JP7027746B2 - Phosphorescent paper and its manufacturing method - Google Patents
Phosphorescent paper and its manufacturing method Download PDFInfo
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- JP7027746B2 JP7027746B2 JP2017175918A JP2017175918A JP7027746B2 JP 7027746 B2 JP7027746 B2 JP 7027746B2 JP 2017175918 A JP2017175918 A JP 2017175918A JP 2017175918 A JP2017175918 A JP 2017175918A JP 7027746 B2 JP7027746 B2 JP 7027746B2
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Description
本発明は、蓄光性のある紙、いわゆる蓄光紙、及びその製造方法に関し、特に、蓄光性が高く、両面に蓄光性があり、更には印刷が可能な蓄光紙及びその製造方法に関する。 The present invention relates to a phosphorescent paper, so-called phosphorescent paper, and a method for producing the same, and more particularly to a phosphorescent paper having high phosphorescent property, having phosphorescent properties on both sides, and being printable, and a method for producing the same.
現在、蓄光性をもつ紙は、後工程で蓄光性顔料等を印刷、又はコーティング等の手法により蓄光性を付与することが一般的に行なわれている。
しかし、印刷によって蓄光性を付与する場合は、絵柄等部分的にしか付与できず、コーティング等により全面塗工すると紙のカールが問題となる。
そこで、原紙の抄紙段階で蓄光性顔料を抄きこむことでこれらを改善し、また表裏両面に安定的に蓄光性を得る方法が知られている（例えば、特許文献１）。
At present, it is generally practiced to impart phosphorescent property to paper having phosphorescent property by printing or coating a phosphorescent pigment or the like in a subsequent process.
However, when the phosphorescent property is imparted by printing, it can be imparted only partially such as a pattern, and if the entire surface is coated by coating or the like, curling of the paper becomes a problem.
Therefore, there is known a method of improving these by injecting a phosphorescent pigment at the papermaking stage of the base paper and stably obtaining phosphorescent properties on both the front and back surfaces (for example, Patent Document 1).
ところが、従来の蓄光性顔料を含む紙においては、高い蓄光性を得るために、蓄光性顔料の粒径を大きくすると、紙への蓄光性顔料の歩留まりが低く、結果として生産性が悪くなることがあった。一方、蓄光性の顔料の粒径を小さくすると、蓄光性（輝度）が低くなることがあった。
本発明は、上記のような事情に鑑みてなされたものであり、生産性が高く、蓄光性（輝度）が高い蓄光紙及びその製造方法を提供することを目的とする。
However, in the conventional paper containing a phosphorescent pigment, if the particle size of the phosphorescent pigment is increased in order to obtain high phosphorescent property, the yield of the phosphorescent pigment on the paper is low, and as a result, the productivity is deteriorated. was there. On the other hand, when the particle size of the phosphorescent pigment is reduced, the phosphorescent property (luminance) may be lowered.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a phosphorescent paper having high productivity and high phosphorescence (luminance) and a method for producing the same.
上記課題を解決するために、本発明の一態様である蓄光紙は、パルプ材に繊維、蓄光性顔料、及び紙力増強剤を含有し、上記蓄光性顔料は、金属酸化物に希土類元素をドープさせてなる蓄光性顔料であり、上記金属酸化物がアルミン酸ストロンチウムであり、上記希土類元素がランタノイド系希土類元素であり、上記蓄光性顔料の粒径が３０μｍ以上５０μｍ以下であり、上記蓄光性顔料が上記パルプ材に対し５０重量％以上５５重量％以下含まれている。
上記課題を解決するために、本発明の他の態様である蓄光紙の製造方法は、蓄光性顔料、パルプ材、繊維、紙力増強剤、及び水を含んでスラリーを精製し、上記スラリーを抄紙して蓄光紙を作製する蓄光紙の製造方法であって、上記蓄光性顔料は、金属酸化物に希土類元素をドープさせてなる蓄光性顔料であり、上記金属酸化物がアルミン酸ストロンチウムであり、上記希土類元素がランタノイド系希土類元素であり、上記蓄光性顔料の粒径が３０μｍ以上５０μｍ以下であり、上記蓄光性顔料が上記スラリーに５０重量％以上５５重量％以下含まれている。
In order to solve the above problems, the phosphorescent paper according to one aspect of the present invention contains fibers, a phosphorescent pigment, and a paper strength enhancer in a pulp material, and the phosphorescent pigment contains a rare earth element in a metal oxide. It is a phosphorescent pigment doped, the metal oxide is strontium aluminate, the rare earth element is a lanthanoid-based rare earth element, the particle size of the phosphorescent pigment is 30 μm or more and 50 μm or less, and the phosphorescent pigment is used. The sex pigment is contained in an amount of 50 % by weight or more and 55% by weight or less based on the above pulp material.
In order to solve the above-mentioned problems, another method of producing phosphorescent paper of the present invention comprises purifying a slurry containing a phosphorescent pigment, a pulp material, a fiber, a paper strength enhancer, and water to obtain the above-mentioned slurry. A method for producing phosphorescent paper by making paper, the phosphorescent pigment is a phosphorescent pigment obtained by doping a metal oxide with a rare earth element, and the metal oxide is strontium aluminate. The rare earth element is a lanthanoid-based rare earth element, the particle size of the phosphorescent pigment is 30 μm or more and 50 μm or less, and the phosphorescent pigment is contained in the slurry in an amount of 50 % by weight or more and 55% by weight or less.
本発明の一態様によれば、生産性が高く、蓄光性（輝度）が高い蓄光紙及びその製造方法を提供することができる。 According to one aspect of the present invention, it is possible to provide a phosphorescent paper having high productivity and high phosphorescence (luminance) and a method for producing the same.
次に、本発明の一実施形態について図面を参照して説明する。
ここで、以下の図面の記載において、同一又は類似の部分には同一又は類似の符号を付している。ただし、図面は模式的なものであり、厚みと平面寸法との関係、各層の厚みの比率等は現実のものとは異なることがあることに留意すべきである。したがって、具体的な厚みや寸法は以下の説明を参酌して判断すべきものである。また、図面相互間においても互いの寸法の関係や比率が異なる部分が含まれていることはもちろんである。なお、以下の説明では、「重量部」を「部」ということがある。
また、以下に示す実施形態は、本発明の技術的思想を具体化するための構成を例示するものであって、本発明の技術的思想は、構成部品の材質、形状、構造等を下記のものに特定するものでない。本発明の技術的思想は、特許請求の範囲に記載された請求項が規定する技術的範囲内において、種々の変更を加えることができる。
Next, an embodiment of the present invention will be described with reference to the drawings.
Here, in the description of the following drawings, the same or similar parts are designated by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the plane dimensions, the ratio of the thickness of each layer, etc. may differ from the actual ones. Therefore, the specific thickness and dimensions should be determined in consideration of the following explanation. In addition, it goes without saying that parts having different dimensional relationships and ratios are included between the drawings. In the following description, the "part by weight" may be referred to as a "part".
Further, the embodiments shown below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention describes the material, shape, structure, etc. of the constituent parts as follows. It is not specific to things. The technical idea of the present invention may be modified in various ways within the technical scope specified by the claims described in the claims.
（構成）
本実施形態の蓄光紙（以下、蓄光シートということがある）は、パルプ材に繊維、蓄光性顔料、及び紙力増強剤を含有してなる。
ここで、本実施形態の蓄光紙に含まれる蓄光性顔料の粒径は、２０μｍ以上５０μｍ以下であり、この蓄光性顔料は、上記パルプ材に対し３５重量％以上５５重量％以下含まれている。本発明における蓄光性顔料の粒径は、レーザー回折・散乱法によって定義される平均粒径である。例えば、Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ Ｌｔｄ製 レーザー回折式粒度分布測定装置（型番：マスターサイザー３０００）を用いてＪＩＳ Ｚ８８２５によりＭｉｅ理論に基づいた条件で蓄光性顔料の粒径を測定した際に示される値である。
(Constitution)
The phosphorescent paper of the present embodiment (hereinafter, may be referred to as a phosphorescent sheet) contains a fiber, a phosphorescent pigment, and a paper strength enhancer in a pulp material.
Here, the particle size of the phosphorescent pigment contained in the phosphorescent paper of the present embodiment is 20 μm or more and 50 μm or less, and the phosphorescent pigment is contained in 35% by weight or more and 55% by weight or less with respect to the pulpwood. .. The particle size of the phosphorescent pigment in the present invention is an average particle size defined by the laser diffraction / scattering method. For example, it is a value shown when the particle size of the phosphorescent pigment is measured by JIS Z8825 under the conditions based on the Mie theory using a laser diffraction type particle size distribution measuring device (model number: Mastersizer 3000) manufactured by Malvern Instruments Ltd.
抄紙段階のスラリーに蓄光性顔料を添加することにより、蓄光性のある抄紙を提供することが可能となる。そして、粒径２０μｍ以上５０μｍ以下の蓄光性顔料を、３５重量％以上５５重量％以下添加することにより、さらに蓄光性の高く、生産性の高い蓄光紙を提供することが可能となる。
また、上記パルプ材は、さらしパルプ又は未さらしパルプのいずれか又は両方を含むことが好ましく、特に、さらしパルプを含むことが好ましい。製紙パルプにさらしパルプを添加することにより、さらに視認性に優れた蓄光性効果の高い蓄光紙を提供することが可能となる。
また、上記繊維は、ガラス繊維又は合成繊維のいずれか又は両方を含むことが好ましい。繊維を添加することにより、さらに強度の高い蓄光紙を提供することが可能となる。
また、本実施形態の蓄光紙の片面、又は両面には、合成樹脂がコーティングされていることが好ましい。
By adding a phosphorescent pigment to the slurry at the papermaking stage, it becomes possible to provide a papermaking having a phosphorescent property. By adding a phosphorescent pigment having a particle size of 20 μm or more and 50 μm or less in an amount of 35% by weight or more and 55% by weight or less, it becomes possible to provide a phosphorescent paper having higher phosphorescence and higher productivity.
Further, the pulp material preferably contains either or both of bleached pulp and unbleached pulp, and particularly preferably contains bleached pulp. By adding the exposed pulp to the papermaking pulp, it becomes possible to provide a phosphorescent paper having further excellent visibility and a high phosphorescent effect.
Further, the fiber preferably contains either or both of glass fiber and synthetic fiber. By adding the fiber, it becomes possible to provide a phosphorescent paper having higher strength.
Further, it is preferable that one side or both sides of the phosphorescent paper of the present embodiment is coated with a synthetic resin.
＜蓄光性顔料＞
本実施形態の蓄光紙に含まれる蓄光性顔料は、金属酸化物に希土類元素をドープさせてなる蓄光性顔料であることが好ましい。なお、上記金属酸化物は、アルミン酸ストロンチウムであり、上記希土類元素がランタノイド系希土類元素であることがより好ましい。希土類酸化物をドープさせた蓄光性顔料を添加することにより、さらに蓄光性の高い蓄光紙を提供することが可能となる。
<Phosphorescent pigment>
The phosphorescent pigment contained in the phosphorescent paper of the present embodiment is preferably a phosphorescent pigment obtained by doping a metal oxide with a rare earth element. The metal oxide is strontium aluminate, and it is more preferable that the rare earth element is a lanthanoid-based rare earth element. By adding a phosphorescent pigment doped with a rare earth oxide, it becomes possible to provide a phosphorescent paper having a higher phosphorescent property.
＜蓄光紙の製造方法＞
本実施形態の蓄光紙の製造方法は、上記構成を満たす蓄光紙を製造する方法であれば、特に限定されない。
本実施形態の蓄光紙の製造方法は、蓄光性顔料を製造する工程と、この蓄光性顔料、パルプ材、繊維、紙力増強剤、及び水を含んでスラリーを精製（調製）する工程と、上記スラリーを抄紙する工程とを備える。
このとき、上記蓄光性顔料を製造する工程においては、その粒径が２０μｍ以上５０μｍ以下になるように調製される。また、上記スラリーを精製する工程においては、上記蓄光性顔料が上記スラリーに３５重量％以上５５重量％以下含まれるように調製される。
<Manufacturing method of phosphorescent paper>
The method for producing the phosphorescent paper of the present embodiment is not particularly limited as long as it is a method for producing the phosphorescent paper satisfying the above configuration.
The method for producing phosphorescent paper of the present embodiment includes a step of producing a phosphorescent pigment, a step of purifying (preparing) a slurry containing the phosphorescent pigment, a pulp material, a fiber, a paper strength enhancer, and water. It is provided with a step of making the above slurry.
At this time, in the step of producing the phosphorescent pigment, the particle size is adjusted to be 20 μm or more and 50 μm or less. Further, in the step of purifying the slurry, the phosphorescent pigment is prepared so as to be contained in the slurry in an amount of 35% by weight or more and 55% by weight or less.
具体的には、例えば、粒径２０μｍ以上５０μｍ以下の蓄光性顔料を、３５重量％以上５５重量％以下の配合率で、補強材としてのガラス繊維、パルプ等と共に水中に分散させ、坪量２００ｇ／ｍ２となるよう手抄きによりすくい取った湿紙を熱ドラムに接触・乾燥させて蓄光紙を作製する。
なお、上述のように手抄きによりすくい取った湿紙を熱ドラムに接触・乾燥させた後、アクリル樹脂（例えば、固形分量が片面２３ｇ／ｍ２、合計４６ｇ／ｍ２）をコーティングしてもよい。このようにすることで、インクジェット印刷等により絵付けが可能である。
Specifically, for example, a phosphorescent pigment having a particle size of 20 μm or more and 50 μm or less is dispersed in water together with glass fiber, pulp or the like as a reinforcing material at a blending ratio of 35% by weight or more and 55% by weight or less, and has a basis weight of 200 g. Wet paper scooped by hand so that it becomes / m 2 is brought into contact with a heat drum and dried to prepare phosphorescent paper.
As described above, the wet paper scooped by hand is contacted with a heat drum and dried, and then coated with an acrylic resin (for example, the solid content is 23 g / m 2 on one side, 46 g / m 2 in total). May be good. By doing so, painting is possible by inkjet printing or the like.
［蓄光性顔料の製造方法］
ここで、蓄光性顔料を製造する工程について具体的に説明する。
蓄光性顔料は、以下の第１工程～第３工程を少なくとも経て作製される。
[Manufacturing method of phosphorescent pigment]
Here, the process of manufacturing the phosphorescent pigment will be specifically described.
The phosphorescent pigment is produced through at least the following first to third steps.
－第１工程－
第１工程は、アルカリ土類金属酸化物に希土類元素をドープさせてなる蓄光性顔料の原料粉末を準備する工程である。アルカリ土類金属酸化物としては、上述したように、アルミン酸ストロンチウム化合物、特にＳｒＡｌ２Ｏ４やＳｒ４Ａｌ１４Ｏ２５が好ましく、希土類元素としてはランタノイド系希土類元素が好ましく、希土類元素は酸化物の形態にて原料粉末に添加され、特にＥｕ２Ｏ３、Ｄｙ２Ｏ３が好ましいが、これに限定されるものではない。
蓄光性顔料の原料粉末は、市販のアルミン酸塩系蓄光性顔料（蓄光性蛍光体）であっても、以下に例示する製造工程によって製造されたアルミン酸系ストロンチウム蓄光性顔料であってもよく、蓄光性顔料の原料粉末を製造する際の工程としては、以下の工程が挙げられるが、これに限定されるものではない。
-First step-
The first step is a step of preparing a raw material powder of a phosphorescent pigment made by doping an alkaline earth metal oxide with a rare earth element. As described above, the alkaline earth metal oxide is preferably a strontium aluminate compound, particularly SrAl 2 O 4 or Sr 4 Al 14 O 25 , and the rare earth element is preferably a lanthanoid-based rare earth element, and the rare earth element is an oxide. It is added to the raw material powder in the form of, and Eu 2 O 3 and Dy 2 O 3 are particularly preferable, but the present invention is not limited thereto.
The raw material powder of the phosphorescent pigment may be a commercially available aluminate-based phosphorescent pigment (phosphorescent phosphor) or an aluminate-based strontium phosphorescent pigment manufactured by the manufacturing process exemplified below. The steps for producing the raw material powder of the phosphorescent pigment include, but are not limited to, the following steps.
上記アルミン酸系ストロンチウム蓄光性顔料を製造する際には、原料粉末として、球形γ‐Ａｌ２Ｏ３、ＳｒＣＯ３、Ｅｕ２Ｏ３、Ｄｙ２Ｏ３及びＨ３ＢＯ３の粉末をそれぞれ準備し、Ａｌ／（Ｓｒ＋Ｅｕ＋Ｄｙ）のモル比率が１．９０～１．９９（好ましくは１．９７～１．９９）の範囲内で、しかも、Ｈ３ＢＯ３の配合量が０．５重量％～２．５重量％（好ましくは２．０重量％～２．５重量％）の範囲内となるように秤量した後、上記の粉末を混合し、得られた混合物をるつぼの中に入れて、還元雰囲気下にて１３５０～１４５０℃で２～４時間加熱し、塊状体とした後、得られた塊状物をボールミリング等により粉砕し、得られた粉砕物をスクリーニングして、均一粒度（好ましくは粒径約２０μｍ以上５０μｍ以下）の蓄光性顔料の原料粉末を得る。
上記の工程により得られた蓄光性顔料原料粉末は、蛍光灯を用いて光照射を行った際に、暗所で黄緑色～青色に発光する。
When producing the above-mentioned aluminic acid-based strontium phosphorescent pigment, spherical γ-Al 2 O 3 , SrCO 3 , Eu 2 O 3 , Dy 2 O 3 and H 3 BO 3 powders are prepared as raw material powders, respectively. , Al / (Sr + Eu + Dy) in the molar ratio of 1.90 to 1.99 (preferably 1.97 to 1.99), and the blending amount of H 3 BO 3 is 0.5% by weight to 2 After weighing so as to be in the range of .5% by weight (preferably 2.0% by weight to 2.5% by weight), the above powders are mixed, and the obtained mixture is placed in a pot and reduced. After heating in an atmosphere at 1350 to 1450 ° C. for 2 to 4 hours to form a lump, the obtained lump is crushed by ball milling or the like, and the obtained crushed product is screened to have a uniform particle size (preferably). A raw material powder of a phosphorescent pigment having a particle size of about 20 μm or more and 50 μm or less) is obtained.
The phosphorescent pigment raw material powder obtained by the above step emits yellowish green to blue light in a dark place when irradiated with light using a fluorescent lamp.
－第２工程－
第２工程では、無機酸とリン酸塩を含む水溶液を準備し、当該水溶液に第１工程で得られた蓄光性顔料の原料粉末を加え、撹拌を行う。この際に使用する無機酸は、塩酸、硝酸及び硫酸から選ばれた少なくとも１種であり、リン酸塩は、リン酸二水素ナトリウム、リン酸二水素アンモニウム及びリン酸水素二アンモニウムから選ばれた少なくとも１種であることが好ましい。この第２工程における撹拌時間は、一般的は２０～３０℃の室温にて１０～６０分であり、３０～５０分がより好ましい。
-Second step-
In the second step, an aqueous solution containing an inorganic acid and a phosphate is prepared, the raw material powder of the phosphorescent pigment obtained in the first step is added to the aqueous solution, and stirring is performed. The inorganic acid used in this case is at least one selected from hydrochloric acid, nitric acid and sulfuric acid, and the phosphate is selected from sodium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate. It is preferably at least one. The stirring time in this second step is generally 10 to 60 minutes at room temperature of 20 to 30 ° C., more preferably 30 to 50 minutes.
この第２工程において使用される水溶液中には、上記の蓄光性顔料の原料粉末１００重量部に対して４～１４重量部、好ましくは６～１１重量部のリン酸二水素ナトリウムが含有されていることが好ましく、当該水溶液中の無機酸の量については、当該水溶液のｐＨが酸性（好ましくは５．０以下）となる量が好ましい。
このような無機酸とリン酸塩を含む水溶液を用いる第２工程（酸／リン酸塩処理工程）によって、蓄光性顔料の原料粉末の表面が水に対し不溶性又は難溶性となり、蓄光性顔料の耐水性が改善される。又、この第２工程によって、蓄光性顔料の原料粉末の表面が削られ、表面凹凸が少なくなり、平滑な表面となる。
The aqueous solution used in this second step contains 4 to 14 parts by weight, preferably 6 to 11 parts by weight of sodium dihydrogen phosphate with respect to 100 parts by weight of the raw material powder of the above phosphorescent pigment. The amount of the inorganic acid in the aqueous solution is preferably such that the pH of the aqueous solution is acidic (preferably 5.0 or less).
By the second step (acid / phosphate treatment step) using such an aqueous solution containing an inorganic acid and a phosphate, the surface of the raw material powder of the phosphoric acid pigment becomes insoluble or sparingly soluble in water, and the phosphoric acid pigment becomes insoluble or sparingly soluble. Water resistance is improved. Further, by this second step, the surface of the raw material powder of the phosphorescent pigment is scraped, the surface unevenness is reduced, and the surface becomes smooth.
－第３工程－
更に、第３工程では、第２工程の酸／リン酸塩処理によって得られた蓄光性顔料を水で洗浄するか、あるいは、アルカリ水溶液で中和処理を行った後に水分を除去（脱水）し、乾燥を行い、蓄光性顔料を得る。この際、水での洗浄は、複数回（好ましくは４～６回）行うことが好ましく、アルカリ水溶液で中和処理を行う場合には、蓄光性顔料を含む水溶液のｐＨを６．８～７．２の範囲に調整することが好ましい。本実施形態では、上記アルカリ水溶液の種類は特に限定されないが、水酸化ナトリウム水溶液が一般的である。
この第３工程における乾燥は室温で行っても、加温下（１００℃以下）で行っても良い。
上記の第３工程により、蓄光性顔料の表面に付着している不純物が洗い流され、未処理の蓄光性顔料（第１工程で準備した未処理の蓄光性顔料の原料粉末）に比べて、高い初期残光輝度特性及び耐水性を備えた蓄光性顔料が得られる。
-Third step-
Further, in the third step, the phosphorescent pigment obtained by the acid / phosphate treatment in the second step is washed with water or neutralized with an alkaline aqueous solution to remove (dehydrate) the water. , Dry to obtain a phosphoric acid pigment. At this time, washing with water is preferably performed a plurality of times (preferably 4 to 6 times), and when the neutralization treatment is performed with an alkaline aqueous solution, the pH of the aqueous solution containing the phosphorescent pigment is 6.8 to 7. It is preferable to adjust to the range of .2. In the present embodiment, the type of the alkaline aqueous solution is not particularly limited, but a sodium hydroxide aqueous solution is generally used.
The drying in the third step may be performed at room temperature or under heating (100 ° C. or lower).
By the above-mentioned third step, impurities adhering to the surface of the phosphorescent pigment are washed away, which is higher than that of the untreated phosphorescent pigment (raw material powder of the untreated phosphorescent pigment prepared in the first step). A phosphorescent pigment having initial afterglow luminance characteristics and water resistance can be obtained.
（他の実施形態）
他の実施形態として、上記のアルカリ処理を行う代わりに、第２工程で得られた蓄光性顔料を溶液から取り出して水で５回洗浄し、蓄光性顔料の表面に付着している不純物を洗い流した後、脱水・乾燥を行い、ｐＨ調整なしの酸／リン酸塩処理グリーン系の蓄光性顔料を得てもよい。
(Other embodiments)
As another embodiment, instead of performing the above-mentioned alkali treatment, the phosphoric acid pigment obtained in the second step is taken out from the solution and washed with water 5 times to wash away impurities adhering to the surface of the phosphoric acid pigment. After that, it may be dehydrated and dried to obtain an acid / phosphate-treated green phosphorescent pigment without pH adjustment.
また、その他の実施形態として、第１工程を次のようにしてもよい。すなわち、市販の球形γ‐Ａｌ２Ｏ３ ２６５０ｇ（２５．９９モル）と、高純度ＳｒＣＯ３ ２１１５ｇ（１４．３３モル）と、Ｅｕ２Ｏ３ ５５ｇ（０．１６モル）と、Ｄｙ２Ｏ３ ３８ｇ（０．１０モル）と、Ｈ３ＢＯ３ １４２ｇ（２．３０モル）を秤量し、これらを湿式方法にて混合することにより固体混合物５ｋｇを得る。そして、この固体混合物をるつぼに入れ、還元雰囲気下にて１４００℃で３時間反応させて塊状体を得、冷却を行った後、この塊状体をボールミルにて粉砕し、スクリーニング（篩分け）を行うことによって、均一な粒度（粒子径約２０μｍ以上５０μｍ以下）を有する未処理の蓄光性顔料の粉末（化学式：Ｓｒ４Ａｌ１４Ｏ２５）を生成させる。その後、上記の第２工程、第３工程を経て、ｐＨ調整ありの酸／リン酸塩処理ブルー系蓄光性顔料と、ｐＨ調整なしの酸／リン酸塩処理ブルー系蓄光性顔料を得ることができる。 Further, as another embodiment, the first step may be performed as follows. That is, commercially available spherical γ-Al 2 O 3 2650 g (25.99 mol), high-purity SrCO 3 2115 g (14.33 mol), Eu 2 O 3 55 g (0.16 mol), and Dy 2 O 3 38 g (0.10 mol) and 142 g (2.30 mol) of H 3 BO 3 are weighed and mixed by a wet method to obtain 5 kg of a solid mixture. Then, this solid mixture is placed in a pot and reacted at 1400 ° C. for 3 hours in a reducing atmosphere to obtain a mass, which is cooled and then pulverized with a ball mill for screening (sieving). By doing so, an untreated phosphorescent pigment powder (chemical formula: Sr 4 Al 14 O 25 ) having a uniform particle size (particle diameter of about 20 μm or more and 50 μm or less) is produced. Then, through the above-mentioned second and third steps, an acid / phosphate-treated blue phosphorescent pigment with pH adjustment and an acid / phosphate-treated blue phosphorescent pigment without pH adjustment can be obtained. can.
以下、実施例及び比較例を示して本発明を具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。
（実施例１）
＜蓄光紙の作製＞
［蓄光性顔料の作製］
第１工程：市販の球形γ‐Ａｌ２Ｏ３ １９７５ｇ（１９．３６モル）と、高純度ＳｒＣＯ３ ２７９３ｇ（１８．９２モル）と、Ｅｕ２Ｏ３ ４９ｇ（０．１４モル）と、Ｄｙ２Ｏ３ ６０ｇ（０．１６モル）と、Ｈ３ＢＯ３ １２３ｇ（２．００モル）を秤量し、これらを湿式方法にて混合することにより固体混合物５ｋｇを得た。そして、この固体混合物をるつぼに入れ、還元雰囲気下にて１４００℃で３時間反応させて塊状体を得、冷却を行った後、この塊状体をボールミルにて粉砕し、スクリーニング（篩分け）を行うことによって、均一な粒度（粒子径約３０μｍ）を有する未処理の蓄光性顔料の粉末（化学式：ＳｒＡｌ２Ｏ４）を生成させた。この粉末に白色のＬＥＤランプを用いて光照射したところ、暗所において黄緑色（イエローグリーン）に発光することが確認された。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.
(Example 1)
<Making phosphorescent paper>
[Preparation of phosphorescent pigment]
First step: Commercially available spherical γ-Al 2 O 3 1975 g (19.36 mol), high-purity SrCO 3 2793 g (18.92 mol), Eu 2 O 3 49 g (0.14 mol), and Dy 2 . O 360 g (0.16 mol) and H 3 BO 3 123 g (2.00 mol) were weighed and mixed by a wet method to obtain 5 kg of a solid mixture. Then, this solid mixture is placed in a pot and reacted at 1400 ° C. for 3 hours in a reducing atmosphere to obtain a mass, which is cooled and then pulverized with a ball mill for screening (sieving). By doing so, an untreated phosphorescent pigment powder (chemical formula: SrAl2O4 ) having a uniform particle size ( particle size of about 30 μm) was produced. When this powder was irradiated with light using a white LED lamp, it was confirmed that it emitted yellowish green (yellow green) in a dark place.
第２工程：５０ｍｌの水をビーカーに入れ、この中にリン酸塩としてＮａＨ２ＰＯ４・２Ｈ２Ｏ ６．３ｇ（０．０４モル）を添加し（ｐＨ４．８）、更にＨＮＯ３水溶液（１２．９Ｎ）３．２ｍｌを添加し、酸／リン酸塩処理溶液（ｐＨ１．２）を調製した。この処理溶液に、第１工程で製造した蓄光性顔料原料粉末６２．５ｇを加え、４０分間攪拌を行った。この時の処理溶液のｐＨは２．５であった。
第３工程：アルカリ水溶液として、ＮａＯＨ水溶液（０．２５Ｎ）を準備し、第２工程で得られた蓄光性顔料を含む溶液に、このアルカリ水溶液６０ｍｌを加えて、溶液のｐＨが７．０になるように調整し、脱水した後、乾燥を行い、ｐＨ調整ありの酸／リン酸塩処理グリーン系の蓄光性顔料を得た。
以上のようにして作製された粒径３０μｍの蓄光性顔料を配合率５０％、補強材としてのガラス繊維、パルプ等を水中に分散させ、坪量２００ｇ／ｍ２となるよう手抄きによりすくい取った湿紙を熱ドラムに接触・乾燥させ、実施例１の蓄光紙を作製した。
Second step: 50 ml of water is placed in a beaker, 6.3 g (0.04 mol) of NaH 2 PO 4.2H 2O is added as a phosphate (pH 4.8), and an aqueous solution of HNO 3 (pH 4.8) is further added. 12.9N) 3.2 ml was added to prepare an acid / phosphate treatment solution (pH 1.2). To this treatment solution, 62.5 g of the phosphorescent pigment raw material powder produced in the first step was added, and the mixture was stirred for 40 minutes. The pH of the treatment solution at this time was 2.5.
Third step: A NaOH aqueous solution (0.25N) is prepared as an alkaline aqueous solution, and 60 ml of this alkaline aqueous solution is added to the solution containing the phosphorescent pigment obtained in the second step to bring the pH of the solution to 7.0. After dehydration, the solution was dried to obtain an acid / phosphate-treated green phosphorescent pigment with pH adjustment.
The phosphorescent pigment having a particle size of 30 μm prepared as described above is blended in a blending ratio of 50%, glass fibers, pulp, etc. as reinforcing materials are dispersed in water, and scooped by hand so as to have a basis weight of 200 g / m 2 . The removed wet paper was brought into contact with a heat drum and dried to prepare the phosphorescent paper of Example 1.
＜評価＞
作製した実施例１の蓄光紙について、以下の要領で「輝度」及び「生産性」を評価した。
［輝度］
実施例１の蓄光紙の（燐光）輝度の測定については、ＪＩＳ Ｚ９１０７（２００８）の副分類ＪＡに準拠した方法で測定を行った。
輝度の測定用の試験片として、７０×１５０ｍｍにサンプルを切り出した後、２０℃、６５％ＲＨ環境に試験片を２４時間放置した。
その後、２０℃６５％ＲＨ環境にて、輝度計（コニカミノルタオプティクス株式会社製、ＬＳ‐１００）を用いて、標準光Ｄ６５を２００ルクスに２０分照射した後、光源を遮断し、２０分後及び６０分後の輝度を測定した。
評価基準として、２０分後の輝度が２４ｍｃｄ／ｍ２以上を〇、２０分後の輝度が２４ｍｃｄ／ｍ２以上かつ６０分後の輝度が７ｍｃｄ／ｍ２以上を◎、その他（２０分後の輝度が２４ｍｃｄ／ｍ２未満）を×として評価した。評価結果を表１に示す。
<Evaluation>
The "luminance" and "productivity" of the prepared phosphorescent paper of Example 1 were evaluated in the following manner.
[Luminance]
Regarding the measurement of the (phosphorescent) luminance of the phosphorescent paper of Example 1, the measurement was carried out by a method according to the subclass JA of JIS Z9107 (2008).
As a test piece for measuring the luminance, a sample was cut out to 70 × 150 mm, and then the test piece was left in a 20 ° C. and 65% RH environment for 24 hours.
Then, in a 20 ° C. 65% RH environment, a luminance meter (LS-100 manufactured by Konica Minolta Optics Co., Ltd.) was used to irradiate 200 lux with standard light D65 for 20 minutes, then shut off the light source, and 20 minutes later. And the brightness after 60 minutes was measured.
As evaluation criteria, the brightness after 20 minutes is 24 mcd / m 2 or more, the brightness after 20 minutes is 24 mcd / m 2 or more and the brightness after 60 minutes is 7 mcd / m 2 or more, and others (after 20 minutes). (Brightness is less than 24 mcd / m 2 ) was evaluated as x. The evaluation results are shown in Table 1.
［生産性（顔料歩留まり）］
実施例１の蓄光紙に対して、抄紙時の脱水廃液の吸光度を測定し、予め作成しておいた検量線から濃度に換算して、１００－（脱水廃液の顔料濃度／添加した顔料濃度）×１００により顔料歩留まりを算出した。この顔料歩留まりが８０％以上を生産性：○とし、顔料歩留まりが８０％未満を生産性：×として評価した。評価結果を表１に示す。
[Productivity (pigment yield)]
For the phosphorescent paper of Example 1, the absorbance of the dehydrated waste liquid at the time of paper making was measured, converted into a concentration from a calibration curve prepared in advance, and 100- (pigment concentration of dehydrated waste liquid / pigment concentration added). The pigment yield was calculated by × 100. The pigment yield of 80% or more was evaluated as productivity: ◯, and the pigment yield of less than 80% was evaluated as productivity: ×. The evaluation results are shown in Table 1.
（実施例２）
実施例１における補強材として、ガラス繊維に替えてポリエステルを混抄させた以外は実施例１と同じ方法で実施例２の蓄光紙を作製した。その後、実施例２の蓄光紙の輝度、及び生産性について実施例１と同様に評価した。実施例１と同様に、実施例２の蓄光紙の詳細と評価結果とを表１に示す。
（実施例３）
坪量を１５０ｇ／ｍ２とした以外は実施例１と同じ方法で実施例３の蓄光紙を作製した。その後、実施例３の蓄光紙の輝度、及び生産性について実施例１と同様に評価した。実施例１と同様に、実施例３の蓄光紙の詳細と評価結果とを表１に示す。
(Example 2)
As a reinforcing material in Example 1, the phosphorescent paper of Example 2 was produced by the same method as in Example 1 except that polyester was mixed in place of glass fiber. Then, the luminance and productivity of the phosphorescent paper of Example 2 were evaluated in the same manner as in Example 1. Similar to Example 1, the details of the phosphorescent paper of Example 2 and the evaluation results are shown in Table 1.
(Example 3)
The phosphorescent paper of Example 3 was produced by the same method as in Example 1 except that the basis weight was 150 g / m 2 . Then, the luminance and productivity of the phosphorescent paper of Example 3 were evaluated in the same manner as in Example 1. Similar to Example 1, the details of the phosphorescent paper of Example 3 and the evaluation results are shown in Table 1.
（比較例１）
粒径１３μｍの蓄光性顔料を使用した以外は実施例１と同じ方法で比較例１の蓄光紙を作製した。その後、比較例１の蓄光紙の輝度、及び生産性について実施例１と同様に評価した。実施例１と同様に、比較例１の蓄光紙の詳細と評価結果とを表１に示す。
（比較例２）
粒径１３μｍの蓄光性顔料を使用した以外は実施例２と同じ方法で比較例２の蓄光紙を作製した。その後、比較例２の蓄光紙の輝度、及び生産性について実施例１と同様に評価した。実施例１と同様に、比較例２の蓄光紙の詳細と評価結果とを表１に示す。
(Comparative Example 1)
The phosphorescent paper of Comparative Example 1 was produced by the same method as in Example 1 except that a phosphorescent pigment having a particle size of 13 μm was used. Then, the luminance and productivity of the phosphorescent paper of Comparative Example 1 were evaluated in the same manner as in Example 1. Similar to Example 1, the details of the phosphorescent paper of Comparative Example 1 and the evaluation results are shown in Table 1.
(Comparative Example 2)
The phosphorescent paper of Comparative Example 2 was produced by the same method as in Example 2 except that a phosphorescent pigment having a particle size of 13 μm was used. Then, the luminance and productivity of the phosphorescent paper of Comparative Example 2 were evaluated in the same manner as in Example 1. Similar to Example 1, the details of the phosphorescent paper of Comparative Example 2 and the evaluation results are shown in Table 1.
（比較例３）
原料に粒径６０μｍの蓄光性顔料を配合率７０％、坪量１５０ｇ／ｍ２とした以外は実施例１と同じ方法で比較例３の蓄光紙を作製した。その後、比較例３の蓄光紙の輝度、及び生産性について実施例１と同様に評価した。実施例１と同様に、比較例３の蓄光紙の詳細と評価結果とを表１に示す。
（比較例４）
原料に粒径３０μｍの蓄光性顔料を使用した以外は比較例３と同じ方法で比較例４の蓄光紙を作製した。その後、比較例４の蓄光紙の輝度、及び生産性について実施例１と同様に評価した。実施例１と同様に、比較例４の蓄光紙の詳細と評価結果とを表１に示す。
(Comparative Example 3)
The phosphorescent paper of Comparative Example 3 was produced by the same method as in Example 1 except that a phosphorescent pigment having a particle size of 60 μm was added to the raw material at a blending ratio of 70% and a basis weight of 150 g / m 2 . Then, the luminance and productivity of the phosphorescent paper of Comparative Example 3 were evaluated in the same manner as in Example 1. Similar to Example 1, the details of the phosphorescent paper of Comparative Example 3 and the evaluation results are shown in Table 1.
(Comparative Example 4)
The phosphorescent paper of Comparative Example 4 was produced by the same method as in Comparative Example 3 except that a phosphorescent pigment having a particle size of 30 μm was used as a raw material. Then, the luminance and productivity of the phosphorescent paper of Comparative Example 4 were evaluated in the same manner as in Example 1. Similar to Example 1, the details of the phosphorescent paper of Comparative Example 4 and the evaluation results are shown in Table 1.
＜評価結果＞
表１から分かるように、実施例１，２の蓄光紙は、ともに輝度が特に高く、蓄光性顔料の歩留が高いため生産性に優れていた。また、実施例３の蓄光紙は、輝度が高く、蓄光性顔料の歩留が高いため生産性に優れていた。
これらに対して、比較例１，２の蓄光紙は、蓄光性顔料の歩留が高く生産性に優れるが、輝度が低かった。また、比較例３の蓄光紙は、輝度は高いが、蓄光性顔料の歩留が低く、生産性に劣っていた。また、比較例４の蓄光紙は、輝度も低く、さらに蓄光性顔料歩の留も低く生産性に劣っていた。
すなわち、本発明の範囲である実施例１～３の蓄光紙では、生産性が高く、蓄光性（輝度）が高いことが分かる。
<Evaluation result>
As can be seen from Table 1, the phosphorescent papers of Examples 1 and 2 were both excellent in productivity because of their particularly high luminance and high yield of the phosphorescent pigment. Further, the phosphorescent paper of Example 3 was excellent in productivity because of its high luminance and high yield of the phosphorescent pigment.
On the other hand, the phosphorescent papers of Comparative Examples 1 and 2 had a high yield of the phosphorescent pigment and were excellent in productivity, but had low brightness. Further, the phosphorescent paper of Comparative Example 3 had high brightness, but the yield of the phosphorescent pigment was low, and the productivity was inferior. Further, the phosphorescent paper of Comparative Example 4 had a low luminance and a low retention of the phosphorescent pigment, and was inferior in productivity.
That is, it can be seen that the phosphorescent papers of Examples 1 to 3 which are the scope of the present invention have high productivity and high phosphorescence (luminance).
Claims (8)
前記蓄光性顔料は、金属酸化物に希土類元素をドープさせてなる蓄光性顔料であり、
前記金属酸化物がアルミン酸ストロンチウムであり、
前記希土類元素がランタノイド系希土類元素であり、
前記蓄光性顔料の粒径が３０μｍ以上５０μｍ以下であり、
前記蓄光性顔料が前記パルプ材に対し５０重量％以上５５重量％以下含まれたことを特徴とする蓄光紙。 Pulpwood contains fiber, phosphorescent pigment, and paper strength enhancer,
The phosphorescent pigment is a phosphorescent pigment obtained by doping a metal oxide with a rare earth element.
The metal oxide is strontium aluminate,
The rare earth element is a lanthanoid-based rare earth element.
The particle size of the phosphorescent pigment is 30 μm or more and 50 μm or less.
A phosphorescent paper containing 50 % by weight or more and 55% by weight or less of the phosphorescent pigment with respect to the pulp material.
前記スラリーを抄紙して蓄光紙を作製する蓄光紙の製造方法であって、
前記蓄光性顔料は、金属酸化物に希土類元素をドープさせてなる蓄光性顔料であり、
前記金属酸化物がアルミン酸ストロンチウムであり、
前記希土類元素がランタノイド系希土類元素であり、
前記蓄光性顔料の粒径が３０μｍ以上５０μｍ以下であり、前記蓄光性顔料が前記スラリーに５０重量％以上５５重量％以下含まれていることを特徴とする蓄光紙の製造方法。 Purify the slurry with a phosphorescent pigment, pulpwood, fiber, paper strength enhancer, and water.
A method for producing phosphorescent paper by making a phosphorescent paper by making the slurry.
The phosphorescent pigment is a phosphorescent pigment obtained by doping a metal oxide with a rare earth element.
The metal oxide is strontium aluminate,
The rare earth element is a lanthanoid-based rare earth element.
A method for producing phosphorescent paper, wherein the phosphorescent pigment has a particle size of 30 μm or more and 50 μm or less, and the slurry contains 50 % by weight or more and 55% by weight or less of the phosphorescent pigment.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002101146A1 (en) | 2001-05-11 | 2002-12-19 | Arina Nakayama | Luminous paper and production method thereof and utilization method thereof |
| JP2007284822A (en) | 2006-04-17 | 2007-11-01 | Oji Paper Co Ltd | Porous filler and method for producing the same, and porous filler slurry and paper |
| JP2012187869A (en) | 2011-03-11 | 2012-10-04 | Kj Specialty Paper Co Ltd | Phosphorescent decorative laminate |
| JP2016098454A (en) | 2014-11-21 | 2016-05-30 | 大日本印刷株式会社 | Form sheet |
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| JP3005026B2 (en) * | 1990-09-04 | 2000-01-31 | 三菱製紙株式会社 | Luminescent nonwoven fabric and method for producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002101146A1 (en) | 2001-05-11 | 2002-12-19 | Arina Nakayama | Luminous paper and production method thereof and utilization method thereof |
| JP2007284822A (en) | 2006-04-17 | 2007-11-01 | Oji Paper Co Ltd | Porous filler and method for producing the same, and porous filler slurry and paper |
| JP2012187869A (en) | 2011-03-11 | 2012-10-04 | Kj Specialty Paper Co Ltd | Phosphorescent decorative laminate |
| JP2016098454A (en) | 2014-11-21 | 2016-05-30 | 大日本印刷株式会社 | Form sheet |
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