JP6082510B2 - Method for producing nano-order dispersed water-based multicolor paint - Google Patents
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本発明は、水性多色塗料に関し、特にナノオーダー分散型水性多色蓄光塗料、ナノオーダー分散型水性多色蛍光塗料、ナノオーダー分散型水性多色再帰反射塗料、ナノオーダー分散型水性多色蓄光再帰反射塗料、ナノオーダー分散型水性多色蛍光再帰反射塗料、ナノオーダー分散型水性多色蓄光蛍光再帰反射塗料、これらナノオーダー分散型水性多色塗料の製造方法及びこれらナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置に関するものである。 The present invention relates to a water-based multicolor paint, and in particular, a nano-order dispersed water-based multicolor phosphorescent paint, a nano-order dispersed water-based multicolor fluorescent paint, a nano-order dispersed water-based multicolor retroreflective paint, and a nano-order dispersed water-based multicolor phosphorescent paint. Retroreflective coating, nano-order dispersed aqueous multicolor fluorescent retroreflective coating, nanoorder dispersed aqueous multicolor phosphorescent retroreflective coating, method for producing these nanoorder dispersed aqueous multicolored paint, and nanoorder dispersed aqueous multicolor The present invention relates to a vacuum stirrer / disperser used in the manufacture of paints.
塗料の用途は多岐に亘っており、そこで要求される特性も様々である。その中で、蓄光、蛍光、再帰反射及びこれらを組み合わせた塗料は各種のサインボード、道路標示、車両や船舶用途をはじめ、照明器具、布帛、建材など、様々に活用されている。 There are many uses for paints, and the properties required there are also various. Among them, phosphorescent, fluorescent, retroreflective and paints combining these are used in various ways such as various sign boards, road markings, vehicles and marine applications, lighting fixtures, fabrics, and building materials.
これら多岐に亘る用途の中で、近年の環境意識の高揚、エコロジー対応の要求から、水性塗料化が望まれていた。しかし、蓄光塗料においては、特に顔料の分離沈降によるポットライフの問題及び塗膜強度の問題から、実用的な水性蓄光、水性蛍光、水性再帰反射及びこれらを組み合わせた水性塗料は存在しなかった。 Among these diverse applications, water-based paints have been desired due to the recent heightened environmental awareness and demand for ecology. However, practical phosphorescent paint, aqueous fluorescence, aqueous retroreflection, and a combination of these have not existed in phosphorescent paints, particularly due to problems of pot life due to pigment separation and sedimentation and film strength problems.
また、蓄光塗料においては、蛍光発光時の呈色と昼光における呈色が異なることが通常であって、蓄光及び蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現する多色塗料は存在しなかった。 Further, in the phosphorescent paint, the coloration at the time of fluorescence emission and the coloration at daylight are usually different, and the coloration at the time of phosphorescence and fluorescence emission is the same or similar to the coloration in daylight. There were no multicolor paints to achieve this.
解決しようとする課題は、水性であってポットライフが長く、且つ実用的な塗膜形成条件でもって成膜出来、耐久性及び耐光性に於いても実用的な塗膜が得られ、蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現する多色蓄光塗料を実現することである。 The problem to be solved is that it is water-based, has a long pot life, can be formed under practical coating film forming conditions, and can provide a practical coating film in terms of durability and light resistance. It is to realize a multicolor phosphorescent paint that realizes multiple colors that are the same as or similar to the coloration in daylight.
これらの課題を解決するため、筆者らは、塗料の調整工程を鋭意検討し、ベースの水性エマルジョンを調製後減圧脱気を行いながら撹拌分散を行うことにより、水性であっても顔料の分離沈降が抑制されてポットライフが長く、成膜特性に優れ、硬度の高い塗膜を得られ、さらに蓄光及び／又は蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現するナノオーダー分散型水性多色蓄光塗料、ナノオーダー分散型水性多色蛍光塗料、ナノオーダー分散型水性多色再帰反射塗料、ナノオーダー分散型水性多色蓄光再帰反射塗料、ナノオーダー分散型水性多色蛍光再帰反射塗料、ナノオーダー分散型水性多色塗料の製造方法及びナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置を見出し、本発明を完成したのである。 In order to solve these problems, the authors diligently studied the process of preparing the paint, and after the base aqueous emulsion was prepared, it was stirred and dispersed while performing vacuum degassing, thereby separating and precipitating the pigment even in the aqueous Can be obtained, and can provide a coating film with long pot life, excellent film forming characteristics and high hardness, and also with multicolor that is equivalent to or close to that of daylighting in color accumulation during phosphorescence and / or fluorescence. Realized nano-order dispersed water-based multicolor phosphorescent paint, nano-order dispersed water-based multicolor fluorescent paint, nano-order dispersed water-based multicolor retroreflective coating, nano-order dispersed water-based multicolor phosphorescent retroreflective coating, nano-order dispersed water-based paint Discovered multicolor fluorescent retroreflective coating, nano-order dispersion type water-based multicolor paint manufacturing method, and vacuum stirring dispersion device used for manufacturing nano-order dispersion type water-based multicolor paint, and completed the present invention. Than it was.
本発明のナノオーダー分散型水性多色蓄光塗料、ナノオーダー分散型水性多色蛍光塗料、ナノオーダー分散型水性多色再帰反射塗料、ナノオーダー分散型水性多色蓄光再帰反射塗料、ナノオーダー分散型水性多色蛍光再帰反射塗料、ナノオーダー分散型水性多色塗料の製造方法及びナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置は、水性であってポットライフが長く、且つ実用的な塗膜形成条件でもって成膜出来、耐久性及び耐光性に於いても実用的な塗膜が得られ、蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現する多色塗料を実現するという利点があり、もって多岐に亘る用途に活用出来、我が国産業の発展に資するものである。 Nano-order dispersed water-based multicolor phosphorescent paint, nano-order dispersed water-based multicolor fluorescent paint, nano-order dispersed water-based multicolor retroreflective coating, nano-order dispersed water-based multicolor phosphorescent retroreflective coating, nano-order dispersed type Water-based multicolor fluorescent retroreflective coating material, nano-order dispersion type water-based multicolor paint manufacturing method and nano-order dispersion type water-based multi-color coating material for vacuum stirring and dispersing apparatus are water-based, have a long pot life, and are practical The film can be formed under various coating conditions, and a practical coating can be obtained in terms of durability and light resistance. It has the advantage of realizing multi-color paints that can be realized, and can be used for a wide range of applications, contributing to the development of Japanese industries.
本発明は、ナノオーダー分散型水性多色塗料及びナノオーダー分散型水性多色塗料の製造方法において、減圧脱気を行いながら撹拌分散を行うことにより、水性であっても顔料の分離沈降が抑制されてポットライフが長く、成膜特性に優れ、塗膜の強度が高く、さらに蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現するナノオーダー分散型水性多色塗料、ナノオーダー分散型水性多色塗料の製造方法及びナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置である。なお、本件特許明細書内で用いる「塗料」には、一般的な塗用のみでなく、所謂インクのように印刷等に用いる濃度のものも含まれる。 In the production method of nano-order dispersion type water-based multicolor paint and nano-order dispersion type water-based multicolor paint, the present invention suppresses separation and sedimentation of pigments even in water by stirring and dispersing while performing degassing under reduced pressure. The nano-order dispersion type water-based solution that has a long pot life, excellent film forming characteristics, high coating strength, and multicolor that is equivalent to or close to the coloration in daylight in the coloration at the time of fluorescence emission. The present invention relates to a color paint, a method for producing a nano-order dispersed water-based multicolor paint, and a vacuum stirring and dispersing apparatus used for producing a nano-order dispersed water-based multi-color paint. The “paint” used in the present patent specification includes not only general application but also a concentration used for printing, such as so-called ink.
本発明に係るナノオーダー分散型水性多色塗料の製造方法に於いては、合成樹脂エマルジョンおよび／または水溶性樹脂と、少なくともストロンチウム、カルシウム、バリウムの何れかとアルミニウムと酸素を含んでなる蓄光性及び／又は蛍光性顔料と、水を含む塗料組成物を、減圧脱気を行いながら撹拌分散を行うことによりナノオーダーの分散を行うことを特徴とする。なお、前記塗料組成物は、さらに増粘剤、分散剤、湿潤剤、消泡剤、抑泡剤、成膜助剤、凍結防止剤、凍結安定剤、防腐剤、沈降防止剤、付着防止剤、乾燥調製剤、或いは熱変換剤・断熱材・遮熱剤などの温度抑制剤、からなる群より選ばれた１種または２種以上の補助剤を含んでもよい。 In the method for producing a nano-order dispersed water-based multicolor paint according to the present invention, a synthetic resin emulsion and / or a water-soluble resin, a phosphorescent property comprising at least one of strontium, calcium and barium, aluminum and oxygen, and It is characterized by performing nano-order dispersion by stirring and dispersing a coating composition containing a fluorescent pigment and / or water while performing degassing under reduced pressure. The coating composition further comprises a thickener, a dispersant, a wetting agent, an antifoaming agent, an antifoaming agent, a film forming aid, an antifreezing agent, a freezing stabilizer, an antiseptic agent, an antisettling agent, and an antiadhesive agent. 1 type, or 2 or more types of adjuvants chosen from the group which consists of drying preparation agents, or temperature control agents, such as a heat conversion agent, a heat insulating material, and a heat shielding agent, may be included.
さらに本発明に係るナノオーダー分散型水性多色塗料は、再帰反射材を含むことが好ましい。また、蓄光或いは蛍光顔料とともに通常の発色を呈する顔料を含んでもよい。また、前記各顔料は、それぞれシリカ等によりコーティングされたものであってもよい。 Furthermore, the nano-order dispersion type water-based multicolor paint according to the present invention preferably contains a retroreflective material. Moreover, you may include the pigment which exhibits normal coloring with phosphorescence or a fluorescent pigment. Each pigment may be coated with silica or the like.
本発明に係るナノオーダー分散型水性多色塗料の製造方法に於いては、水性エマルジョン塗料組成物を、減圧脱気を行いながら撹拌分散を行うことによりナノオーダーの分散を行う。
図１は、本発明に係るナノオーダー分散型水性多色蓄光塗料の製造方法の工程のフローチャートである。まず、合成樹脂エマルジョンおよび／または水溶性樹脂と、少なくともストロンチウム、カルシウム、バリウムの何れかとアルミニウムと酸素を含んでなる蓄光性顔料或いは蛍光性顔料と、水を含む塗料組成物を、合成樹脂エマルジョンおよび／または水溶性樹脂を１００重量部、蓄光性顔料或いは蛍光性顔料を５重量部乃至５０重量部、水を５０重量部乃至２００重量部の範囲で混合して塗料組成物原料を調製する。ここで、塗料組成物原料にはさらに増粘剤、分散剤、湿潤剤、消泡剤、抑泡剤、成膜助剤、凍結防止剤、凍結安定剤、防腐剤、沈降防止剤、付着防止剤、乾燥調製剤、或いは熱変換剤・断熱材・遮熱剤などの温度抑制剤、からなる群より選ばれた１種または２種以上の補助剤を含んでもよい。さらに本発明に係るナノオーダー分散型水性多色塗料は、再帰反射材を含むことが好ましい。また、蓄光或いは蛍光顔料とともに通常の発色を呈する顔料を含んでもよい。また、前記各顔料は、それぞれシリカ等によりコーティングされたものであってもよい。
In the method for producing a nano-order dispersion type water-based multicolor paint according to the present invention, nano-order dispersion is performed by stirring and dispersing an aqueous emulsion paint composition while performing degassing under reduced pressure.
FIG. 1 is a flowchart of the steps of a method for producing a nano-order dispersed water-based multicolor phosphorescent paint according to the present invention. First, a synthetic resin emulsion and / or a water-soluble resin, a phosphorescent pigment or fluorescent pigment containing at least one of strontium, calcium, and barium, aluminum and oxygen, and water, and a coating composition containing water, the synthetic resin emulsion and A coating composition material is prepared by mixing 100 parts by weight of water-soluble resin, 5 to 50 parts by weight of phosphorescent pigment or fluorescent pigment, and 50 to 200 parts by weight of water. Here, the coating composition raw material further includes a thickener, a dispersant, a wetting agent, an antifoaming agent, an antifoaming agent, a film forming aid, an antifreezing agent, a freezing stabilizer, an antiseptic, an antisettling agent, and an anti-adhesion agent. One or two or more auxiliary agents selected from the group consisting of an agent, a drying preparation agent, or a temperature suppressing agent such as a heat conversion agent, a heat insulating material, and a heat shielding agent may be included. Furthermore, the nano-order dispersion type water-based multicolor paint according to the present invention preferably contains a retroreflective material. Moreover, you may include the pigment which exhibits normal coloring with phosphorescence or a fluorescent pigment. Each pigment may be coated with silica or the like.
図２は、本発明に係るナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置の概念図である。本発明に係るナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置は、フランジを有して容器部と蓋部が開閉出来るようになっており、前記塗料組成物原料を容器部に投入後フランジを密着させて容器部と蓋部を締め付け、容器体内を減圧出来るようになっている。 FIG. 2 is a conceptual diagram of a vacuum stirring and dispersing apparatus used for producing a nano-order dispersed water-based multicolor paint according to the present invention. The vacuum stirring and dispersing apparatus used in the production of the nano-order dispersion type water-based multicolor paint according to the present invention has a flange so that the container part and the lid part can be opened and closed, and the paint composition raw material is used in the container part. After the charging, the container part and the lid part are tightened by closely contacting the flange so that the inside of the container can be decompressed.
前記塗料組成物原料を容器部に投入後してフランジの締め付けを行った後、真空ポンプを作動させて容器体内を減圧し、またプロペラを回転させて撹拌分散を行う。なお、本発明に係るナノオーダー分散型水性多色蓄光塗料の製造方法に於いては、撹拌分散工程中の容器体内の圧力は１Ｐａ乃至５００００Ｐａに調整することが望ましい。容器体内の圧力は１Ｐａ乃至５０００Ｐａに調整することがさらに望ましく、１Ｐａ乃至５００Ｐａに調整することがより望ましい。容器体内に設置されたプロペラを回転させて撹拌分散を行う工程と減圧工程は交互に繰り返して行うか、或いは同時に行われる。 After the raw material of the coating composition is put into the container part and the flange is tightened, the vacuum pump is operated to depressurize the container body, and the propeller is rotated to disperse the mixture. In the method for producing a nano-order dispersed water-based multicolor phosphorescent paint according to the present invention, it is desirable to adjust the pressure in the container during the stirring and dispersing step to 1 Pa to 50000 Pa. The pressure in the container body is more preferably adjusted to 1 Pa to 5000 Pa, and more preferably adjusted to 1 Pa to 500 Pa. The step of stirring and dispersing by rotating the propeller installed in the container and the step of reducing pressure are alternately repeated or simultaneously performed.
容器体内に設置されたプロペラは、エマルジョン粒子を切断分散させる形状であることが撹拌分散に有効である。また、撹拌分散工程中のプロペラの回転数は２００ｒｐｍ乃至５０００ｒｐｍの範囲に維持することが望ましい。減圧及び／又は撹拌分散工程は、トータルで５分以上２４時間以下の範囲で行うことが望ましい。減圧及び／又は撹拌分散工程は、トータルで３０分以上１２時間以下の範囲で行うことがさらに望ましく、１時間以上６時間以下の範囲で行うことがより望ましく、２時間以上４時間以下の範囲で行うことがより望ましい。 It is effective for stirring and dispersing that the propeller installed in the container has a shape in which emulsion particles are cut and dispersed. Moreover, it is desirable to maintain the rotation speed of the propeller during the stirring and dispersing step in a range of 200 rpm to 5000 rpm. The decompression and / or stirring / dispersing step is desirably performed in a total range of 5 minutes to 24 hours. The decompression and / or stirring dispersion step is more preferably performed in a range of 30 minutes to 12 hours in total, more preferably in a range of 1 hour to 6 hours, and more preferably in a range of 2 hours to 4 hours. More desirable to do.
特に好ましいナノ化工程は、減圧工程と撹拌分散工程を交互に繰り返すことである。もちろん、撹拌分散工程中にも圧力を調整した上で減圧を行うことも有効である。この場合、特に低速回転での減圧撹拌分散、高速回転での減圧撹拌分散、の順に工程を繰り返すことがさらに有効である。前記の交互に低速及び高速回転での減圧撹拌分散を行う場合は、低速回転での減圧撹拌分散を１分以上３０分以内、高速回転での減圧撹拌分散を５分以上３時間以内の工程を１セットとして繰り返すことがさらに望ましい。 A particularly preferred nanonization step is to alternately repeat the pressure reduction step and the stirring dispersion step. Of course, it is also effective to reduce the pressure after adjusting the pressure during the stirring and dispersing step. In this case, it is more effective to repeat the steps in the order of reduced pressure stirring dispersion at low speed rotation and reduced pressure stirring dispersion at high speed rotation. In the case of alternately performing the reduced pressure stirring dispersion at the low speed and the high speed rotation as described above, the steps of the reduced pressure stirring dispersion at the low speed rotation within 1 minute to 30 minutes and the reduced pressure stirring dispersion at the high speed rotation within 5 minutes to 3 hours. It is more desirable to repeat as one set.
前記の減圧下での撹拌分散工程を経た本発明に係るナノオーダー分散型水性多色塗料は、水性であってポットライフが長く、且つ実用的な塗膜形成条件でもって成膜出来、耐久性及び耐光性に於いても実用的な塗膜が得られ、蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現する多色蓄光、多色蛍光、及び多色再帰反射性塗料を実現するものであった。 The nano-order dispersed water-based multicolor paint according to the present invention that has undergone the stirring and dispersing step under reduced pressure is water-based, has a long pot life, can be formed under practical coating film forming conditions, and is durable. In addition, a practical coating film can be obtained in terms of light resistance, and multicolor phosphorescence, multicolor fluorescence, and multicolor that achieves multiple colors that are the same as or similar to the coloration in daylight in coloration during fluorescence emission. A retroreflective coating was realized.
以下、本発明に係るナノオーダー分散型水性多色蓄光塗料、ナノオーダー分散型水性多色蛍光塗料、ナノオーダー分散型水性多色再帰反射塗料、ナノオーダー分散型水性多色蓄光再帰反射塗料、ナノオーダー分散型水性多色蛍光再帰反射塗料、ナノオーダー分散型水性多色蓄光蛍光再帰反射塗料、これらナノオーダー分散型水性多色塗料の製造方法及びこれらナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置を、実施例に基づいて詳細に説明する。 Hereinafter, nano-order dispersed water-based multicolor phosphorescent paint, nano-order dispersed water-based multicolor fluorescent paint, nano-order dispersed water-based multicolor retroreflective coating, nano-order dispersed water-based multicolor phosphorescent retroreflective coating, nano Order-dispersed water-based multicolor fluorescent retroreflective coating, nanoorder-dispersed water-based multicolor phosphorescent retroreflective coating, method for producing these nano-order-dispersed water-based multicolored paints, and production of these nano-order-dispersed water-based multicolored paints The vacuum stirring and dispersing apparatus will be described in detail based on examples.
本実施例に於いては、ナノオーダー分散型水性多色蓄光塗料の製造を行った。ここでは、本発明に係るナノオーダー分散型水性多色蓄光塗料の製造方法の例について説明し、同時にナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置についても説明する。 In this example, a nano-order dispersed water-based multicolor phosphorescent paint was produced. Here, an example of a method for producing a nano-order dispersed water-based multicolor phosphorescent paint according to the present invention will be described, and at the same time, a vacuum stirring and dispersing apparatus used for producing a nano-order dispersed water-based multicolor paint will be described.
本実施例に於いては、ナノオーダー分散型水性多色蓄光塗料の原料エマルジョンとして、アクリル酸エステル共重合体水性エマルジョンを水に分散させて用いた。なお、本発明に用いられる原料エマルジョンとしては、本実施例に係る材料に限定されるものではなく、各種の合成樹脂エマルジョンおよび／または水溶性樹脂を好適に用いることが出来る。 In this example, an acrylic ester copolymer aqueous emulsion was dispersed in water as a raw material emulsion for a nano-order dispersion type water-based multicolor phosphorescent paint. In addition, as raw material emulsion used for this invention, it is not limited to the material which concerns on a present Example, Various synthetic resin emulsions and / or water-soluble resin can be used suitably.
本実施例に於いては、上記アクリル酸エステル共重合体水性エマルジョン１００重量部に水１１０重量部を加え、さらに消泡剤２．５重量部、湿潤剤及び抑泡剤各０．４重量部、乾燥調製剤２．５重量部を加えて撹拌を行った。ここで、添加剤としては求められる塗料の特性により、塗料組成物原料にはさらに増粘剤、分散剤、湿潤剤、消泡剤、抑泡剤、成膜助剤、凍結防止剤、凍結安定剤、防腐剤、沈降防止剤、付着防止剤、乾燥調製剤、或いは熱変換剤・断熱材・遮熱剤などの温度抑制剤、からなる群より選ばれた１種または２種以上の補助剤を含んでもよい。 In this example, 110 parts by weight of water was added to 100 parts by weight of the acrylic ester copolymer aqueous emulsion, and 2.5 parts by weight of an antifoaming agent and 0.4 parts by weight of a wetting agent and an antifoaming agent. Then, 2.5 parts by weight of the dry preparation agent was added and stirred. Here, depending on the properties of the paint required as additives, the coating composition raw materials further include thickeners, dispersants, wetting agents, antifoaming agents, antifoaming agents, film forming aids, antifreeze agents, and freeze stability. 1 type or 2 types or more of auxiliary agents selected from the group consisting of agents, preservatives, anti-settling agents, anti-adhesion agents, drying preparation agents, or temperature inhibitors such as heat conversion agents, heat insulating materials, and heat shielding agents May be included.
かかる水性エマルジョンに、さらに蓄光顔料と光拡散剤を加えて撹拌し、水性蓄光塗料原料を得て、これをさらに減圧撹拌分散工程によりナノ化を行って、ナノオーダー分散型水性多色蓄光塗料を得た。本実施例においては、前記水性エマルジョン１００重量部に対してストロンチウム・アルミニウム・オキサイドを主成分とする蓄光顔料を２５重量部、光拡散剤を５重量部加えて撹拌することにより、ナノオーダー分散型水性多色蓄光塗料を得たが、本発明はこれら材料及びこれらの配合比に限定されるものではない。 To this aqueous emulsion, a phosphorescent pigment and a light diffusing agent are further added and stirred to obtain an aqueous phosphorescent paint raw material, which is further nanosized by a vacuum stirring and dispersing process to produce a nano-order dispersed aqueous multicolor phosphorescent paint. Obtained. In the present example, 25 parts by weight of a phosphorescent pigment containing strontium aluminum oxide as a main component and 5 parts by weight of a light diffusing agent are added to 100 parts by weight of the aqueous emulsion, and the mixture is stirred. Although a water-based multicolor phosphorescent paint was obtained, the present invention is not limited to these materials and their blend ratios.
本発明に用いる蓄光顔料としては少なくともストロンチウム、カルシウム、バリウムの何れかとアルミニウムと酸素を含んでなる任意の材料を用いることが出来る。また、配合比も水性エマルジョンに対して任意に設定することが出来る。さらに、光拡散剤及びその配合比も任意に設定することが出来る他、光拡散剤を添加しなくても良い。 As the phosphorescent pigment used in the present invention, any material containing at least one of strontium, calcium, and barium, aluminum, and oxygen can be used. Also, the blending ratio can be arbitrarily set with respect to the aqueous emulsion. Furthermore, the light diffusing agent and the compounding ratio thereof can be arbitrarily set, and the light diffusing agent may not be added.
前記の混合組成物を十分に撹拌混合した後、水性エマルジョン塗料組成物をナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置に投入して、減圧撹拌分散を行うことにより、本発明に係るナノオーダー分散型水性多色蓄光塗料が得られた。 After sufficiently mixing the above-mentioned mixed composition with stirring, the aqueous emulsion coating composition is put into a vacuum stirring and dispersing apparatus used for producing a nano-order dispersion-type aqueous multicolor coating, and the vacuum stirring and dispersing is performed. A nano-order dispersion-type water-based multicolor phosphorescent paint was obtained.
本発明に係るナノオーダー分散型水性多色蓄光塗料の製造に用いる減圧撹拌分散装置の概念図が、図２に示される。本発明に係るナノオーダー分散型水性多色蓄光塗料の製造に用いる減圧撹拌分散装置は、フランジを有して容器部と蓋部が開閉出来るようになっており、前記塗料組成物原料を容器部に投入後フランジを密着させて容器部と蓋部を締め付け、容器体内を減圧出来るようになっている。 FIG. 2 shows a conceptual diagram of a vacuum stirring and dispersing apparatus used for producing a nano-order dispersion type water-based multicolor phosphorescent paint according to the present invention. The vacuum stirring and dispersing apparatus used for producing the nano-order dispersion type water-based multicolor phosphorescent coating material according to the present invention has a flange so that the container part and the lid part can be opened and closed, and the coating composition raw material is used as the container part. After charging, the container part and the lid part are tightened by tightly attaching the flange so that the inside of the container can be decompressed.
前記塗料組成物原料を容器部に投入後してフランジの締め付けを行った後、真空ポンプを作動させて容器体内を減圧し、またプロペラを回転させて撹拌分散を行った。なお、本発明に係るナノオーダー分散型水性多色蓄光塗料の製造方法に於いては、撹拌分散工程中の容器体内の圧力は１Ｐａ乃至５００００Ｐａに調整することが望ましい。容器体内の圧力は１Ｐａ乃至５０００Ｐａに調整することがさらに望ましく、１Ｐａ乃至５００Ｐａに調整することがより望ましい。本実施例においては、工程中でエマルジョン中に残留する空気の量により容器体内の圧力は変動するが、適宜容器体内のエマルジョンの発泡の程度を観察して、バルブにより減圧度を調整した。 After the coating composition raw material was put into the container part and the flange was tightened, the inside of the container was depressurized by operating a vacuum pump, and the propeller was rotated to perform stirring and dispersion. In the method for producing a nano-order dispersed water-based multicolor phosphorescent paint according to the present invention, it is desirable to adjust the pressure in the container during the stirring and dispersing step to 1 Pa to 50000 Pa. The pressure in the container body is more preferably adjusted to 1 Pa to 5000 Pa, and more preferably adjusted to 1 Pa to 500 Pa. In this example, the pressure in the container fluctuated depending on the amount of air remaining in the emulsion during the process, but the degree of foaming of the emulsion in the container was observed as appropriate, and the degree of pressure reduction was adjusted with a valve.
容器体内に設置されたプロペラは、エマルジョン粒子を切断分散させる形状であることが撹拌分散に有効である。また、撹拌分散工程中のプロペラの回転数は２００ｒｐｍ乃至５０００ｒｐｍの範囲に維持することが望ましい。減圧及び／又は撹拌分散工程は、トータルで５分以上２４時間以下の範囲で行うことが望ましい。減圧及び／又は撹拌分散工程は、トータルで３０分以上１２時間以下の範囲で行うことがさらに望ましく、１時間以上６時間以下の範囲で行うことがより望ましく、２時間以上４時間以下の範囲で行うことがより望ましい。 It is effective for stirring and dispersing that the propeller installed in the container has a shape in which emulsion particles are cut and dispersed. Moreover, it is desirable to maintain the rotation speed of the propeller during the stirring and dispersing step in a range of 200 rpm to 5000 rpm. The decompression and / or stirring / dispersing step is desirably performed in a total range of 5 minutes to 24 hours. The decompression and / or stirring dispersion step is more preferably performed in a range of 30 minutes to 12 hours in total, more preferably in a range of 1 hour to 6 hours, and more preferably in a range of 2 hours to 4 hours. More desirable to do.
容器体内に設置されたプロペラを回転させて撹拌分散を行う工程と減圧工程は交互に繰り返して行うか、或いは同時に行われる。特に好ましいナノ化工程は、減圧工程と撹拌分散工程を交互に繰り返すことである。本実施例においては、まずフランジを密封後、プロペラを１０００ｒｐｍ以下で低速回転させながら１０分間の減圧を行い、その後プロペラの回転速度を１５００ｒｐｍ以上に上げて３０分間の減圧撹拌分散を行った。その後、再度低速回転で１０分間の減圧を行い、さらに高速回転で１時間の減圧撹拌分散を行った。最後に、低速回転で１０分間の減圧撹拌分散を行い、ナノオーダー分散型水性多色蓄光塗料を得た。 The step of stirring and dispersing by rotating the propeller installed in the container and the step of reducing pressure are alternately repeated or simultaneously performed. A particularly preferred nanonization step is to alternately repeat the pressure reduction step and the stirring dispersion step. In this example, first, after sealing the flange, pressure reduction was performed for 10 minutes while rotating the propeller at a low speed of 1000 rpm or less, and then the rotation speed of the propeller was increased to 1500 rpm or more for 30 minutes under reduced pressure stirring dispersion. Thereafter, the pressure was reduced again for 10 minutes at a low speed rotation, and further, stirring and dispersing under reduced pressure for 1 hour was performed at a high speed rotation. Finally, the mixture was stirred and dispersed under reduced pressure for 10 minutes at a low speed to obtain a nano-order dispersed water-based multicolor phosphorescent paint.
実施例１で用いた蓄光塗料を蛍光塗料に変更することにより、同様の装置を用い、同様の工程でもって、ナノオーダー分散型水性多色蛍光塗料が得られた。さらに、これらに再帰反射剤を添加分散することにより、ナノオーダー分散型水性多色再帰反射塗料、ナノオーダー分散型水性多色蓄光再帰反射塗料、ナノオーダー分散型水性多色蛍光再帰反射塗料を得ることが出来た。 By changing the phosphorescent paint used in Example 1 to a fluorescent paint, a nano-order dispersed water-based multicolor fluorescent paint was obtained in the same process using the same apparatus. Furthermore, a nano-order dispersed water-based multicolor retroreflective coating material, a nano-order dispersed water-based multicolor phosphorescent retroreflective coating material, and a nano-order dispersed water-based multicolor fluorescent retroreflective coating material are obtained by adding and dispersing a retroreflective agent. I was able to do it.
ここで、本発明に係るナノオーダー分散型水性多色塗料は、水性であるが、前記の条件で撹拌分散することによりエマルジョン径を１０μm以下としたことにより、沈降速度が小さく、ポットライフが長い蓄光塗料であった。さらに、エマルジョン径を５μm以下にすることが望ましく、エマルジョン径を１μm以下にすることがさらに望ましく、エマルジョン径を0.5μm以下にすることがさらに望ましい。 Here, the nano-order-dispersed water-based multicolor paint according to the present invention is water-based, but by stirring and dispersing under the above conditions, the emulsion diameter is set to 10 μm or less, so that the sedimentation speed is small and the pot life is long. It was a phosphorescent paint. Furthermore, the emulsion diameter is preferably 5 μm or less, more preferably 1 μm or less, and further preferably 0.5 μm or less.
一般の蓄光塗料等、特に水性の蓄光塗料等に於いては、顔料を含むエマルジョンの径が大きいため沈降し易く、数日から数週間の保管において沈殿を生じて成膜性が悪化する。しかし、本発明に係るナノオーダー分散型水性多色塗料は水性であるにも関わらず顔料を含むエマルジョンの径が非常に小さいナノオーダーまで分散されているため、沈降速度が遅く、１年以上の保管期間を経ても十分に成膜性の良い塗料であった。 In general phosphorescent paints and the like, especially water-based phosphorescent paints and the like, the emulsion containing the pigment has a large diameter, so that it tends to settle, and precipitation occurs during storage for several days to several weeks, resulting in deterioration of film formability. However, the nano-order dispersion type water-based multicolor paint according to the present invention is dispersed to the nano-order in which the diameter of the emulsion containing the pigment is very small despite being water-based, so that the sedimentation rate is slow and it is 1 year or more. Even after a storage period, it was a paint having a sufficiently good film forming property.
また、本発明に係るナノオーダー分散型水性多色塗料は水性であるため環境負荷が低く、非常にエコロジカルな蓄光塗料として多様な用途に用いることが出来る。 Moreover, since the nano-order dispersion type water-based multicolor paint according to the present invention is water-based, it has a low environmental load and can be used for various applications as a very ecological phosphorescent paint.
さらに、本発明に係るナノオーダー分散型水性多色塗料は、ナノオーダーの分散を行っているため、蓄光／蛍光発光時の呈色に於いても昼光における呈色と同等或いは近似した呈色を生じる。一般の多色蓄光塗料では、昼光においては多色を呈するものの蛍光発光時は蓄光塗料の発光色（一般には黄緑色等）になってしまうため、例えば道路標示や標識等の用途では夜間の外観に問題があったが、本発明に於いてはかかる点が改良され、視認性及び表示性が格段に向上する。また、これらに再帰反射材を添加することにより、さらに視認性の高い塗膜の得られる塗料が実現された。 Furthermore, since the nano-order dispersion type water-based multicolor paint according to the present invention performs nano-order dispersion, the coloration at the time of phosphorescence / fluorescence emission is the same as or similar to the coloration in daylight. Produce. In general multicolor phosphorescent paints, although they exhibit multiple colors in daylight, the fluorescent color of the phosphorescent paint (generally yellowish green, etc.) will be emitted at the time of fluorescent light emission. Although there was a problem with the appearance, this point is improved in the present invention, and the visibility and display are greatly improved. Also, by adding a retroreflective material to these, a paint that can provide a highly visible coating film was realized.
また、本発明に係るナノオーダー分散型水性多色塗料は、ナノオーダーの分散を行っているため、成膜性が良好で、塗布、スプレー等様々な成膜方法に於いて良好な塗膜を得ることが出来る。また、塗膜の付着強度、塗膜自身の強度、耐候性、耐光性等の特性も良好であった。さらに、重ね塗りにより厚膜を得ることも容易で、様々な用途に対応可能な特性を有している。 In addition, the nano-order dispersion type water-based multicolor paint according to the present invention has nano-order dispersion, so that the film formability is good, and a good coating film can be formed by various film forming methods such as coating and spraying. Can be obtained. Moreover, the characteristics such as the adhesion strength of the coating film, the strength of the coating film itself, the weather resistance, and the light resistance were also good. Furthermore, it is easy to obtain a thick film by overcoating, and it has characteristics that can be used for various applications.
本発明は、ナノオーダー分散型水性多色塗料及びナノオーダー分散型水性多色塗料の製造方法において、減圧脱気を行いながら撹拌分散を行うことにより、完全水性であっても顔料の沈降が抑制されてポットライフが長く、成膜特性に優れ、さらに蓄光／蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現するナノオーダー分散型水性多色塗料、ナノオーダー分散型水性多色塗料の製造方法及びナノオーダー分散型水性多色塗料の製造に用いる減圧撹拌分散装置を実現し、水性であってポットライフが長く、且つ実用的な塗膜形成条件でもって成膜出来、耐久性及び耐光性に於いても実用的な塗膜が得られ、蓄光／蛍光発光時の呈色においても昼光における呈色と同等或いは近似した多色を実現する多色塗料を実現し、もって多岐に亘る用途に活用出来、我が国産業の発展に資するものである。 In the production method of the nano-order dispersion type water-based multicolor paint and the nano-order dispersion type water-based multicolor paint, the present invention suppresses the precipitation of the pigment even if it is completely aqueous by stirring and dispersing while performing degassing under reduced pressure. Nano order dispersed water-based multi-color coating material that has a long pot life, excellent film formation characteristics, and realizes multicolor that is equivalent to or close to the coloration in daylight in color storage during phosphorescence / fluorescence. A method for producing a dispersion-type water-based multicolor paint and a vacuum stirring and dispersing apparatus used for producing a nano-order-dispersion-type water-based multicolor paint are realized, which is water-based, has a long pot life, and has practical film forming conditions. A multi-color paint that can produce a film that is practical in terms of film finish, durability, and light resistance, and that achieves multiple colors that are equivalent to or similar to those in daylight, even in color storage during phosphorescence / fluorescence. Fruit Then, it can be utilized in applications where a wide variety have, is not conducive to the development of Japanese industry.
１ 容器体部
２ 撹拌分散用プロペラ
３ 高速回転軸
４ 低速回転軸
５ 真空ポンプ
６ 操作盤
DESCRIPTION OF SYMBOLS 1 Container body part 2 Propeller for stirring
Claims (10)
合成樹脂エマルジョンおよび／または水溶性樹脂と、少なくともストロンチウム、カルシウム、バリウムの何れかとアルミニウムと酸素を含んでなる蓄光性或いは蛍光性顔料及び水を含む塗料組成物を配合する工程と、Blending a synthetic resin emulsion and / or a water-soluble resin with a paint composition containing at least one of strontium, calcium and barium, a luminous or fluorescent pigment containing aluminum and oxygen, and water;
該塗料組成物を撹拌釜に投入し、撹拌して水性エマルジョンを得る混合工程と、A mixing step of charging the coating composition into a stirring vessel and stirring to obtain an aqueous emulsion;
該水性エマルジョンを容器体中で減圧し、プロペラを用いて撹拌する撹拌分散工程であって、該撹拌分散工程中のプロペラの回転数は２００ｒｐｍ乃至５０００ｒｐｍの範囲で行われ、且つ、該減圧脱気の圧力が１Ｐａ乃至５００００Ｐａの条件下で減圧脱気を行いながら撹拌分散を行うことによりナノオーダーの分散を行う減圧撹拌分散工程と、A stirring and dispersing step in which the aqueous emulsion is depressurized in a container and stirred with a propeller, and the propeller rotation speed in the stirring and dispersing step is in a range of 200 rpm to 5000 rpm, and the vacuum degassing Under reduced pressure stirring and dispersing step of performing nano-order dispersion by stirring and dispersing while performing vacuum degassing under conditions of 1 Pa to 50000 Pa under pressure,
を経ることにより、By going through
エマルジョン径を１０μm以下に調製したことを特徴とする、The emulsion diameter is adjusted to 10 μm or less,
ナノオーダー分散型水性多色塗料の製造方法。A method for producing a nano-order dispersed water-based multicolor paint.
合成樹脂エマルジョンおよび／または水溶性樹脂を１００重量部、蓄光性顔料或いは蛍光性顔料を５重量部乃至５０重量部、水を５０重量部乃至２００重量部の範囲で混合した塗料組成物原料エマルジョンを用いることを特徴とする、A coating composition raw material emulsion prepared by mixing 100 parts by weight of a synthetic resin emulsion and / or a water-soluble resin, 5 to 50 parts by weight of a luminous pigment or fluorescent pigment, and 50 to 200 parts by weight of water. It is characterized by using
請求項１記載のナノオーダー分散型水性多色塗料の製造方法。A method for producing a nano-order dispersed water-based multicolor paint according to claim 1.
該塗料組成物は再帰反射材を含むことを特徴とする、The coating composition includes a retroreflective material,
請求項１又は２記載のナノオーダー分散型水性多色塗料の製造方法。A method for producing a nano-order dispersed water-based multicolor paint according to claim 1 or 2.
請求項１乃至３の何れか一に記載のナノオーダー分散型水性多色塗料の製造方法。The method for producing a nano-order dispersed water-based multicolor paint according to any one of claims 1 to 3.
請求項４記載のナノオーダー分散型水性多色塗料の製造方法。The manufacturing method of the nano order dispersion type water-based multicolor coating material of Claim 4.
請求項５記載のナノオーダー分散型水性多色塗料の製造方法。A method for producing a nano-order dispersed water-based multicolor paint according to claim 5.
請求項１乃至３の何れか一に記載のナノオーダー分散型水性多色塗料の製造方法。The method for producing a nano-order dispersed water-based multicolor paint according to any one of claims 1 to 3.
請求項７記載のナノオーダー分散型水性多色塗料の製造方法。A method for producing a nano-order dispersed water-based multicolor paint according to claim 7.
請求項８記載のナノオーダー分散型水性多色塗料の製造方法。The manufacturing method of the nano order dispersion type water-based multicolor coating material of Claim 8.
請求項１乃至９の何れか一に記載のナノオーダー分散型水性多色塗料の製造方法。A method for producing a nano-order dispersed water-based multicolor paint according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015013969A (en) * | 2013-07-08 | 2015-01-22 | 株式会社アマケンテック | Nano-order dispersion type antimicrobial coating and production method thereof |
| JP2016138186A (en) * | 2015-01-27 | 2016-08-04 | 株式会社アマケンテック | Nano-order dispersion type thermal conversion heat-blocking paint, and nano-order dispersion type waterproof agent, method for manufacturing nano-order dispersion type anti-thermal-conversion heat-blocking paint, and method for manufacturing nano-order dispersion type waterproof agent |
| JP6549963B2 (en) * | 2015-10-13 | 2019-07-24 | 株式会社アマケンテック | Water proofing method of grass surface of pavement and road bridge using water-based paint |
| CN106256859A (en) * | 2016-08-25 | 2016-12-28 | 上海磐彩环保科技股份有限公司 | A kind of colorful environmental protection coating material of nanometer high durable and preparation method thereof |
| CN106084961A (en) * | 2016-08-26 | 2016-11-09 | 上海磐彩环保科技股份有限公司 | A kind of aqueous, environmental protective elasticity multicolor finish and preparation method thereof |
| KR102319923B1 (en) * | 2021-06-04 | 2021-11-01 | (주)에스이에프코리아 | Manufacturing method of inorganic coating composition and inorganic coating composition manufactured thereby |
| CN113831790A (en) * | 2021-10-19 | 2021-12-24 | 黄明彦 | Preparation method of environment-friendly water-based paint |
| CN116574435B (en) * | 2023-05-10 | 2024-06-18 | 武汉大学 | Preparation method of water-based fluorescent paint based on nanoparticle composite |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5118250B2 (en) * | 1972-01-25 | 1976-06-08 | ||
| JPS5433573A (en) * | 1977-08-19 | 1979-03-12 | Toyota Motor Corp | Reclaming of waste paint |
| JPS5439438A (en) * | 1977-09-02 | 1979-03-26 | Toyota Kagaku Kougiyou Kk | Regenerating method of coating material |
| JPS5839459B2 (en) * | 1980-08-18 | 1983-08-30 | 日本パ−カライジング株式会社 | Water-based coating agent and its manufacturing method |
| JPS5930868A (en) * | 1982-08-13 | 1984-02-18 | Hayashi Kagaku Kogyo Kk | Coating film with reflective ability |
| EP0423611A1 (en) * | 1989-10-19 | 1991-04-24 | Henkel Kommanditgesellschaft auf Aktien | Rapid rain resistant grouting masses |
| FR2729406B1 (en) * | 1995-01-16 | 1997-04-18 | Rhone Poulenc Chimie | USE AS ANTI-ADHERENT AND / OR WATER-REPELLANT OF FUNCTIONALIZED POLYORGANOSILOXANES, GRAFTS |
| JPH0912933A (en) * | 1995-06-26 | 1997-01-14 | Kao Corp | Production of magnetic coating material |
| JPH11130991A (en) * | 1997-10-27 | 1999-05-18 | Nippon Paint Co Ltd | Luminous coating composition for precoat, film-forming method, and luminous coated article |
| JPH11140351A (en) * | 1997-11-07 | 1999-05-25 | Kowa Chem Ind Co Ltd | Water-based phosphorescent coating composition and method for applying same |
| JP2002322426A (en) * | 2001-04-26 | 2002-11-08 | Sakura Color Prod Corp | Coloring material composition having stone grain tone |
| JP2004267991A (en) * | 2003-03-12 | 2004-09-30 | Mitsubishi Paper Mills Ltd | Method of manufacturing gas phase process silica aqueous dispersion and inkjet recording material using the same |
| JP4074833B2 (en) * | 2003-05-12 | 2008-04-16 | 独立行政法人産業技術総合研究所 | Method for producing photocatalyst paint |
| CN102352045A (en) * | 2005-06-03 | 2012-02-15 | 三菱化学株式会社 | Method for producing aqueous resin dispersion |
| US7816470B2 (en) * | 2006-08-23 | 2010-10-19 | Ppg Industries Ohio, Inc. | Aqueous-based polymers for sound deadening applications |
| JP2008100374A (en) * | 2006-10-17 | 2008-05-01 | Canon Inc | Method of manufacturing mixed liquid under decompression environment, method of manufacturing coating liquid, and method of manufacturing medium to be recorded for inkjet recording |
| JP2008121006A (en) * | 2006-10-19 | 2008-05-29 | Kansai Paint Co Ltd | Fancy coating film-forming composition, and method for finishing fancy coating |
| JP2008266612A (en) * | 2007-03-26 | 2008-11-06 | Semiconductor Energy Lab Co Ltd | Phosphor material and method for manufacturing the same |
| JP5305069B2 (en) * | 2008-06-06 | 2013-10-02 | 公益財団法人鉄道総合技術研究所 | Non-contact measurement target surface forming method |
| JP5586135B2 (en) * | 2008-09-05 | 2014-09-10 | 株式会社サクラクレパス | Water-based drawing material |
-
2012
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