區域C中所照射之紫外線被吸收,結果,於紫外線相機中攝影為黑色。另外,潛影GS1QR編碼之讀取性評價中,實施例2-8及實施例2-9中均可讀取潛影GS1QR編碼。尤其是,實施例2-9中,潛影GS1QR編碼及可見圖像均可視認到,但潛影GS1QR編碼中所內建之資訊亦正確地表示。藉此,亦可知於實施例2-8及實施例2-9之兩者中,可正確地讀取潛影GS1QR編碼。 Next, as shown in Table 11, when the ultraviolet ray with a wavelength of 320 nm was irradiated to the ingots of Examples 2-8 and 2-9, the latent image was printed by the latent image water-based ink composition B. The ultraviolet rays irradiated in the shadow area A are absorbed, and as a result, the image is black in the ultraviolet camera. On the other hand, the ultraviolet rays irradiated in the non-latent image region B that was not printed with the latent image water-based ink composition B were reflected, and as a result, the photograph was white in the ultraviolet camera. However, in Example 2-8, in the other non-latent image area C printed by using the water-based ink composition B of the visible image of green No. 3, the visible image was latent imaged, and as a result, it was photographed in an ultraviolet camera. Is white and the visible image cannot be recognized. On the other hand, in Example 2-9, the ultraviolet rays irradiated in the other non-latent image region C printed by the aqueous ink composition A for visible images using carbon black were absorbed, and as a result, photographed in an ultraviolet camera It's black. In addition, in the readability evaluation of the latent image GS1QR code, the latent image GS1QR code can be read in both Examples 2-8 and 2-9. In particular, in Example 2-9, the latent image GS1QR code and the visible image were both visually recognized, but the information built into the latent image GS1QR code was also correctly represented. This also shows that in both Examples 2-8 and 2-9, the latent image GS1 QR code can be read correctly.
(實施例3-1) (Example 3-1)
使用由前述之潛影用水性墨組成物A構成之潛影用水性墨,藉由噴墨記錄方法對素錠(日商京都藥品工業(股份公司)製造,商品名:安慰劑錠(Placebo tablet))進行潛影之印刷。印刷係僅對素錠之一面進行,且使用噴墨印表機(KC 600dpi搭載有列印頭之印字治具),以單程(one pass)方式進行。印刷條件係將液滴每1滴之質量設為7ng,將液滴量設 為7pl。另外,印刷後,使印刷圖像面藉由24小時之自然乾燥而乾燥。 Using the latent image water-based ink composed of the latent image water-based ink composition A described above, a plain tablet (manufactured by Nissho Kyoto Pharmaceutical Industry Co., Ltd.) was marketed by an inkjet recording method, and its trade name was Placebo tablet. )) Printing of latent images. Printing is performed on only one side of the plain ingot, and is performed in one pass using an inkjet printer (KC 600dpi printing fixture equipped with a print head). The printing conditions were such that the mass of each droplet was 7 ng, and the amount of droplets was 7 pl. After printing, the printed image surface was dried by natural drying for 24 hours.
其次,於螢光燈照射之室內環境下,對印刷有潛影之素錠照射波長260nm至400nm之紫外線而使潛影顯影化(顯影化步驟),進而進行經顯影化之潛影之識別性之評價(檢查步驟)。作為照射機構,使用日商朝日分光(股份公司)製造之氙光源(商品名:MAX-303)。照射機構之光源之光強度係設為約100000μW/cm2。另外,潛影之識別性係將於室內環境下能夠讀取潛影之情形設為○,將無法讀取之情形設為×。結果示於下述表12。 Secondly, in the indoor environment irradiated with a fluorescent lamp, the plain ingot printed with the latent image is irradiated with ultraviolet rays having a wavelength of 260 nm to 400 nm to develop the latent image (developing step), and then the developed latent image is recognized. Evaluation (inspection procedure). As the irradiation mechanism, a xenon light source (trade name: MAX-303) manufactured by Nissho Asahi Kogyo Co., Ltd. was used. The light intensity of the light source of the irradiation mechanism is set to about 100,000 μW / cm 2 . In addition, the recognizability of the latent image is set to ○ when the latent image can be read in an indoor environment, and X when it cannot be read. The results are shown in Table 12 below.
(實施例3-2) (Example 3-2)
本實施例中,與實施例3-1相比,將潛影用水性墨組成物A變更為潛影用水性墨組成物B。除此以外,以與實施例3-1相同之方式,進行素錠表面所印刷之潛影之識別性之評價。結果示於下述表12。 In this example, compared with Example 3-1, the latent image water-based ink composition A was changed to a latent image water-based ink composition B. Other than that, evaluation of the recognizability of the latent image printed on the surface of the plain ingot was performed in the same manner as in Example 3-1. The results are shown in Table 12 below.
(結果3) (Result 3)
如表12所示,各實施例之素錠上所印刷之潛影於螢光燈照射之室內環境下無法識別。進而,若於室內環境下對素錠照射紫外線,則於各實施例之素錠上所印刷之潛影區域A之潛影中,該紫外線被吸收,結果,可以目視確認到黑色之印刷圖像。另一方面,確認到未印刷潛影之非潛影區域B中,以所照射之紫外線作為激發光而產生可見光區域之螢光。藉此,確認到使用含有氧化鈦奈米粒子之潛影用水性墨組成物A、或含有氧化鋅奈米粒子之潛影用水性墨組成物B而印刷有潛影之各素錠中,可不特地使用紫外線相機等攝影裝置地於可見光照射之通常之室內環境下使潛影容易地識別。 As shown in Table 12, the latent images printed on the plain ingots of each of the examples could not be recognized under the indoor environment illuminated by fluorescent lamps. Furthermore, if the plain ingot is irradiated with ultraviolet rays in an indoor environment, the latent image in the latent image area A printed on the plain ingots of each example is absorbed, and as a result, a black printed image can be visually confirmed. . On the other hand, it was confirmed that in the non-latent image region B in which the latent image is not printed, fluorescent light in a visible light region was generated using the irradiated ultraviolet rays as excitation light. Accordingly, it was confirmed that the latent image printed on the ladle image using the latent image aqueous ink composition A containing titanium oxide nano particles or the latent image aqueous ink composition B containing zinc oxide nano particles was not required. A latent image can be easily identified in a normal indoor environment irradiated with visible light by using a photographing device such as an ultraviolet camera.
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