JP2005319453A - Method for forming designed coating film - Google Patents

Method for forming designed coating film Download PDF

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JP2005319453A
JP2005319453A JP2005061412A JP2005061412A JP2005319453A JP 2005319453 A JP2005319453 A JP 2005319453A JP 2005061412 A JP2005061412 A JP 2005061412A JP 2005061412 A JP2005061412 A JP 2005061412A JP 2005319453 A JP2005319453 A JP 2005319453A
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coating film
resin
forming
powder
granular material
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JP4562552B2 (en
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Tsutomu Kodera
努 小寺
Hiroyuki Nishida
博幸 西田
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SK Kaken Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a designed coating film which can provide a novel design with good appearance and is excellent in weathering resistance and durability and can maintain the design function for a long period of time. <P>SOLUTION: This method for forming a designed coating film comprises the steps of (1) coating an undercoating material onto a base material, (2) spreading a flat powder/granular material before the undercoating material is dried and solidified, and (3) coating a transparent or semi-transparent overcoating material having a resin solid content of 50 to 95% by weight while pressing the powder/granular material with a roller. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、新規な意匠性を提供する意匠性塗膜の形成方法に関する。   The present invention relates to a method for forming a designable coating film that provides novel design properties.

従来、住宅、工場、倉庫、スポーツ施設等の建築物の床面や屋上、あるいは、道路、歩道、歩道橋、プラットホーム、公園、広場、庭等の屋外床面に対し、塗料による塗装を施し、美観性等を付与することが行われている。このような床面に対し、美観性を付与する方法として、例えば、結合剤と着色粉体を混合した着色塗材を塗付する方法や、床面に着色粉体を散布し美観性を表現する方法等がある。   Traditionally, the floor and rooftops of buildings such as houses, factories, warehouses, and sports facilities, or outdoor floors such as roads, sidewalks, pedestrian bridges, platforms, parks, plazas, and gardens, have been painted with paint, and are beautiful. It is done to give sex. As a method for imparting aesthetics to such a floor surface, for example, a method of applying a colored coating material in which a binder and a colored powder are mixed, or a colored powder is sprayed on the floor surface to express aesthetics. There are ways to do this.

このうち、床面に着色粉体を散布する方法によれば、比較的簡便な方法で美観性を付与することができ、結合剤と着色材を混合した着色粉体を塗付する場合とは異なった意匠性、独特な意匠性を表現することができる。例えば、特許文献1では、床仕上用組成物を塗り付けた後、特定粒子径の粒子を散布することにより、意匠性を表現している。   Among these, according to the method of spraying the colored powder on the floor surface, it is possible to impart aesthetics by a relatively simple method, and when applying a colored powder mixed with a binder and a coloring material. Different design characteristics and unique design characteristics can be expressed. For example, in Patent Document 1, design properties are expressed by applying particles having a specific particle size after applying a floor finishing composition.

着色粉体の散布によって美観性を付与する方法は、上述のような床面のみでなく建築物の壁面等に対して適用することもできる。例えば特許文献2には、壁面等の被装飾体上に液状接着剤を塗布した後、小片状の装飾材を付着させる方法が記載されている。   The method of imparting aesthetics by spraying colored powder can be applied not only to the floor surface as described above but also to the wall surface of a building. For example, Patent Document 2 describes a method in which a small piece of decorative material is attached after applying a liquid adhesive onto an object to be decorated such as a wall surface.

しかしながら、上述の特許文献に記載の方法では、その仕上状態において粒子が実質表面に晒された状態となっており、耐候性、耐久性に劣る場合がある。さらに、粒子が取れ落ち、意匠性に欠けたものとなる場合もある。   However, in the method described in the above-mentioned patent document, the particles are substantially exposed to the surface in the finished state, which may be inferior in weather resistance and durability. Furthermore, the particles may fall off and may lack design properties.

特開平9−279824号公報JP-A-9-279824 特開2003−341298号公報JP 2003-341298 A

本発明は上記課題を解決するために、鋭意検討をした結果、下塗材を塗付した後、下塗材が乾燥固化する前に、平板状の粉粒体を散布し、次いで、特定の樹脂固形分濃度の透明又は半透明の上塗材を、ローラーを用いて該粉粒体を押しつけながら塗付することにより、美観性のある新規な意匠が提供でき、耐候性、耐久性に優れ、長期に亘り意匠性が維持できることを見出し、本発明の完成に到った。   In order to solve the above-mentioned problems, the present invention has been intensively studied. As a result, after applying the undercoat material, before the undercoat material is dried and solidified, the plate-like powder is sprayed, By applying a transparent or semi-transparent topcoat material while pressing the granular material using a roller, it is possible to provide a new design with aesthetics, excellent weather resistance, durability, and long-term As a result, it was found that the designability can be maintained, and the present invention has been completed.

即ち、本発明は、以下の特徴を有するものである。
1.(1)基材に対し、下塗材を塗付する工程、
(2)下塗材が乾燥固化する前に、平板状の粉粒体を散布する工程、
(3)樹脂固形分濃度が50〜95重量%である透明又は半透明の上塗材を、ローラーを用いて該粉粒体を押しつけながら塗付する工程、
からなることを特徴とする意匠性塗膜の形成方法。
2.上塗材が、架橋性結合剤を含有することを特徴とする項1.に記載の意匠性塗膜の形成方法。
3.平板状の粉粒体が、長径が2mm以上、厚さが1mm以下であることを特徴とする項1.または項2.に記載の意匠性塗膜の形成方法。
4.基材が床面を構成するものである項1.〜項3.のいずれかに記載の意匠性塗膜の形成方法。
That is, the present invention has the following characteristics.
1. (1) A step of applying a primer to the base material,
(2) before the undercoat material is dried and solidified, a step of spraying flat powder particles;
(3) A step of applying a transparent or semi-transparent topcoat material having a resin solid content concentration of 50 to 95% by weight while pressing the powder particles using a roller,
A method for forming a designable coating film, comprising:
2. Item 1. The coating material contains a crosslinkable binder. The forming method of the designable coating film as described in 2.
3. Item 1. The flat granular material has a major axis of 2 mm or more and a thickness of 1 mm or less. Or item 2. The forming method of the designable coating film as described in 2.
4). Item 1. The base material constitutes a floor surface. To Section 3. The forming method of the designable coating film in any one of.

本発明によれば、美観性に優れた新規な意匠性塗膜を簡便に形成できる。しかも、本発明によって形成された塗膜は、耐候性、耐久性等に優れ、美観性のある意匠性を長期に亘り維持することができる。本発明方法を床面に対して適用する場合は、その優れた乾燥性により、翌日には歩行可能とすることもできる。   ADVANTAGE OF THE INVENTION According to this invention, the novel designable coating film excellent in aesthetics can be formed simply. And the coating film formed by this invention is excellent in a weather resistance, durability, etc., and can maintain the designability with aesthetics over a long period of time. When the method of the present invention is applied to the floor surface, it can be made walkable on the next day due to its excellent drying property.

以下、本発明を、実施するための最良の形態とともに詳細に説明する。   Hereinafter, the present invention will be described in detail together with the best mode for carrying out the invention.

本発明第1の工程では、基材に対し、下塗材を塗付する。
本発明を床面に適用する場合、基材としては、例えば、住宅、工場、倉庫、スポーツ施設等の建築物の床面や屋上、あるいは、道路、歩道、歩道橋、プラットホーム、公園、広場、庭等の屋外床面を構成するものであれば特に限定されず使用することができる。具体的な材質としては、例えば、硬質の土面や石面、コンクリート、モルタル、アスファルト等が挙げられる。また、インターロッキング、ポーラスコンクリート等の既存の床面を改修、改装する目的で用いることもできる。本発明を壁面に適用する場合の基材としては、例えば、コンクリート、モルタル、繊維混入セメント板、セメント珪酸カルシウム板、スラグセメントパーライト板、石綿セメント板、ALC板、サイディング板、押出成形板、石膏ボード、合板、鋼板、プラスチック板等が挙げられる。これら基材の表面は、何らかの表面処理(例えば、シーラー、サーフェーサー、フィラー等)が施されたものであってもよい。
In the first step of the present invention, an undercoat material is applied to the substrate.
When the present invention is applied to the floor surface, the base material may be, for example, a floor surface or rooftop of a building such as a house, factory, warehouse, or sports facility, or a road, a footpath, a footbridge, a platform, a park, a square, a garden. As long as it constitutes an outdoor floor surface such as, it can be used without any particular limitation. Specific examples of the material include hard soil surface, stone surface, concrete, mortar, and asphalt. Moreover, it can also be used for the purpose of repairing and refurbishing existing floors such as interlocking and porous concrete. Examples of the base material when the present invention is applied to a wall surface include concrete, mortar, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, asbestos cement board, ALC board, siding board, extruded board, and plaster. Examples include boards, plywood, steel plates, and plastic plates. The surface of these base materials may have been subjected to some surface treatment (for example, a sealer, a surfacer, a filler, etc.).

第1の工程における下塗材としては、上記基材への密着性を有するとともに、次工程の粉粒体を固定化可能なものであれば特に限定されず使用することができる。このような下塗材は、結合剤等を必須成分として含むものである。
結合剤としては、水溶性樹脂、水分散性樹脂、溶剤可溶形樹脂、非水分散形樹脂、無溶剤形樹脂、粉末樹脂、セメント、石膏、シリカ等の各種結合剤、あるいはこれらを複合化した結合剤等を使用することができる。本発明では特に、無溶剤形樹脂が好適に用いられる。使用可能な樹脂の種類としては、例えば、エチレン樹脂、酢酸ビニル樹脂、ポリエステル樹脂、アルキッド樹脂、塩化ビニル樹脂、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、シリコーン樹脂、フッ素樹脂、セルロース、ポリビニルアルコール等、あるいはこれらの複合系等を挙げることができる。このうち、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、あるいはこれらの複合系を使用することが好ましい。
The undercoat material in the first step is not particularly limited as long as it has adhesion to the substrate and can fix the powder in the next step. Such an undercoating material contains a binder or the like as an essential component.
As binders, various binders such as water-soluble resins, water-dispersible resins, solvent-soluble resins, non-water-dispersed resins, solvent-free resins, powder resins, cement, gypsum and silica, or composites of these. Can be used. In the present invention, a solventless resin is particularly preferably used. Usable types of resin include, for example, ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, silicone resin, fluororesin, cellulose, polyvinyl alcohol, etc. These composite systems can be mentioned. Among these, it is preferable to use an acrylic resin, a urethane resin, an epoxy resin, or a composite system thereof.

さらに下塗材には、着色顔料、体質顔料、繊維、増粘剤、造膜助剤、レベリング剤、可塑剤、凍結防止剤、pH調整剤、防腐剤、防黴剤、防藻剤、抗菌剤、分散剤、消泡剤、紫外線吸収剤、酸化防止剤等の添加剤も使用可能である。   In addition, undercoat materials include coloring pigments, extender pigments, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreezing agents, pH adjusters, antiseptics, antifungal agents, antialgae agents, and antibacterial agents. Additives such as dispersants, antifoaming agents, ultraviolet absorbers and antioxidants can also be used.

また、下塗材としては、透明又は半透明のものが好ましく、その隠ぺい率は80%以下(好ましくは60%以下、より好ましくは40%以下、さらに好ましくは20%以下)程度であればよい。このような範囲であることにより、鮮鋭性や深み感を付与することができる。
なお、隠ぺい率は、乾燥膜厚が100μmとなるようにフィルムアプリケータで隠ぺい率試験紙に塗り付け、温度23℃、相対湿度50%下にて48時間乾燥させることによって作製した試験片を、黒地上塗膜と白地上塗膜の視感反射率を色彩色差計「CR−300」(ミノルタ株式会社製)を用いて測定し、算出した値である。
The undercoat material is preferably transparent or translucent, and the concealment ratio may be about 80% or less (preferably 60% or less, more preferably 40% or less, and further preferably 20% or less). By being in such a range, sharpness and a deep feeling can be provided.
In addition, the concealment rate is a test piece prepared by applying the cover rate test paper with a film applicator so that the dry film thickness is 100 μm, and drying it at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours. It is the value which measured and calculated the luminous reflectance of the black ground coating film and the white ground coating film using the color difference meter "CR-300" (made by Minolta Co., Ltd.).

下塗材を塗装する方法としては、特に限定されず、刷毛、コテ、スプレー、ローラー等の塗装器具を用いて塗装すればよい。塗付量も特に限定されないが、通常50〜500g/m程度(乾燥膜厚0.03〜0.5mm程度)で塗装すればよい。 The method for applying the primer is not particularly limited, and it may be applied using a coating tool such as a brush, a trowel, a spray, or a roller. The coating amount is not particularly limited, but it may be usually applied at about 50 to 500 g / m 2 (dry film thickness of about 0.03 to 0.5 mm).

本発明第2の工程では、下塗材が乾燥固化する前に平板状の粉粒体を散布する。粉粒体を散布するタイミングは、下塗材が乾燥固化する前であれば特に限定されないが、通常は下塗材を塗付後1〜15分程度であればよい。下塗材が乾燥固化する前に粉粒体を散布することにより、下塗材と粉粒体の密着性に優れた意匠性塗膜が形成可能である。   In the second step of the present invention, a flat granular material is sprayed before the undercoating material is dried and solidified. Although the timing which spreads a granular material will not be specifically limited if it is before an undercoat material dries and solidifies, it will usually be about 1 to 15 minutes after applying an undercoat material. By spraying the granular material before the undercoating material is dried and solidified, it is possible to form a design coating film having excellent adhesion between the undercoating material and the granular material.

平板状の粉粒体としては、例えば、長径が2mm以上、(好ましくは2〜30mm、さらに好ましくは3〜25mm)、また、厚さは、1mm以下(好ましくは0.8mm以下、さらに好ましくは0.5mm以下)の粉粒体を用いることが好ましい。このような平板状の粉粒体を散布することにより、下塗材の塗装面に沿って粉粒体が平滑に配置されやすく、比較的少ない量で全面を覆うこともできる。また、長径の大きい粉粒体を用いて大柄模様の意匠性も簡便に形成可能である。
平板状の粉粒体の形状としては、円、楕円状、多角形状、あるいはランダムな形状等特に限定されることはないが、長径と厚さの関係が、厚さ/長径で、好ましくは1/3以下、さらに好ましくは1/5以下であることが好ましい。なお、本発明でいう長径とは、各種粉粒体の形状における最長の長さのことである。
As a flat granular material, for example, the major axis is 2 mm or more (preferably 2 to 30 mm, more preferably 3 to 25 mm), and the thickness is 1 mm or less (preferably 0.8 mm or less, more preferably It is preferable to use a granular material of 0.5 mm or less. By spraying such a flat granular material, the granular material is easily arranged along the coating surface of the undercoat material, and the entire surface can be covered with a relatively small amount. Moreover, the design property of a large pattern can be simply formed using the powder body with a long major axis.
The shape of the flat granular material is not particularly limited, such as a circle, an ellipse, a polygon, or a random shape, but the relationship between the major axis and the thickness is the thickness / major axis, preferably 1. / 3 or less, more preferably 1/5 or less. In addition, the long diameter as used in the field of this invention is the longest length in the shape of various granular materials.

粉粒体としては、上記条件を満たしていれば特に限定されないが、例えば、雲母(マイカ)等の天然石・加工石フレーク、アルミニウムフレーク、銅フレーク、パールフレーク等の金属フレーク、アクリル樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリエチレン樹脂等の樹脂フレーク、ガラスフレーク、あるいは、これらを着色したフレーク等が挙げられる。また、フレーク状の貝殻片、ゴム片、木片等を使用することもできる。
このような粉粒体は、1種でもよいし、2種以上を混合したものでもよい。本発明では、美観性のある意匠性を表現するため、異なる2種以上粉粒体を混合して用いることが好ましい。
The powder is not particularly limited as long as the above conditions are satisfied. For example, natural stone / processed stone flake such as mica (mica), metal flake such as aluminum flake, copper flake, pearl flake, acrylic resin, polychlorinated Resin flakes such as vinyl resin, polyvinyl acetate resin, and polyethylene resin, glass flakes, and flakes colored with these. In addition, flake-shaped shell pieces, rubber pieces, wood pieces and the like can be used.
Such a granular material may be one kind or a mixture of two or more kinds. In the present invention, it is preferable to use a mixture of two or more kinds of different granular materials in order to express a design with aesthetics.

粉粒体を散布する方法としては、特に限定されないが、手で散布する方法、ふるいにより散布する方法、吹き付けにより散布する方法のほか、公知の散布装置を用いて散布する方法等を適宜採用することができる。散布回数は、1回でもよいし、複数回にわけて散布することも可能である。
また粉粒体が過剰に散布された場合は、刷毛やホウキ、掃除機等を用いて取り除いてもよい。この際、下塗材が完全またはある程度乾燥した状態で、過剰に散布された粉粒体を取り除けばよい。
There are no particular restrictions on the method of spraying the powder, but a method of spraying by hand, a method of spraying with a sieve, a method of spraying by spraying, a method of spraying using a known spraying device, etc. is appropriately adopted. be able to. The number of times of spraying may be one, or it may be sprayed in multiple times.
Further, when the powder particles are excessively dispersed, they may be removed using a brush, broom, vacuum cleaner or the like. At this time, it is only necessary to remove the excessively dispersed powder particles in a state where the undercoat material is completely or partially dried.

本発明第3の工程では、樹脂固形分濃度が50〜95重量%である透明又は半透明の上塗材を、ローラーを用いて該粉粒体を押しつけながら塗付する。塗付するタイミングとしては、特に限定されず、下塗材が完全またはある程度乾燥した状態で、塗付すればよい。
この工程では、樹脂固形分濃度が50〜95重量%(好ましくは50〜80重量%)である上塗材を使用することにより、塗膜の最表面に上塗塗膜が確実に形成でき、優れた耐久性・耐候性を示すことができるとともに、所定の塗膜厚に1回または少ない回数で塗付することができるため、施工が容易で、工期短縮が可能である。また、揮発成分が少なく、乾燥性に優れ、床面においては翌日には歩行可能な状態に設定することができる。さらに、適度な乾燥収縮性を有するため、浮き状態の粉粒体を平滑に押さえつけることができる。
樹脂固形分濃度が50重量%より小さい場合は、上塗材が粉粒体等へ浸透し、最表面に上塗塗膜が確実に形成できない場合がある。また確実に形成するためには複数回塗り重ねなければならない。樹脂固形分濃度が95重量%より多い場合は粘度が高くなり、効率よく塗付できない場合があり、また、浮き状態の粉粒体を平滑に押さえつける効果が期待できない場合もある。
このような上塗材を、ローラーを用いて、粉粒体を押しつけながら塗付することによって、粉粒体が基材に沿って平滑に配列され、美観性のある意匠性が表現でき、さらに粉粒体を確実に固着することができる。
In the third step of the present invention, a transparent or semi-transparent topcoat material having a resin solid content concentration of 50 to 95% by weight is applied while pressing the granular material using a roller. The application timing is not particularly limited, and it may be applied in a state where the undercoat material is completely or partially dried.
In this step, by using a top coating material having a resin solid content concentration of 50 to 95% by weight (preferably 50 to 80% by weight), a top coating film can be reliably formed on the outermost surface of the coating film, which is excellent. It can exhibit durability and weather resistance, and can be applied to a predetermined coating thickness once or less, so that construction is easy and the construction period can be shortened. Moreover, there are few volatile components, it is excellent in drying property, and it can set to the state which can be walked on the next day on a floor surface. Furthermore, since it has an appropriate drying shrinkage, the floating granular material can be pressed down smoothly.
When the resin solid content concentration is less than 50% by weight, the top coating material may penetrate into the powder and the like, and the top coating film may not be reliably formed on the outermost surface. Moreover, in order to form reliably, it has to be applied several times. When the resin solid content concentration is more than 95% by weight, the viscosity becomes high, and it may not be applied efficiently, and the effect of smoothly pressing the floating granular material may not be expected.
By applying such a top coating material using a roller while pressing the granular material, the granular material is arranged smoothly along the base material, and an aesthetic design can be expressed. The particles can be securely fixed.

また、第3の工程における上塗材としては、透明又は半透明のものを使用する。上塗材の透明性の程度は、粉粒体により表現される意匠性を損なわない範囲内であれば、特に限定されないが、通常は隠ぺい率が80%以下(好ましくは60%以下、より好ましくは40%以下、さらに好ましくは20%以下)程度であればよい。このような範囲であることにより、鮮鋭性や深み感を付与することができる。なお、上塗材の隠ぺい率は、下塗材の隠ぺい率と同様の方法で測定した値である。   In addition, as the top coating material in the third step, a transparent or translucent material is used. The degree of transparency of the top coating material is not particularly limited as long as it does not impair the design properties expressed by the granular material, but usually the concealment rate is 80% or less (preferably 60% or less, more preferably 40% or less, more preferably 20% or less). By being in such a range, sharpness and a deep feeling can be provided. In addition, the concealment rate of the top coating material is a value measured by the same method as the concealment rate of the undercoating material.

上塗材としては、上記条件を満たすものであれば特に限定されず、各種樹脂を必須成分として含むものが使用できる。上塗材における樹脂としては、水溶性樹脂、水分散性樹脂、溶剤可溶形樹脂、非水分散形樹脂、無溶剤形樹脂、粉末樹脂等、あるいはこれらを複合化した樹脂等を使用することができる。本発明では特に、溶剤可溶形樹脂が好適に用いられる。使用可能な樹脂の種類としては、例えば、エチレン樹脂、酢酸ビニル樹脂、ポリエステル樹脂、アルキッド樹脂、塩化ビニル樹脂、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、シリコーン樹脂、フッ素樹脂、セルロース、ポリビニルアルコール等、あるいはこれらの複合系等を挙げることができる。このうち、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、あるいはこれらの複合系を使用することが好ましい。   The top coating material is not particularly limited as long as it satisfies the above conditions, and materials containing various resins as essential components can be used. As the resin in the top coating material, it is possible to use a water-soluble resin, a water-dispersible resin, a solvent-soluble resin, a non-water-dispersed resin, a solvent-free resin, a powder resin, or a resin obtained by combining these. it can. In the present invention, a solvent-soluble resin is particularly preferably used. Usable types of resin include, for example, ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, silicone resin, fluororesin, cellulose, polyvinyl alcohol, etc. These composite systems can be mentioned. Among these, it is preferable to use an acrylic resin, a urethane resin, an epoxy resin, or a composite system thereof.

上塗材における樹脂としては、特に、架橋性樹脂を含有するものが好ましい。架橋性樹脂を用いることにより、形成塗膜の強度向上とともに、低汚染性、耐候性、耐薬品性等にもより優れた塗膜が得ることができ、好ましい。架橋による収縮等により、浮き状態にある粉粒体を平滑に押さえつけることもできる。
架橋に用いられる反応性官能基の組合せとしては、例えば、エポキシ−アミン、ポリオール−イソシアネート、カルボキシル−エポキシ、カルボキシル−金属イオン、カルボキシル−カルボジイミド、カルボキシル−オキサゾリン、カルボニル−ヒドラジド、加水分解性シリル基どうし等が挙げられる。このうち、カルボキシル−エポキシ、カルボキシル−金属イオン、カルボキシル−カルボジイミド、カルボキシル−オキサゾリン、カルボニル−ヒドラジド、加水分解性シリル基同士等の組合せが好適に用いられ、特にポリオール−イソシアネートの組合せが好ましい。
As the resin in the top coating material, one containing a crosslinkable resin is particularly preferable. By using a crosslinkable resin, it is possible to obtain a coating film that is improved in strength of the formed coating film, and more excellent in low contamination, weather resistance, chemical resistance, and the like. Due to shrinkage due to crosslinking, etc., the floating granular material can be pressed down smoothly.
Examples of combinations of reactive functional groups used for crosslinking include, for example, epoxy-amine, polyol-isocyanate, carboxyl-epoxy, carboxyl-metal ion, carboxyl-carbodiimide, carboxyl-oxazoline, carbonyl-hydrazide, and hydrolyzable silyl groups. Etc. Among these, a combination of carboxyl-epoxy, carboxyl-metal ion, carboxyl-carbodiimide, carboxyl-oxazoline, carbonyl-hydrazide, hydrolyzable silyl groups and the like is preferably used, and a combination of polyol-isocyanate is particularly preferable.

さらに上塗材には、着色顔料、体質顔料、繊維、増粘剤、造膜助剤、レベリング剤、可塑剤、凍結防止剤、pH調整剤、防腐剤、防黴剤、防藻剤、抗菌剤、分散剤、消泡剤、紫外線吸収剤、酸化防止剤、溶剤等の添加剤も使用可能である。   Furthermore, the top coating material includes coloring pigments, extender pigments, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreezing agents, pH adjusters, antiseptics, antifungal agents, antialgae agents, and antibacterial agents. Additives such as dispersants, antifoaming agents, ultraviolet absorbers, antioxidants and solvents can also be used.

このような上塗材を、ローラーを用いて、粉粒体を平滑に押着しながら塗付することによって、下塗材に対し未付着状態の粉粒体や、半付着状態の粉粒体、あるいは、浮き状態の粉粒体等を押着することができ、その結果、確実に平滑にすることができる。さらに粉粒体の固着性を向上させ、長期に亘り、美観性のある意匠性を維持することができる。
本発明上塗材の厚みとしては、乾燥膜厚で、0.1mm〜3mm程度とすればよいが、本発明は、比較的薄膜であっても、上記効果が得ることができる。このような場合、乾燥膜厚は、0.1mm〜1mm、好ましくは0.1mm〜0.5mm未満となるように設定すればよい。
By applying such an overcoating material using a roller while pressing the particles smoothly, the non-adhered particles, semi-adhered particles, or The floating granular material can be pressed, and as a result, it can be surely smoothed. Furthermore, the adherability of the granular material can be improved, and the designability with aesthetics can be maintained over a long period of time.
The thickness of the overcoating material of the present invention may be a dry film thickness of about 0.1 mm to 3 mm, but the present invention can achieve the above effects even if it is a relatively thin film. In such a case, the dry film thickness may be set to 0.1 mm to 1 mm, preferably 0.1 mm to less than 0.5 mm.

本発明は、既存の床面、壁面等に対して適用することができ、各工程は常温下(通常0〜40℃程度、好ましくは5〜35℃程度)で行うことができる。必要に応じ工場等におけるライン塗装に適用することも可能であり、この場合は加熱処理を行うこともできる。とりわけ本発明は、床面に対して好適な工法である。床面に適用した場合、コテで平滑に塗り仕上げる方法(流し延べ工法)等に比べ、粉粒体が平滑に強固に固着するため、美観性のある斬新な意匠性を、長期に亘り維持することができる。   The present invention can be applied to existing floor surfaces, wall surfaces, and the like, and each step can be performed at room temperature (usually about 0 to 40 ° C., preferably about 5 to 35 ° C.). If necessary, it can also be applied to line coating in a factory or the like, and in this case, heat treatment can also be performed. Especially this invention is a suitable construction method with respect to a floor surface. When applied to the floor, compared to the method of smooth finishing with a trowel (casting method), etc., the powder and particles are firmly and firmly fixed, so that the aesthetic and innovative design is maintained for a long time. be able to.

以下に実施例及び比較例を示し、本発明の特徴をより明確にするが、本発明はこの実施例に限定されない。   Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.

(実施例1)
スレート板(600mm×600mm×4mm)を水平に置き、その上に、表1に示す原料を用いて表2に示す配合で調整した下塗材Aを、ローラーで300g/m塗付した後、5分後に下塗材Aが乾燥する前に、フレークAとフレークBを1:1の割合で混合したフレークを手で全面に散布した。
標準状態(温度23℃、相対湿度50%)で16時間静置後、過剰に散布したフレークを刷毛とホウキで取り除き、表1に示す原料で表2に示す配合で調整した上塗材Aをローラーを用いて、塗付量350g/mで、平滑に押しつけながら塗付し、試験体を作製した。
作製した試験体は、上塗材A塗付時に、未付着状態の粉粒体や、半付着状態の粉粒体、あるいは、浮き状態の粉粒体を平滑に押さえ固着させたため、触感的にも毛羽立ち感のない、平滑性のある塗膜が形成された。また、試験体面全面に平板状の粉粒体が平滑に配列されている為、粉粒体ひとつひとつが際立ち、多彩感のある斬新的な意匠性が得られた。また、得られた試験体は、標準状態で24時間静置後、ほぼ硬化した塗膜を形成しており、歩行可能な状態であった。なお、上塗材Aの乾燥膜厚は、0.2mmであった。
また、作製した試験体について次のような評価を行った。
(付着強さ評価)
スレート板(600mm×600mm×4mm)を標準モルタル(70mm×70mm×20mm)に替えた以外は、上記と同様の方法で試験体を得た。
得られた試験体を標準状態で7日間静置後、JIS A 6909−2003 7.9「付着強さ試験」において、付着強度を測定した。その結果、標準モルタル以上の付着強度3N/mm以上を示すことが確認された。
(耐候性評価)
スレート板(600mm×600mm×4mm)をコンクリート板(300mm×300mm×100mm)に替えた以外は、上記と同様の方法で試験体を得た。
得られた試験体を大阪府茨木市で南向き45度傾斜にて、1ヶ月屋外暴露した後、目視にて色相変化を確認したところ、色相変化は全く認められなかった。3ヵ月、6ヵ月経過後においても異常は認められなかった。
(Example 1)
A slate plate (600 mm × 600 mm × 4 mm) was placed horizontally, and then a primer A adjusted with the composition shown in Table 2 using the raw materials shown in Table 1 was applied with 300 g / m 2 with a roller. Before the undercoat material A was dried after 5 minutes, flakes in which the flakes A and B were mixed at a ratio of 1: 1 were spread on the entire surface by hand.
After standing for 16 hours in a standard state (temperature 23 ° C., relative humidity 50%), the excessively spread flakes are removed with a brush and a broom, and the coating material A prepared by mixing the ingredients shown in Table 1 with the ingredients shown in Table 2 is used as a roller. Was applied at a coating amount of 350 g / m 2 while being pressed smoothly to prepare a test specimen.
Since the prepared test specimen was smoothly pressed and fixed to the non-adhered, semi-adhered, or floating powder when the top coat A was applied, it was also tactilely A smooth and smooth coating film was formed. Moreover, since the flat powder particles were arranged smoothly on the entire surface of the test body, each of the powder particles stood out, and a novel and colorful design was obtained. Moreover, the obtained test body formed a substantially cured coating film after being allowed to stand for 24 hours in a standard state, and was in a walkable state. In addition, the dry film thickness of the top coating material A was 0.2 mm.
Moreover, the following evaluation was performed about the produced test body.
(Adhesion strength evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with standard mortar (70 mm × 70 mm × 20 mm).
The obtained test specimen was allowed to stand in a standard state for 7 days, and the adhesion strength was measured in JIS A 6909-2003 7.9 “Adhesion Strength Test”. As a result, it was confirmed that an adhesion strength of 3 N / mm 2 or higher than standard mortar was exhibited.
(Weather resistance evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with a concrete plate (300 mm × 300 mm × 100 mm).
The obtained specimen was exposed outdoors in Ibaraki City, Osaka, Japan at a 45 ° inclination to the south for one month, and when the hue change was visually confirmed, no hue change was observed. No abnormalities were observed even after 3 and 6 months.

(比較例1)
スレート板(600mm×600mm×4mm)を水平に置き、その上に、表1に示す原料を用いて表2に示す配合で調整した下塗材Aを、ローラーで300g/m塗付した後、5分後に下塗材Aが乾燥する前に、フレークAとフレークBを1:1の割合で混合したフレークを手で全面に散布した。
標準状態で16時間静置後、過剰に散布したフレークを刷毛及びホウキで取り除き、表1に示す原料で表2に示す配合で調整した上塗材Bをローラーを用いて、塗付量約350g/mで、平滑に押しつけながら塗付し、試験体を作製した。
作製した試験体は、上塗材Bの固形分が本発明の規定する樹脂固形分より外れるため、塗付時に未付着状態の粉粒体や、半付着状態の粉粒体、あるいは、浮き状態の粉粒体を十分に平滑に押さえることができなった。そのため、触感的にも毛羽立ち感が際立った、平滑性に欠ける塗膜が形成された。また、粉粒体が被塗装面に対して乱雑に配列され、粉粒体ひとつひとつが際立たず、多彩感に欠ける意匠性となってしまった。なお、上塗材Bの乾燥膜厚は、0.12mmであった。
また、作製した試験体について次のような評価を行った。
(付着強さ評価)
スレート板(600mm×600mm×4mm)を標準モルタル(70mm×70mm×20mm)に替えた以外は、上記と同様の方法で試験体を得た。
得られた試験体を標準状態で7日間静置後、JIS A 6909−2003 7.9「付着強さ試験」において、付着強度を測定した。その結果、標準モルタル以上の付着強度3N/mm以上を示すことが確認された。
(耐候性評価)
スレート板(600mm×600mm×4mm)をコンクリート板(300mm×300mm×100mm)に替えた以外は、上記と同様の方法で試験体を得た。
試験体を大阪府茨木市で南向き45度傾斜にて、1ヶ月屋外暴露した後、目視にて色相変化を確認したところ、若干の汚れと色相変化が認められた。
(Comparative Example 1)
A slate plate (600 mm × 600 mm × 4 mm) was placed horizontally, and then a primer A adjusted with the composition shown in Table 2 using the raw materials shown in Table 1 was applied with 300 g / m 2 with a roller. Before the undercoat material A was dried after 5 minutes, flakes in which the flakes A and B were mixed at a ratio of 1: 1 were spread on the entire surface by hand.
After standing for 16 hours in the standard state, the excessively spread flakes were removed with a brush and a broom, and the coating material B prepared with the ingredients shown in Table 1 with the formulation shown in Table 2 was applied using a roller to a coating amount of about 350 g / At m 2 , coating was performed while pressing smoothly to prepare a test specimen.
Since the solid content of the overcoating material B deviates from the resin solid content defined by the present invention, the prepared test body is not adhered, semi-adhered, or floated during coating. The granular material could not be pressed sufficiently smoothly. For this reason, a coating film lacking in smoothness was formed, which was noticeably tactile and tactile. In addition, the powder particles are randomly arranged with respect to the surface to be coated, and each powder particle does not stand out, resulting in a design lacking versatility. In addition, the dry film thickness of the top coating material B was 0.12 mm.
Moreover, the following evaluation was performed about the produced test body.
(Adhesion strength evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with standard mortar (70 mm × 70 mm × 20 mm).
The obtained test specimen was allowed to stand in a standard state for 7 days, and the adhesion strength was measured in JIS A 6909-2003 7.9 “Adhesion Strength Test”. As a result, it was confirmed that an adhesion strength of 3 N / mm 2 or higher than standard mortar was exhibited.
(Weather resistance evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with a concrete plate (300 mm × 300 mm × 100 mm).
When the specimen was exposed outdoors in Ibaraki City, Osaka, at a 45 ° angle to the south for one month and then checked for hue change, a slight stain and hue change were observed.

(比較例2)
スレート板(600mm×600mm×4mm)を水平に置き、その上に、表1に示す原料を用いて表に示す配合で調整した下塗材Aを、ローラーで300g/m塗付した後、5分後に下塗材Aが乾燥する前に、フレークAとフレークBを1:1の割合で混合したフレークを手で全面に散布した。
標準状態で16時間静置後、過剰に散布したフレークを刷毛とホウキで取り除き、表1に示す原料で表に示す配合で調整した上塗材Cを、乾燥膜厚が約0.2mmとなるように流しこみ、コテを用いて、平滑に塗り仕上げ(流し延べ工法)、試験体を作製した。
作製した試験体は、未付着状態の粉粒体や、半付着状態の粉粒体、あるいは、浮き状態の粉粒体が、上塗塗膜へ混入し、被塗装面に対して乱雑に配列され、粉粒体ひとつひとつが際立たず、多彩感に欠ける意匠性となってしまった。
また、作製した試験体について次のような評価を行った。
(付着強さ評価)
スレート板(600mm×600mm×4mm)を標準モルタル(70mm×70mm×20mm)に替えた以外は、上記と同様の方法で試験体を得た。
得られた試験体を標準状態で7日間静置後、JIS A 6909−2003 7.9「付着強さ試験」において、付着強度を測定した。その結果、標準モルタル以上の付着強度3N/mm以上を示すことが確認された。
(耐候性評価)
スレート板(600mm×600mm×4mm)をコンクリート板(300mm×300mm×100mm)に替えた以外は、上記と同様の方法で試験体を得た。
試験体を大阪府茨木市で南向き45度傾斜にて、1ヶ月屋外暴露した後、目視にて色相変化を確認したところ、上塗塗膜自体の変色が認められ、意匠性の低下が認められてた。
(Comparative Example 2)
A slate plate (600 mm × 600 mm × 4 mm) was placed horizontally, and then a primer A prepared by mixing the raw materials shown in Table 1 with the composition shown in the table was applied with 300 g / m 2 with a roller. Before the base material A was dried after a minute, flakes in which flakes A and B were mixed at a ratio of 1: 1 were spread on the entire surface by hand.
After standing for 16 hours in the standard state, flakes excessively dispersed are removed with a brush and a broom, and the coating material C prepared with the ingredients shown in Table 1 with the formulation shown in the table is adjusted so that the dry film thickness is about 0.2 mm. Using a trowel and a trowel, a smooth coating finish (casting method) was made to prepare a test specimen.
In the prepared specimen, unattached, semi-attached, or floating powder is mixed in the top coating film and randomly arranged on the surface to be coated. As a result, each individual granular material was inconspicuous, resulting in a design lacking versatility.
Moreover, the following evaluation was performed about the produced test body.
(Adhesion strength evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with standard mortar (70 mm × 70 mm × 20 mm).
The obtained test specimen was allowed to stand in a standard state for 7 days, and the adhesion strength was measured in JIS A 6909-2003 7.9 “Adhesion Strength Test”. As a result, it was confirmed that an adhesion strength of 3 N / mm 2 or higher than standard mortar was exhibited.
(Weather resistance evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with a concrete plate (300 mm × 300 mm × 100 mm).
The specimen was exposed outdoors in Ibaraki City, Osaka, at a 45 degree angle southward for 1 month, and when the hue change was confirmed by visual inspection, discoloration of the top coating film itself was observed, and a deterioration in design was observed. It was.

(比較例3)
スレート板(600mm×600mm×4mm)を水平に置き、その上に、表1に示す原料を用いて表2に示す配合で調整した下塗材Aを、ローラーで300g/m塗付した後、5分後に下塗材Aが乾燥する前に、フレークAとフレークBを1:1の割合で混合したフレークを手で全面に散布した。
標準状態で16時間乾燥後、過剰に散布したフレークを刷毛及びホウキで取り除き、試験体を作製した。
作製した試験体は、上塗材を塗付していないため、未付着状態の粉粒体や、半付着状態の粉粒体、あるいは、浮き状態の粉粒体が多数存在し、触感的にも毛羽立ち感が際立った、平滑性に欠ける意匠性が形成された。また、粉粒体が被塗装面に対して乱雑に配列され、粉粒体ひとつひとつが際立たず、多彩感に欠ける意匠性となってしまった。
また、作製した試験体について次のような評価を行った。
(付着強さ評価)
スレート板(600mm×600mm×4mm)を標準モルタル(70mm×70mm×20mm)に替えた以外は、上記と同様の方法で試験体を得た。
得られた試験体を標準状態で7日間静置後、JIS A 6909−2003 7.9「付着強さ試験」において、付着強度を測定した。その結果、0.3N/mmであった。
(耐候性評価)
スレート板(600mm×600mm×4mm)をコンクリート板(300mm×300mm×100mm)に替えた以外は、上記と同様の方法で試験体を得た。
試験体を大阪府茨木市で南向き45度傾斜にて、1ヶ月屋外暴露した後、目視にて色相変化を確認したところ、色相変化が顕著に認められた。
(Comparative Example 3)
A slate plate (600 mm × 600 mm × 4 mm) was placed horizontally, and then a primer A adjusted with the composition shown in Table 2 using the raw materials shown in Table 1 was applied with 300 g / m 2 with a roller. Before the base material A was dried after 5 minutes, flakes in which the flakes A and B were mixed at a ratio of 1: 1 were sprayed over the entire surface by hand.
After drying for 16 hours in a standard state, flakes excessively spread were removed with a brush and a broom to prepare a test specimen.
Since the prepared test specimen is not coated with an overcoat material, there are a large number of unadhered, semi-adhered, or floating powders, which are also tactile. The design which lacks in smoothness and the feeling of fuzz was remarkable was formed. In addition, the powder particles are randomly arranged with respect to the surface to be coated, and each powder particle does not stand out, resulting in a design lacking versatility.
Moreover, the following evaluation was performed about the produced test body.
(Adhesion strength evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with standard mortar (70 mm × 70 mm × 20 mm).
The obtained test specimen was allowed to stand in a standard state for 7 days, and the adhesion strength was measured in JIS A 6909-2003 7.9 “Adhesion Strength Test”. As a result, it was 0.3 N / mm 2 .
(Weather resistance evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with a concrete plate (300 mm × 300 mm × 100 mm).
When the specimen was exposed outdoors in Ibaraki City, Osaka Prefecture at a 45 degree inclination southward for one month, and the hue change was visually confirmed, the hue change was noticeable.

(実施例2)
スレート板(600mm×600mm×4mm)を垂直方向に立て、このスレート板の表面に、下塗材Aをローラーで300g/m塗付した後、5分後に下塗材Aが乾燥する前に、フレークAとフレークBを1:1の割合で混合したフレークを吹き付けにより全面に散布した。
標準状態で16時間静置後、過剰に散布したフレークを刷毛で取り除き、上塗材Aをローラーを用いて塗付量350g/mで平滑に押しつけながら塗付し、試験体を作製した。
作製した試験体は、上塗材A塗付時に、未付着状態の粉粒体や、半付着状態の粉粒体、あるいは、浮き状態の粉粒体を平滑に押さえ固着させたため、触感的にも毛羽立ち感のない、平滑性のある塗膜が形成された。また、試験体面全面に平板状の粉粒体が平滑に配列されている為、粉粒体ひとつひとつが際立ち、多彩感のある斬新的な意匠性が得られた。また、得られた試験体は、標準状態で24時間静置後、ほぼ硬化した塗膜を形成していた。なお、上塗材Aの乾燥膜厚は、0.2mmであった。
また、作製した試験体について次のような評価を行った。
(耐候性評価)
スレート板(600mm×600mm×4mm)をコンクリート板(300mm×300mm×100mm)に替えた以外は、上記と同様の方法で試験体を得た。
得られた試験体を大阪府茨木市で南向き45度傾斜にて、1ヶ月屋外暴露した後、目視にて色相変化を確認したところ、色相変化は全く認められなかった。3ヵ月、6ヵ月経過後においても異常は認められなかった。
(Example 2)
A slate plate (600 mm × 600 mm × 4 mm) is set up in the vertical direction, and after the primer A is applied to the surface of the slate plate with a roller at 300 g / m 2 , the flakes before the primer A is dried after 5 minutes. Flakes mixed with A and flakes B at a ratio of 1: 1 were sprayed on the entire surface by spraying.
After standing for 16 hours in a standard state, flakes excessively dispersed were removed with a brush, and the top coating material A was applied while being pressed smoothly at a coating amount of 350 g / m 2 using a roller to prepare a test specimen.
Since the prepared test specimen was smoothly pressed and fixed to the non-adhered, semi-adhered, or floating powder when the top coat A was applied, it was also tactilely A smooth and smooth coating film was formed. In addition, since the flat powder particles are arranged smoothly on the entire surface of the test body, each of the powder particles stands out, and a novel and colorful design is obtained. Moreover, the obtained test body formed the coating film substantially hardened after leaving still for 24 hours in a standard state. In addition, the dry film thickness of the top coating material A was 0.2 mm.
Moreover, the following evaluation was performed about the produced test body.
(Weather resistance evaluation)
A specimen was obtained in the same manner as described above except that the slate plate (600 mm × 600 mm × 4 mm) was replaced with a concrete plate (300 mm × 300 mm × 100 mm).
The obtained specimen was exposed outdoors for 1 month at 45 degrees southward in Ibaraki City, Osaka, Japan. When the hue change was visually confirmed, no hue change was observed. No abnormalities were observed even after 3 and 6 months.

Figure 2005319453
Figure 2005319453

Figure 2005319453
Figure 2005319453

Claims (4)

(1)基材に対し、下塗材を塗付する工程、
(2)下塗材が乾燥固化する前に、平板状の粉粒体を散布する工程、
(3)樹脂固形分濃度が50〜95重量%である透明又は半透明の上塗材を、ローラーを用いて該粉粒体を押しつけながら塗付する工程、
からなることを特徴とする意匠性塗膜の形成方法。
(1) A step of applying a primer to the base material,
(2) before the undercoat material is dried and solidified, a step of spraying flat powder particles;
(3) A step of applying a transparent or semi-transparent topcoat material having a resin solid content concentration of 50 to 95% by weight while pressing the granular material using a roller,
A method for forming a designable coating film, comprising:
上塗材が、架橋性結合剤を含有することを特徴とする請求項1に記載の意匠性塗膜の形成方法。   The method for forming a designable coating film according to claim 1, wherein the top coating material contains a crosslinkable binder. 平板状の粉粒体が、長径が2mm以上、厚さが1mm以下であることを特徴とする請求項1または請求項2に記載の意匠性塗膜の形成方法。   3. The method for forming a designable coating film according to claim 1, wherein the flat granular material has a major axis of 2 mm or more and a thickness of 1 mm or less. 基材が床面を構成するものである請求項1〜請求項3のいずれかに記載の意匠性塗膜の形成方法。   The method for forming a designable coating film according to any one of claims 1 to 3, wherein the base material constitutes a floor surface.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010030266A (en) * 2008-02-01 2010-02-12 Bekku Kk Laminate and method for manufacturing the same

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JPH073193A (en) * 1991-08-23 1995-01-06 Sk Kaken Co Ltd Coating material excellent in applicability with trowel
JP2002086058A (en) * 2000-09-13 2002-03-26 Dainippon Toryo Co Ltd Designed coating film formation method
JP2002126632A (en) * 2000-10-18 2002-05-08 Dainippon Toryo Co Ltd Method for forming fancy coating film
JP2002301427A (en) * 2001-04-03 2002-10-15 Sekisui Chem Co Ltd Method for forming designable coating film
JP2003080164A (en) * 2001-09-10 2003-03-18 Kankyo Hozen Service:Kk Irregularly reflective coating treatment method and method for producing irregularly reflective coating material and irregular reflector

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH073193A (en) * 1991-08-23 1995-01-06 Sk Kaken Co Ltd Coating material excellent in applicability with trowel
JP2002086058A (en) * 2000-09-13 2002-03-26 Dainippon Toryo Co Ltd Designed coating film formation method
JP2002126632A (en) * 2000-10-18 2002-05-08 Dainippon Toryo Co Ltd Method for forming fancy coating film
JP2002301427A (en) * 2001-04-03 2002-10-15 Sekisui Chem Co Ltd Method for forming designable coating film
JP2003080164A (en) * 2001-09-10 2003-03-18 Kankyo Hozen Service:Kk Irregularly reflective coating treatment method and method for producing irregularly reflective coating material and irregular reflector

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010030266A (en) * 2008-02-01 2010-02-12 Bekku Kk Laminate and method for manufacturing the same

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