JP6712710B1 - Water-based phosphorescent paint - Google Patents
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Abstract
【課題】高輝度耐水性蓄光顔料を含有する水系エマルション塗料の提供。【解決手段】ａ）水系エマルション樹脂２０〜３０重量％、ｂ）５０〜１５０μｍの粒径を有し、酸／リン酸塩処理された耐水性蓄光顔料３５〜５５重量％、ｃ）セルロース系増粘剤０．０５〜０．３重量％、ｄ）ポリアクリル酸系増粘剤０．２〜０．６重量％、ｅ）ウレタン系増粘剤０．４〜０．７重量％、ｆ）消泡剤、成膜助剤、防腐剤及び凍結防止剤から成るグループより選ばれた少なくとも１種の補助剤０．５〜１．５重量％、及びｇ）総量が１００％となる量の水を含み、Ｂ型回転粘度計（ＢＭ型）を用いて測定された当該塗料の粘度（ＪＩＳ Ｋ ５６００−２−３：１９９９を準用）が９００〜３０００ｍＰａ・ｓであることを特徴とする。【選択図】なしPROBLEM TO BE SOLVED: To provide an aqueous emulsion paint containing a high-luminance water-resistant phosphorescent pigment. SOLUTION: a) 20 to 30% by weight of an aqueous emulsion resin, b) 35 to 55% by weight of an acid/phosphate-treated water-resistant phosphorescent pigment having a particle size of 50 to 150 μm, and c) a cellulose-based additive. Viscosity agent 0.05 to 0.3% by weight, d) Polyacrylic acid type viscosity agent 0.2 to 0.6% by weight, e) Urethane type viscosity agent 0.4 to 0.7% by weight, f) 0.5 to 1.5% by weight of at least one auxiliary agent selected from the group consisting of defoaming agents, film forming aids, preservatives and antifreezing agents, and g) water in an amount that makes the total amount 100%. And the viscosity of the coating material (JIS K 5600-2-3:1999 is applied mutatis mutandis) measured using a B-type rotational viscometer (BM type) is 900 to 3000 mPa·s. [Selection diagram] None
Description
本発明は、水系蓄光塗料、特に、高輝度耐水性蓄光顔料を含有する水系エマルション塗料に関する。 The present invention relates to a water-based phosphorescent paint, and more particularly to a water-based emulsion paint containing a high-brightness water-resistant phosphorescent pigment.
一般的な従来タイプの蓄光顔料は耐水性がないので、このような蓄光顔料を塗料用顔料として使用した場合には、扱いやすい水系エマルション塗料とすることができず、現在では油性塗料のみが製品化されている。また、蓄光顔料を含む油性蓄光塗料は、油性であるために扱いにくく、しかも、蓄光顔料の含有率が低く中輝度であるために、蓄光塗料としての普及が進んでいない。 Since conventional conventional type phosphorescent pigments do not have water resistance, when such phosphorescent pigments are used as paint pigments, it is not possible to make water-based emulsion paints that are easy to handle, and currently only oil-based paints are available. Has been converted. In addition, oil-based phosphorescent paints containing a phosphorescent pigment are difficult to handle because they are oily, and because the phosphorescent pigment content is low and the brightness is medium, they have not been widely used as phosphorescent paints.
このような問題を解決するために、例えば下記の特許文献１には、水系蓄光塗料組成物が提案されており、従来タイプで中輝度の蓄光顔料の耐水性をわずかに改良し、短時間の耐水性を確保し、短時間の間に、蓄光塗料組成物と合成樹脂エマルションまたは水性塗料と混合して、蓄光塗膜を形成する塗装方法も提案されている。
しかしながら、特許文献１に記載の蓄光顔料（蓄光塗料組成物）の耐水性は完全ではなかったために、塗膜形成時に合成樹脂エマルションまたは水性塗料と混合する必要があり、塗装の現場で蓄光塗料を混合することになるため、作業性が良くないという問題点があった。又、従来の蓄光顔料はわずかでも水分があるとりん光輝度が低下し、形成された蓄光塗膜のりん光輝度が低下するという問題点もあった。
In order to solve such a problem, for example, Patent Document 1 below proposes a water-based phosphorescent coating composition, which slightly improves the water resistance of a conventional type and medium-luminance phosphorescent pigment, and A coating method has also been proposed which secures water resistance and mixes a phosphorescent coating composition with a synthetic resin emulsion or a water-based coating material in a short time to form a phosphorescent coating film.
However, since the water resistance of the phosphorescent pigment (phosphorescent coating composition) described in Patent Document 1 is not perfect, it is necessary to mix it with a synthetic resin emulsion or a water-based coating when forming a coating film. Since they are mixed, workability is not good. In addition, the conventional phosphorescent pigments have a problem that the phosphorescent luminance is lowered when even a small amount of water is present, and the phosphorescent luminance of the formed phosphorescent coating is lowered.
更に、今日までに、水系エマルション蓄光塗料の一例として、紫外線耐性や耐候性に優れたシリコン変性アクリル樹脂をベースとする塗料が市販されており、この塗料は、屋外仕様、硬質で変形のない縁石や非常用階段の安全対策設備用として用いられている。しかしながら、高比重の蓄光顔料を分散する技術が確立されていないために、コロイド的性質を有する塗料の状態では長時間塗料状態で貯蔵した場合に、２〜３週間レベルで蓄光顔料の凝集、沈降や固化（ハードケーキ化）が見られ、使用できなくなるという貯蔵安定性に関する問題点もあった。 Furthermore, to date, as an example of a water-based emulsion phosphorescent coating, a coating based on a silicone-modified acrylic resin having excellent UV resistance and weather resistance has been marketed, and this coating is an outdoor specification, hard and undeformed curb. It is also used as a safety measure facility for emergency stairs. However, since a technique for dispersing a phosphorescent pigment having a high specific gravity has not been established, when the paint having colloidal properties is stored in a paint state for a long time, the phosphorescent pigment aggregates and precipitates at a level of 2-3 weeks. There was also a problem with regard to storage stability in that it was hardened (hard cake) and could not be used.
尚、下記の特許文献２には、残光輝度特性及び耐水性に優れた蓄光顔料を製造するための方法が開示されており、この製造方法では、蓄光顔料原料粉末の表面が水に対して不溶性又は難溶性となることによって蓄光顔料の耐水性が改善されるが、この特許文献２には、蓄光顔料をコロイド状に分散させ安定化させて水系蓄光塗料とするための塗料組成に関する記述は一切存在しておらず、上記の蓄光顔料を従来の水系塗料中に分散させても、保存時に高比重の蓄光顔料が沈降することになる。 In addition, the following Patent Document 2 discloses a method for producing a phosphorescent pigment excellent in afterglow brightness characteristics and water resistance, and in this production method, the surface of the phosphorescent pigment raw material powder is against water. The water resistance of the phosphorescent pigment is improved by making it insoluble or sparingly soluble. However, in Patent Document 2, there is described a coating composition for dispersing and stabilizing the phosphorescent pigment in a colloidal state to form an aqueous phosphorescent paint. Even if the above-mentioned phosphorescent pigment is not present at all and is dispersed in a conventional water-based paint, the phosphorescent pigment having a high specific gravity will settle during storage.
本発明は、上述の従来技術における問題点を解決し、高比重の高輝度耐水性蓄光顔料の分散技術を確立して、貯蔵安定性（分散安定性）に優れ、下地材の素材や用途に最適な水系エマルション塗料（水系蓄光塗料）を提供することを課題とする。
本発明者等は、種々検討を行った結果、前記特許文献２に記載された高輝度耐水性蓄光顔料を用い、この蓄光顔料を水系エマルション樹脂液中に、特定量の増粘剤（セルロース系増粘剤とポリアクリル酸系増粘剤とウレタン系増粘剤）と補助剤と共に混合撹拌し、当該蓄光顔料を分散させて特定の粘度範囲の塗料組成物とした場合に、塗料の貯蔵安定性に優れ、塗布した後に形成される塗膜が高輝度の蓄光性能を発揮し、優れた屋外耐候性や洗濯耐久性が得られることを見出して、本発明を完成した。
The present invention solves the above-mentioned problems in the prior art and establishes a dispersion technology for a high-brightness, high-luminance, water-resistant phosphorescent pigment, which is excellent in storage stability (dispersion stability) and can be used as a base material or application. An object is to provide an optimum water-based emulsion paint (water-based phosphorescent paint).
As a result of various studies, the inventors of the present invention used the high-luminance water-resistant phosphorescent pigment described in Patent Document 2 and used the phosphorescent pigment in an aqueous emulsion resin liquid in a specific amount of a thickener (cellulosic adhesive). Storage stability of the paint when the thickener, polyacrylic acid thickener, urethane thickener) and auxiliary agent are mixed and stirred to disperse the phosphorescent pigment to form a paint composition with a specific viscosity range. The present invention was completed based on the finding that the coating film formed after application has excellent properties and exhibits high-luminance phosphorescence performance, and that excellent outdoor weather resistance and washing durability can be obtained.
上記の課題を解決可能な本発明の水系蓄光塗料は、蓄光顔料を含有する水系エマルション塗料であって、当該塗料が、
ａ）水系エマルション樹脂 ２０〜３０重量％、
ｂ）５０〜１５０μｍの粒径を有し、酸／リン酸塩処理された耐水性蓄光顔料 ３５〜５５重量％、
ｃ）セルロース系増粘剤 ０．０５〜０．３重量％、
ｄ）ポリアクリル酸系増粘剤 ０．２〜０．６重量％、
ｅ）ウレタン系増粘剤 ０．４〜０．７重量％、
ｆ）消泡剤、成膜助剤、防腐剤及び凍結防止剤から成るグループより選ばれた少なくとも１種の補助剤 ０．５〜１．５重量％、及び
ｇ）総量が１００％となる量の水
を含み、
Ｂ型回転粘度計（ＢＭ型）を用いて測定された当該塗料の粘度（ＪＩＳ Ｋ ５６００−２−３：１９９９を準用）が９００〜３０００ｍＰａ・ｓであること、及び
前記Ｂ型回転粘度計の回転数６ｒｐｍにおける粘度と回転数６０ｒｐｍにおける粘度の比を表すチキソ係数が２．０〜８．０であることを特徴とする。
The water-based phosphorescent paint of the present invention capable of solving the above problems is a water-based emulsion paint containing a phosphorescent pigment, wherein the paint is
a) Aqueous emulsion resin 20 to 30% by weight,
b) Acid/phosphate treated waterproof phosphorescent pigment 35-55% by weight, having a particle size of 50-150 μm,
c) Cellulosic thickener 0.05 to 0.3% by weight,
d) Polyacrylic acid-based thickener 0.2 to 0.6% by weight,
e) Urethane thickener 0.4 to 0.7% by weight,
f) at least one auxiliary selected from the group consisting of an antifoaming agent, a film forming auxiliary, an antiseptic and an antifreezing agent, 0.5 to 1.5% by weight, and g) an amount with which the total amount becomes 100%. Including water,
The viscosity of the coating material (JIS K 5600-2-3:1999 is applied mutatis mutandis) measured using a B type rotational viscometer (BM type) is 900 to 3000 mPa·s ; and
The B-type rotational viscometer is characterized in that the thixotropy coefficient representing the ratio of the viscosity at a rotation speed of 6 rpm and the viscosity at a rotation speed of 60 rpm is 2.0 to 8.0 .
又、本発明は、上記の特徴を有した水系蓄光塗料において、前記水系エマルション樹脂が、アクリル系エマルション樹脂、エポキシ系エマルション樹脂、ウレタン系エマルション樹脂、シリコン系エマルション樹脂、フッ素系エマルション樹脂、これら樹脂の共重合物および混合物から成るグループより選ばれたものであることを特徴とするものである。 Further, the present invention is a water-based phosphorescent coating having the above characteristics, wherein the water-based emulsion resin is an acrylic emulsion resin, an epoxy emulsion resin, a urethane emulsion resin, a silicon emulsion resin, a fluorine emulsion resin, or these resins. Is selected from the group consisting of copolymers and mixtures of the above.
更に、本発明は、上記の特徴を有した水系蓄光塗料において、前記耐水性蓄光顔料が、アルミン酸ストロンチウム化合物にランタノイド系希土類元素をドープさせてなる蓄光顔料原料粉末を、塩酸、硝酸及び硫酸から選ばれた少なくとも１種の無機酸と、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種のリン酸塩を含む水溶液を用いて酸／リン酸塩処理した後、水で洗浄又はアルカリ水溶液で中和処理された蓄光顔料であることを特徴とするものでもある。 Further, the present invention is a water-based phosphorescent coating having the above characteristics, wherein the water-resistant phosphorescent pigment is a phosphorescent raw material powder obtained by doping a strontium aluminate compound with a lanthanoid rare earth element, from hydrochloric acid, nitric acid and sulfuric acid. Acid/phosphate using an aqueous solution containing at least one inorganic acid selected and at least one phosphate selected from sodium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate It is also characterized in that it is a phosphorescent pigment which has been washed with water or neutralized with an aqueous alkaline solution after the treatment.
本発明の水系蓄光塗料は、塗料中に高輝度耐水性蓄光顔料が安定した状態で分散されているので、沈降や固化が生じにくく、塗装作業性、貯蔵安定性の点で優れており、この塗料を塗布して形成される塗膜は、高輝度の蓄光性能を発揮し、水に浸漬させた後においても、りん光輝度の低下が少ない。
又、本発明の水系蓄光塗料は、柔軟な素材の表面にも硬質素材の表面にも塗布することができるので、各種製品（例えば、夜光標識や夜光衣服や防災対策用品や建築資材等）に広く利用可能である。
The water-based phosphorescent paint of the present invention, since the high-brightness water-resistant phosphorescent pigment is dispersed in the paint in a stable state, is unlikely to cause sedimentation or solidification, and is excellent in coating workability and storage stability. A coating film formed by applying a coating material exhibits a high brightness phosphorescent property, and the phosphorescence brightness is not significantly reduced even after being immersed in water.
Further, the water-based phosphorescent coating of the present invention can be applied to both the surface of a flexible material and the surface of a hard material, so that it can be applied to various products (for example, luminescent markers, luminescent clothing, disaster prevention products, building materials, etc.). Widely available.
まず、本発明の水系蓄光塗料中に含まれる各成分について説明する。
本発明の水系蓄光塗料中に含まれる成分ａ）は水系エマルション樹脂であり、この成分ａ）の前記塗料中の配合割合は２０〜３０重量％であり、本発明の水系蓄光塗料を調製する際には、蓄光顔料が分散し易いように、樹脂固形分が４０〜５５重量％、好ましくは４５〜５０重量％である水系エマルション樹脂液を準備し、成分ａ）の配合割合が上記の範囲となるように水系エマルション樹脂液を配合（前記水系エマルション樹脂液を４０〜５５重量％、好ましくは４５〜５０重量％配合）するのが好ましく、この樹脂液には、樹脂固形分の他に乳化剤などの添加剤が１．０〜５．０重量％程度含まれる。
本願明細書において「水系エマルション樹脂」とは、乳化剤によって親水化され、水中に分散した状態で存在している微粒子状の樹脂を意味する。
First, each component contained in the water-based phosphorescent paint of the present invention will be described.
The component a) contained in the water-based phosphorescent paint of the present invention is a water-based emulsion resin, and the compounding ratio of this component a) in the paint is 20 to 30% by weight, and when preparing the water-based phosphorescent paint of the present invention. In order to facilitate dispersion of the phosphorescent pigment, an aqueous emulsion resin liquid having a resin solid content of 40 to 55% by weight, preferably 45 to 50% by weight is prepared, and the mixing ratio of the component a) is within the above range. It is preferable to add an aqueous emulsion resin liquid so that the content of the aqueous emulsion resin liquid is 40 to 55% by weight, preferably 45 to 50% by weight. The additive is contained in an amount of about 1.0 to 5.0% by weight.
In the present specification, the "aqueous emulsion resin" means a finely divided resin which is hydrophilized by an emulsifier and exists in a state of being dispersed in water.
本発明の水系蓄光塗料中に含まれる成分ａ）の水系エマルション樹脂は、アクリル系エマルション樹脂、エポキシ系エマルション樹脂、ウレタン系エマルション樹脂、シリコン系エマルション樹脂、フッ素系エマルション樹脂、これら樹脂の共重合物および混合物から成るグループより選ばれたものであることが好ましい。
本発明において、成分ａ）の水系エマルション樹脂としてアクリル系エマルション樹脂を選択した場合には、紫外線耐性、耐候性は低いが、室内用向きで安価な水系蓄光塗料となり、エポキシ系エマルション樹脂を選択した場合には、紫外線耐性、耐候性は低いが、熱硬化性で、比較的高温になる環境下でも使用可能な水系蓄光塗料となる。
又、ウレタン系エマルション樹脂を選択した場合には、塗膜に弾力性を付与することができ、繊維や皮革など弾力性、屈曲性、柔軟性が要求される素材への塗布に適したものとなり、シリコン系・フッ素系エマルション樹脂を選択した場合には、比較的高価な塗料となるが、屋外などで高耐久性、高耐候性を要求される素材への塗布に適したものとなる。本発明では、成分ａ）の水系エマルション樹脂として、シリコン変性アクリルエマルション樹脂やシリコン変性ウレタンエマルション樹脂を用いることも可能である。
The water-based emulsion resin of the component a) contained in the water-based phosphorescent coating composition of the present invention is an acrylic-based emulsion resin, an epoxy-based emulsion resin, a urethane-based emulsion resin, a silicon-based emulsion resin, a fluorine-based emulsion resin, or a copolymer of these resins. And selected from the group consisting of mixtures.
In the present invention, when an acrylic emulsion resin is selected as the water-based emulsion resin of the component a), the epoxy-based emulsion resin is selected because it has a low UV resistance and a low weather resistance, but it is an indoor-use and inexpensive water-based phosphorescent paint. In this case, the water-based phosphorescent coating is thermosetting and can be used even in an environment of relatively high temperature, although it has low UV resistance and weather resistance.
Also, when urethane-based emulsion resin is selected, elasticity can be imparted to the coating film, making it suitable for application to materials such as fibers and leather that require elasticity, flexibility, and flexibility. If a silicone-based/fluorine-based emulsion resin is selected, it will be a relatively expensive coating material, but it will be suitable for application to materials that require high durability and high weather resistance outdoors. In the present invention, it is also possible to use a silicone-modified acrylic emulsion resin or a silicone-modified urethane emulsion resin as the aqueous emulsion resin of the component a).
本発明の水系蓄光塗料中に含まれる成分ｂ）の蓄光顔料は、５０〜１５０μｍ、好ましくは６０〜１２０μｍの粒径を有し、酸／リン酸塩処理された耐水性蓄光顔料であり、この成分ｂ）の前記塗料中の配合割合は３５〜５５重量％、好ましくは４０〜５０重量％である。上記の粒径及び塗料中の配合割合に限定されるのは、高いりん光性能を有した塗膜を得るためである。尚、この蓄光顔料は、本発明の水系蓄光塗料中にコロイド状で分散している。
このような耐水性蓄光顔料としては、例えば前記特許文献２の製造方法により製造された蓄光顔料が好適であり、この蓄光顔料は、アルミン酸ストロンチウム化合物にランタノイド系希土類元素をドープさせてなる蓄光顔料原料粉末を準備し、この蓄光顔料原料粉末を、塩酸、硝酸及び硫酸から選ばれた少なくとも１種の無機酸と、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種のリン酸塩を含む水溶液に加え（この際、蓄光顔料原料粉末：前記リン酸塩の重量比率を１００：４〜１４とし、水溶液中の無機酸の量を、水溶液のｐＨが５．０以下となる量とする）、２０〜３０℃の温度にて撹拌し、酸／リン酸塩処理を行い、その後、得られた蓄光顔料を水で洗浄、もしくは、アルカリ水溶液で中和処理し、乾燥を行うことにより製造される。
The component b) phosphorescent pigment contained in the water-based phosphorescent paint of the present invention has a particle size of 50 to 150 μm, preferably 60 to 120 μm, and is an acid/phosphate treated water resistant phosphorescent pigment. The proportion of component b) in the coating composition is 35 to 55% by weight, preferably 40 to 50% by weight. The particle size and the blending ratio in the coating material are limited in order to obtain a coating film having high phosphorescence performance. In addition, this phosphorescent pigment is dispersed in a colloidal state in the water-based phosphorescent paint of the present invention.
As such a water-resistant phosphorescent pigment, for example, a phosphorescent pigment produced by the production method of Patent Document 2 is suitable, and the phosphorescent pigment is a phosphorescent pigment obtained by doping a strontium aluminate compound with a lanthanoid rare earth element. A raw material powder is prepared, and this phosphorescent pigment raw material powder is selected from at least one inorganic acid selected from hydrochloric acid, nitric acid and sulfuric acid, and sodium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate. In addition to the aqueous solution containing at least one phosphate (at this time, the weight ratio of the phosphorescent pigment raw material powder: the phosphate is 100:4 to 14), the amount of the inorganic acid in the aqueous solution is The amount is 5.0 or less), the mixture is stirred at a temperature of 20 to 30° C., acid/phosphate treatment is performed, and then the obtained phosphorescent pigment is washed with water or neutralized with an alkaline aqueous solution. It is manufactured by treating and drying.
本発明の水系蓄光塗料においては、蓄光顔料の凝集や沈降や固化を防止し、貯蔵安定性を高めるために複数種の増粘剤が配合されている。
そのうちの１種である成分ｃ）のセルロース系増粘剤は、塗料中に０．０５〜０．３重量％の割合で配合されており、市販のセルロース系増粘剤が種々利用できる。又、本発明の水系蓄光塗料には、成分ｄ）のポリアクリル酸系増粘剤が０．２〜０．６重量％配合されており、更に成分ｅ）のウレタン系増粘剤が０．４〜０．７重量％配合されており、ポリアクリル酸系増粘剤、ウレタン系増粘剤についても市販品が利用可能である。
上記成分ｃ）〜ｅ）の増粘剤はいずれも、前記の蓄光顔料と水系エマルション樹脂をコロイド状に分散し安定化させるために添加され、これら増粘剤を組み合わせて配合することにより、蓄光顔料の凝集・沈降が抑制できる。尚、上記成分ｃ）〜ｅ）の増粘剤の少なくとも１種の配合割合が上記範囲から外れた場合には、塗料の粘度が後述する適性粘度の下限値よりも小さくなるか、貯蔵時に、蓄光含量の沈降が生じ、塗装作業性も悪くなり、塗布形成された塗膜が水と接触した際に蓄光顔料のりん光輝度の低下が生じる。
In the water-based phosphorescent paint of the present invention, a plurality of types of thickeners are blended in order to prevent aggregation, sedimentation and solidification of the phosphorescent pigment and to enhance storage stability.
The cellulosic thickener as component c), which is one of them, is blended in the paint at a ratio of 0.05 to 0.3% by weight, and various commercially available cellulosic thickeners can be used. Further, the water-based phosphorescent coating composition of the present invention contains 0.2 to 0.6% by weight of the polyacrylic acid-based thickener as the component d), and the urethane-based thickener as the component e) of 0.1. It is blended in an amount of 4 to 0.7% by weight, and commercially available polyacrylic acid thickeners and urethane thickeners are also available.
Any of the thickeners of the above components c) to e) is added in order to disperse and stabilize the above-mentioned phosphorescent pigment and the water-based emulsion resin in a colloidal state. Aggregation and sedimentation of the pigment can be suppressed. When the blending ratio of at least one of the thickeners of the above components c) to e) is out of the above range, the viscosity of the coating material becomes smaller than the lower limit value of the suitable viscosity described below, or during storage, The phosphorescent content is settled, the coating workability is deteriorated, and the phosphorescent brightness of the phosphorescent pigment is lowered when the coating film formed by coating is brought into contact with water.
本発明の水系蓄光塗料中に含まれる成分ｆ）の補助剤は、消泡剤、成膜助剤、防腐剤及び凍結防止剤から成るグループより選ばれたものであって、市販品が種々利用でき、成分ｆ）全体の配合割合は０．５〜１．５重量％である。上記の消泡剤、成膜助剤、防腐剤及び凍結防止剤はそれぞれ、消泡性、成膜性、防腐性、凍結防止性を高める目的で添加され、それぞれの配合割合は適宜選択できる。
尚、本発明では、塗料中に分散状態で存在する蓄光顔料の分散安定性を維持する目的で、塗料のｐＨが６．８以下になる恐れがあるときに、ｐＨ調整剤（アルカリ水溶液）を添加することが好ましく、ｐＨ調整剤の添加によって塗料のｐＨを６．８〜７．２、好ましくは６．９〜７．１に維持することが好ましい。
又、本発明では、必要とされる色相に応じて着色顔料を、一般に２．０重量％以下の添加量にて添加しても良く、白色タイプの蛍光顔料やクリアタイプの蛍光顔料を添加することが可能である。
The auxiliary agent of the component f) contained in the water-based phosphorescent coating composition of the present invention is selected from the group consisting of antifoaming agents, film forming assistants, preservatives and antifreezing agents, and various commercially available products are used. It is possible, and the compounding ratio of the entire component f) is 0.5 to 1.5% by weight. The above defoaming agents, film-forming aids, preservatives and antifreezing agents are added for the purpose of enhancing defoaming properties, film-forming properties, antiseptic properties and antifreezing properties, and the respective mixing ratios can be appropriately selected.
In the present invention, in order to maintain the dispersion stability of the phosphorescent pigment existing in a dispersed state in the paint, when the pH of the paint may be 6.8 or less, a pH adjuster (alkaline aqueous solution) is used. It is preferable to add it, and it is preferable to maintain the pH of the coating material at 6.8 to 7.2, preferably 6.9 to 7.1 by adding a pH adjuster.
Further, in the present invention, a coloring pigment may be added in an addition amount of generally 2.0% by weight or less depending on a required hue, and a white type fluorescent pigment or a clear type fluorescent pigment is added. It is possible.
本発明の水系蓄光塗料における成分ｇ）は、上記成分ａ）〜ｆ）を含む塗料の総量が１００重量％となる量の水である。 The component g) in the water-based phosphorescent paint of the present invention is water in such an amount that the total amount of the paint containing the above components a) to f) becomes 100% by weight.
本発明の水系蓄光塗料において、前記蓄光顔料が安定して分散状態を維持するための粘度は、ＪＩＳ Ｋ ５６００−２−３：１９９９を準用して、ブルックフィールド回転粘度計（Ｂ型回転粘度計のＢＭ型）を用いて測定した際の粘度（測定温度：２３±０．２℃）が９００〜３０００ｍＰａ・ｓの範囲である。より好ましい粘度は１５００〜３０００ｍＰａ・ｓであり、特に好ましい粘度は１７００〜２９００ｍＰａ・ｓである。
上記粘度を有する本発明の水系蓄光塗料は、各種のコーティング法により塗布を行うことができ、例えば、繊維布帛の表面にスクリーン印刷法にて塗布することも可能である。
In the water-based phosphorescent paint of the present invention, the viscosity for stably maintaining the dispersed state of the phosphorescent pigment is the Brookfield rotational viscometer (B type rotational viscometer, according to JIS K 5600-2-3:1999). Viscosity (measurement temperature: 23±0.2° C.) in the range of 900 to 3000 mPa·s. A more preferable viscosity is 1500 to 3000 mPa·s, and a particularly preferable viscosity is 1700 to 2900 mPa·s.
The water-based phosphorescent coating composition of the present invention having the above viscosity can be applied by various coating methods, for example, it is also possible to apply it on the surface of the fiber cloth by a screen printing method.
尚、上記成分ａ）〜ｇ）を含む本発明の水系蓄光塗料は、上記Ｂ型回転粘度計（ローターＮｏ．２を使用）を用いた際の回転数６ｒｐｍにおける粘度と回転数６０ｒｐｍにおける粘度の比を表すチキソ係数（Ｔｉ値、揺変性の程度を表す指数）が２．０〜８．０であり、３．７〜５．０の範囲がより好ましい。 The water-based phosphorescent coating composition of the present invention containing the components a) to g) has a viscosity at a rotation speed of 6 rpm and a viscosity at a rotation speed of 60 rpm when using the B-type rotational viscometer (using rotor No. 2). The thixotropy coefficient (Ti value, index indicating the degree of thixotropy) indicating the ratio is 2.0 to 8.0, and the range of 3.7 to 5.0 is more preferable.
以下、本発明の実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples of the present invention, but the present invention is not limited to the following Examples.
[実施例１]
本発明の水系蓄光塗料を調製するに際し、以下の原料を準備した。
・成分ａ）の水系エマルション樹脂として、
ポリゾールAP-4765N：昭和電工株式会社製
パーマリンUA-368T：三洋化成株式会社製
・成分ｂ）の耐水性蓄光顔料として、
耐水性蓄光顔料GDK11060WP：エルティーアイ株式会社製（特許第５９６７７８７号公報記載の製法にて製造された蓄光顔料）
・成分ｃ）のセルロース系増粘剤として、
セロサイズQP4400：ダウ・ケミカルジャパン株式会社製
・成分ｄ）のポリアクリル酸系増粘剤として、
プライマルASE60：ダウ・ケミカルジャパン株式会社製
・成分ｅ）のウレタン系増粘剤として
アデカノールUH-420：株式会社ADEKA製
・成分ｆ）の消泡剤、成膜助剤、防腐剤として、
消泡剤：BYK-024、BYK Additive＆Instruments社製
成膜助剤：CS-12、チッソ株式会社製
防腐剤：スラオフ8800、大阪ガスケミカル株式会社製
[Example 1]
In preparing the water-based phosphorescent coating of the present invention, the following raw materials were prepared.
-As the water-based emulsion resin of component a),
Polysol AP-4765N: Showa Denko Co., Ltd. Permarin UA-368T: Sanyo Kasei Co., Ltd. ・Component b) water resistant phosphorescent pigment
Water-resistant phosphorescent pigment GDK11060WP: manufactured by LTI Corporation (phosphorescent pigment manufactured by the method described in Japanese Patent No. 5967787)
-As the cellulosic thickener of component c),
Cellosize QP4400: As a polyacrylic acid-based thickener of component d) manufactured by Dow Chemical Japan,
Primal ASE60: made by Dow Chemical Japan Co., as component e) urethane-based thickener Adecanol UH-420: made by ADEKA Co., Ltd., component f) as defoaming agent, film forming aid, preservative,
Defoaming agent: BYK-024, BYK Additive & Instruments Co., Ltd. Film forming aid: CS-12, manufactured by Chisso Corporation Preservative: Slaoff 8800, manufactured by Osaka Gas Chemicals Co., Ltd.
以下の表１に記載される水系エマルション樹脂液（固形分４７％）５０重量部に、表１記載のセルロース系増粘剤０．１重量部を混合・撹拌した後、耐水性蓄光顔料（ＬＴＩ社製）４０重量部を混合して撹拌した。その後、上記の混合物に、表１記載のポリアクリル酸系増粘剤０．３重量部、ウレタン系増粘剤０．６重量部、添加剤（消泡剤０．３重量部、成膜助剤０．５重量部、防腐剤０．２重量部）１．０重量部、水８．０重量部を添加し、混合・撹拌した。
このようにして調製された塗料の、ＢＭ型回転粘度計（（株）トキメック製）を用いて上記測定条件にて測定された粘度は２５００ｍＰａであり、チキソ係数は４．０であった。
50 parts by weight of an aqueous emulsion resin liquid (solid content 47%) shown in Table 1 below was mixed with 0.1 part by weight of the cellulosic thickener shown in Table 1 and stirred to obtain a water resistant phosphorescent pigment (LTI). 40 parts by weight) was mixed and stirred. Then, to the above mixture, 0.3 part by weight of the polyacrylic acid-based thickener shown in Table 1, 0.6 part by weight of the urethane-based thickener, additives (0.3 parts by weight of defoaming agent, film-forming aid) 0.5 parts by weight of agent, 0.2 parts by weight of preservative) 1.0 part by weight, and 8.0 parts by weight of water were added, and mixed and stirred.
The viscosity of the thus-prepared coating material measured by using a BM type rotational viscometer (manufactured by Tokimec Co., Ltd.) under the above-mentioned measurement conditions was 2500 mPa and the thixotropy coefficient was 4.0.
[実施例２〜８]
上記実施例１と同様にして、表１に記載される組成の塗料（実施例２〜８）をそれぞれ調製し、各塗料について粘度及びチキソ係数を測定した。
[Examples 2 to 8]
Paints (Examples 2 to 8) each having the composition shown in Table 1 were prepared in the same manner as in Example 1 above, and the viscosity and the thixotropy coefficient were measured for each paint.
[比較例１〜８]
上記実施例１と同様にして、表２に記載される組成の塗料（比較例１〜８）をそれぞれ調製し、各塗料について、粘度及びチキソ係数を測定した。
[Comparative Examples 1 to 8]
Paints (Comparative Examples 1 to 8) having the compositions shown in Table 2 were prepared in the same manner as in Example 1, and the viscosity and the thixotropy coefficient were measured for each paint.
以下の表１及び表２には、本発明の水系蓄光塗料（実施例１〜８）及び比較品（比較例１〜８）についての組成と物性が要約されており、表１、表２に示された「浸水後の輝度」、「貯蔵後の蓄光顔料の沈降、ハードケーキ化」、「塗装作業性」の試験方法は以下の通りである。
・浸水後の輝度
基材としてのアクリル板上に、各塗料をハケ塗りし、７日乾燥後、１時間浸水×１０サイクル後の輝度を浸水前品と比較した。
◎：輝度低下はほとんど見られなかった、○：若干の輝度低下は見られたが、実用上問題なし、△：輝度低下が見られ、実用上問題あり、×：著しい輝度低下が見られた
・貯蔵後の蓄光顔料の沈降、ハードケーキ化
１か月２０℃放置後の容器中の状態を目視にて観察した。
◎：沈降、ハードケーキ化はほとんど観察されなかった、○：沈降、ハードケーキ化が少し観察されたが、実用上問題なし、×：沈降、ハードケーキ化が観察された
・塗装作業性
調製直後にアクリル板の表面にハケ塗りし、垂直にして乾燥後塗膜の外観を観察した。
◎：タレはほとんど見られず、塗装作業性良好、○：若干のタレが生じたが、実用上問題なし、×：タレが見られ、塗装作業性不良
Tables 1 and 2 below summarize the compositions and physical properties of the water-based phosphorescent paints of the present invention (Examples 1 to 8) and comparative products (Comparative Examples 1 to 8). The test methods of the "brightness after water immersion", "precipitation of the phosphorescent pigment after storage, formation of a hard cake", and "painting workability" are shown below.
-Brightness after immersion in water Each paint was applied by brush onto an acrylic plate as a base material, and after drying for 7 days, the brightness after immersion for 1 hour x 10 cycles was compared with that before the immersion.
⊚: Almost no decrease in brightness was observed, ∘: Some decrease in brightness was observed, but there was no problem in practical use, Δ: There was a decrease in brightness, there was a problem in practical use, x: Significant decrease in brightness was observed -Settling of the phosphorescent pigment after storage and formation of a hard cake The state in the container after standing at 20°C for 1 month was visually observed.
⊚: Almost no sedimentation or hard cake formation was observed. ○: A small amount of sedimentation or hard cake formation was observed, but there was no practical problem. ×: Sedimentation or hard cake formation was observed.・Painting workability Immediately after preparation Then, the surface of the acrylic plate was applied with a brush, and after verticalizing, the appearance of the coating film was observed.
⊚: Little sagging, good workability for coating, ○: Slight sagging, no practical problems, ×: Sagging, poor coating workability
上記表１に示されるように、本発明の水系蓄光塗料（実施例１〜８）を用いて塗布形成された塗膜はいずれも、１時間浸水×１０サイクル後の浸水試験後において、良好な蓄光性能を示し、耐水性も良好であった。又、実施例１〜８の塗料はいずれも、２０℃で１か月放置した後においても蓄光顔料の沈降やハードケーキ化を起こすことなく、貯蔵安定性の点でも優れており、調製直後に塗布した際の乾燥後塗膜の外観の点でも良好であった。上記実施例１〜８の塗料の粘度は２０００〜２８００ｍＰａ・ｓの範囲内であり、チキソ係数は３．７〜５．０の範囲内であった。
これに対して、上記比較品（比較例１〜８の塗料）の場合には、浸水後の輝度測定において輝度の低下が見られ、又、２０℃で１か月放置した後において蓄光顔料の沈降やハードケーキ化が観察された。更に、調製直後に塗布した際にタレが生じ、塗装作業性が良くないことも確認された。尚、増粘剤の配合割合が少ない比較例１、５の塗料の粘度は８５０ｍＰａ以下であり、増粘剤の配合割合が多い比較例２〜４、６〜８の塗料の粘度は３２００ｍＰａ以上であり、これら比較例１〜８の塗料のチキソ係数はいずれも１．８以下であった。
又、本発明の水系蓄光塗料（実施例１〜８）を用いて塗布形成された塗膜が発揮する蓄光性能を評価したところ、りん光輝度（ＪＩＳ Ｚ ９１０７ ２００８に準拠）ＪＣ（高輝度）規格及び／又はＪＤ（超高輝度）規格以上に適合するものであることが確認された。
As shown in Table 1 above, all the coating films formed by coating using the water-based phosphorescent paints of the present invention (Examples 1 to 8) were good after the water immersion test after 1 hour water immersion×10 cycles. It showed light storage performance and good water resistance. Further, all of the paints of Examples 1 to 8 are excellent in storage stability without causing sedimentation or hard cake formation of the phosphorescent pigment even after standing at 20° C. for 1 month, and immediately after preparation. The appearance of the coating film after drying when applied was also good. The viscosity of the coating materials of Examples 1 to 8 was in the range of 2000 to 2800 mPa·s, and the thixotropy was in the range of 3.7 to 5.0.
On the other hand, in the case of the above-mentioned comparative products (paints of Comparative Examples 1 to 8), a decrease in brightness was observed in the brightness measurement after water immersion, and after leaving at 20°C for 1 month, Sedimentation and hard cake formation were observed. Further, it was also confirmed that sagging occurred when applied immediately after preparation, and the coating workability was not good. In addition, the viscosity of the paints of Comparative Examples 1 and 5 in which the mixing ratio of the thickening agent is small is 850 mPa or less, and the viscosity of the paints of Comparative Examples 2 to 4 and 6 to 8 in which the mixing ratio of the thickening agent is large is 3200 mPa or more. However, the thixotropy coefficient of each of the paints of Comparative Examples 1 to 8 was 1.8 or less.
Further, when the luminous performance exhibited by the coating film formed by using the water-based luminous paint of the present invention (Examples 1 to 8) was evaluated, phosphorescence luminance (according to JIS Z 9107 2008) JC (high luminance) It was confirmed that the standard and/or the JD (ultra high brightness) standard or more were met.
〔繊維布帛上に塗布した際の耐洗濯性評価結果〕
繊維布帛基材として、綿１００％布帛（３２０ｇ／ｍ２）、綿５０％ポリエステル５０％布帛（２６０ｇ／ｍ２）、ポリエステル１００％布帛（５０ｇ／ｍ２）、を準備し、各布帛の表面にスクリーン印刷法を用いて上記実施例１の塗料を２回塗布し、乾燥塗布量が約６００ｇ／ｍ２であるプリント部を有する試験布帛を作製した。
上記で得られた試験布帛について、ＪＩＳ Ｌ １９３０：２０１４ Ｃ４Ｍ法吊干しに従ってプリント部の耐洗濯性を評価した。
その結果、本発明の水系蓄光塗料を塗布して作製された試験布帛は、洗濯回数１回及び５回の両方において、洗濯後の外観は良好であり、変退色は４〜５級であり、ブリードについても５級であることが確認された。
又、洗濯を行う前の布帛と、５回洗濯を行った後の布帛について、ＪＩＳ Ｚ ９１０７：２００８によりりん光輝度を比較したところ、りん光輝度の低下はほとんど見られなかった。
以上の耐洗濯性評価結果から、本発明の水系蓄光塗料は繊維用の塗料としても有用であることが確認された。
[Results of evaluation of washing resistance when applied on fiber cloth]
As the fiber cloth base material, 100% cotton cloth (320 g/m 2 ), 50% cotton 50% polyester cloth (260 g/m 2 ), 100% polyester cloth (50 g/m 2 ) were prepared, and the surface of each cloth was prepared. Was applied twice with the screen printing method to prepare a test cloth having a printed portion with a dry coating amount of about 600 g/m 2 .
With respect to the test cloth obtained above, the washing resistance of the printed part was evaluated according to JIS L 1930:2014 C4M method hanging.
As a result, the test cloth produced by applying the water-based phosphorescent coating of the present invention has a good appearance after washing and a discoloration of 4 to 5 grades in both 1 and 5 times of washing. It was also confirmed that the bleed was grade 5.
Further, when the phosphorescence brightness of the cloth before being washed and the cloth after being washed 5 times were compared according to JIS Z 9107:2008, almost no decrease in the phosphorescence brightness was observed.
From the above washing resistance evaluation results, it was confirmed that the water-based phosphorescent paint of the present invention is also useful as a paint for fibers.
本発明の水系蓄光塗料は、塗料中に存在する耐水性蓄光顔料の分散安定性が優れており、沈降や固化が生じにくく、塗装作業性の点でも優れている。そして、この水系蓄光塗料を塗布して形成される塗膜は、高輝度の蓄光性能を発揮し、水に浸漬させた後においても、りん光輝度の低下が少なく、屋外用途や衣類にも広く利用できる。
尚、本発明の水系蓄光塗料は、繊維、皮革などの柔軟素材表面および、金属材、木材、石材、タイル材、コンクリート材、合成樹脂材などの硬質素材表面に形成される塗膜並びに当該塗膜を形成してなる衣類、靴類、鞄バッグ類、文房具、玩具、シート状の繊維材料、テント、リック、アウトドア用品、防災対策用品、避難対策用品、安全対策用品、建材、内装材、外装材、寝具、家具、建具等などの幅広い用途に利用可能である。
The water-based phosphorescent paint of the present invention is excellent in dispersion stability of the water-resistant phosphorescent pigment present in the paint, is unlikely to cause sedimentation or solidification, and is also excellent in coating workability. A coating film formed by applying this water-based phosphorescent coating exhibits high-luminance phosphorescent performance, and even after being immersed in water, phosphorescence luminance is not significantly reduced, and is widely used for outdoor applications and clothes. Available.
The water-based phosphorescent coating of the present invention is a coating film formed on a flexible material surface such as fiber or leather and a hard material surface such as metal material, wood, stone material, tile material, concrete material or synthetic resin material, and the coating. Membrane-formed clothing, shoes, bags, stationery, toys, sheet-shaped fiber materials, tents, licks, outdoor products, disaster prevention products, evacuation protection products, safety products, building materials, interior materials, exteriors. It can be used for a wide range of applications such as timber, bedding, furniture, and joinery.
Claims (2)
ａ）水系エマルション樹脂 ２０〜３０重量％、
ｂ）５０〜１５０μｍの粒径を有し、酸／リン酸塩処理された耐水性蓄光顔料 ３５〜５５重量％、
ｃ）セルロース系増粘剤 ０．０５〜０．３重量％、
ｄ）ポリアクリル酸系増粘剤 ０．２〜０．６重量％、
ｅ）ウレタン系増粘剤 ０．４〜０．７重量％、
ｆ）消泡剤、成膜助剤、防腐剤及び凍結防止剤から成るグループより選ばれた少なくとも１種の補助剤 ０．５〜１．５重量％、及び
ｇ）総量が１００％となる量の水
を含み、
Ｂ型回転粘度計（ＢＭ型）を用いて測定された当該塗料の粘度（ＪＩＳ Ｋ ５６００−２−３：１９９９を準用）が９００〜３０００ｍＰａ・ｓであること、及び
前記Ｂ型回転粘度計の回転数６ｒｐｍにおける粘度と回転数６０ｒｐｍにおける粘度の比を表すチキソ係数が２．０〜８．０であることを特徴とする水系蓄光塗料。 An aqueous emulsion paint containing a phosphorescent pigment, the paint comprising:
a) Aqueous emulsion resin 20 to 30% by weight,
b) Acid/phosphate treated waterproof phosphorescent pigment 35-55% by weight, having a particle size of 50-150 μm,
c) Cellulosic thickener 0.05 to 0.3% by weight,
d) Polyacrylic acid-based thickener 0.2 to 0.6% by weight,
e) Urethane thickener 0.4 to 0.7% by weight,
f) at least one auxiliary selected from the group consisting of an antifoaming agent, a film forming auxiliary, an antiseptic and an antifreezing agent, 0.5 to 1.5% by weight, and g) an amount with which the total amount becomes 100%. Including water,
The viscosity of the coating material (JIS K 5600-2-3:1999 is applied mutatis mutandis) measured using a B type rotational viscometer (BM type) is 900 to 3000 mPa·s ; and
A water-based phosphorescent coating having a thixotropy of 2.0 to 8.0, which represents the ratio of the viscosity at a rotation speed of 6 rpm and the viscosity at a rotation speed of 60 rpm of the B-type rotary viscometer .
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