JP4877941B2 - Coating laminate - Google Patents

Coating laminate Download PDF

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JP4877941B2
JP4877941B2 JP2006157885A JP2006157885A JP4877941B2 JP 4877941 B2 JP4877941 B2 JP 4877941B2 JP 2006157885 A JP2006157885 A JP 2006157885A JP 2006157885 A JP2006157885 A JP 2006157885A JP 4877941 B2 JP4877941 B2 JP 4877941B2
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coating
resin
coating layer
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matte
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誠一 尾上
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SK Kaken Co Ltd
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本発明は、建築物や土木構造物等の表面化粧として用いられる塗膜積層体に関するものである。   The present invention relates to a coating film laminate used as a surface makeup for buildings, civil engineering structures, and the like.

従来、建築物や土木構造物等の表面化粧用塗料として、種々の艶グレードのものが提供されている。このうち、艶消しの塗膜が形成可能な塗料は、落ち着きのある独特の質感が得られることから、近年人気が高まりつつある。   2. Description of the Related Art Conventionally, various gloss grades have been provided as surface cosmetic paints for buildings and civil engineering structures. Among these, paints capable of forming a matte coating film have been gaining popularity in recent years because they can provide a calm and unique texture.

艶消し塗料としては、JIS K5663「合成樹脂エマルションペイント」に規定されている塗料が一般的である。この他、JIS A6909に規定される建築用仕上塗材、例えば、リシン塗料等の薄付け仕上塗材、スタッコ塗料等の厚付け仕上塗材、その他石材調仕上塗材、砂岩調仕上塗材等においても、艶消しの外観を呈するものがあり、凹凸模様が形成可能な厚膜タイプの材料として広く使用されている。   As the matte paint, paints defined in JIS K5663 “Synthetic resin emulsion paint” are generally used. In addition, architectural finish coating materials specified in JIS A6909, for example, thin finish coating materials such as ricin paint, thick finish coating materials such as stucco paint, other stone finish finish coating materials, sandstone finish finish coating materials, etc. Some of them have a matte appearance, and are widely used as thick film type materials capable of forming an uneven pattern.

ところで、近年、都市部等においては、自動車等からの排出ガスによって大気中に油性の汚染物質等が浮遊している状況である。上述の如き艶消し塗料においても、その塗膜表面にこれら汚染物質が付着堆積し、美観性が損われる場合がある。   By the way, in recent years, in urban areas and the like, oily pollutants and the like are floating in the atmosphere due to exhaust gas from automobiles and the like. Even in the matte paint as described above, these contaminants may be deposited on the surface of the coating film, resulting in a loss of aesthetics.

塗膜表面に適用可能な防汚処理剤として、特許文献1には、樹脂、酸化物ゾル有機溶剤、及び水からなる組成物が記載されている。
しかし、艶消し塗膜に対し特許文献1の如き汚染防止剤を適用すると、初期の艶の状態とは異なる仕上がりになるおそれがある。また、塗膜の色相が黒っぽく変化する現象、所謂濡れ色が発生する場合がある。さらには、被膜の一部が虹色を呈する干渉むらが生じる場合もある。このように、特許文献1の如き汚染防止剤では、当初の艶消し塗膜の質感が損なわれやすいという問題がある。そもそも、このような汚染防止剤は、自動車外板塗膜等の光沢感を有する塗膜に対する材料として設計されたものであり、その対象を艶消し塗膜とすることについては想定されていない。
As an antifouling treatment agent applicable to the coating film surface, Patent Document 1 describes a composition comprising a resin, an oxide sol organic solvent, and water.
However, when the antifouling agent as disclosed in Patent Document 1 is applied to the matte coating film, the finish may be different from the initial glossy state. In addition, a phenomenon that the hue of the coating film changes to black, that is, a so-called wet color may occur. Furthermore, interference unevenness in which a part of the film has a rainbow color may occur. As described above, the antifouling agent as disclosed in Patent Document 1 has a problem that the texture of the original matte coating film is easily impaired. In the first place, such an antifouling agent is designed as a material for a glossy coating film such as a coating film on an automobile outer plate, and it is not assumed that the object is a matte coating film.

本発明は、上述のような問題点に鑑みなされたものであり、艶消し塗膜の質感を保持しつつ、その塗膜表面の耐汚染性を高めることを目的とするものである。   The present invention has been made in view of the above-described problems, and an object thereof is to improve the stain resistance of the coating film surface while maintaining the texture of the matte coating film.

WO99/54414号公報WO99 / 54414

本発明者は、上記目的を達成するため鋭意検討を行った結果、艶消し塗膜層の表面に対し、有機質樹脂及びシリカを主成分とする特定被覆層を設けた塗膜積層体に想到し、本発明を完成させるに到った。   As a result of intensive studies to achieve the above object, the present inventor has come up with a coating laminate in which a specific coating layer mainly composed of an organic resin and silica is provided on the surface of the matte coating layer. The present invention has been completed.

すなわち、本発明は以下の特徴を有するものである。
1.艶消し塗膜層の表面に、該艶消し塗膜層が視認可能な状態で被覆層が設けられ、
前記被覆層は、有機質樹脂及びシリカを固形分重量比率100:50〜100:500で含むものであり、
前記被覆層に含まれるシリカは、平均一次粒子径1〜200nmのシリカゾルに由来する凝集体であり、
前記被覆層の塗付量は固形分で0.1〜50g/mであることを特徴とする塗膜積層体。
2.前記シリカゾルが、pH5.0以上8.5未満の水分散性シリカゾルであることを特徴とする1.記載の塗膜積層体。
That is, the present invention has the following characteristics.
1. A coating layer is provided on the surface of the matte coating layer in a state where the matting coating layer is visible,
The coating layer includes an organic resin and silica in a solid content weight ratio of 100: 50 to 100: 500,
Silica contained in the coating layer is an aggregate derived from silica sol having an average primary particle diameter of 1 to 200 nm,
The coating amount of the coating layer is 0.1 to 50 g / m 2 in terms of solid content.
2. The silica sol is a water-dispersible silica sol having a pH of 5.0 or more and less than 8.5. The coating film laminated body of description.

本発明によれば、艶消し塗膜の質感を保持しつつ、その塗膜表面の耐汚染性を高めることができる。   ADVANTAGE OF THE INVENTION According to this invention, the stain resistance of the coating-film surface can be improved, maintaining the texture of a matt coating film.

以下、本発明を実施するための最良の形態について説明する。   Hereinafter, the best mode for carrying out the present invention will be described.

本発明の塗膜積層体は、艶消し塗膜層の表面に被覆層が設けられたものであり、主に建築物や土木構造物等の表面化粧用、特に風雨や太陽光等に晒される外装面の化粧用として好ましく適用できるものである。   The coating laminate of the present invention has a matte coating layer provided with a coating layer, and is mainly exposed to surface cosmetics such as buildings and civil engineering structures, particularly to wind and rain. It can be preferably applied to cosmetics for exterior surfaces.

このうち艶消し塗膜層は、艶消し塗料によって形成される。このような艶消し塗料としては、JIS K5663「合成樹脂エマルションペイント」に規定される塗料が挙げられる。このタイプの塗料は、一般にフラット塗料と呼ばれるものである。この他の艶消し塗料としては、JIS A6909に規定されるリシン塗料等の薄付け仕上塗材、スタッコ塗料等の厚付け仕上塗材等、その他石材調仕上塗材、砂岩調仕上塗材等の各種建築用仕上塗材が挙げられる。このような建築用仕上塗材は、凹凸模様が形成可能な厚膜タイプの材料として使用できるものである。   Of these, the matte coating layer is formed of a matte paint. Examples of such matte paints include paints defined in JIS K5663 “Synthetic Resin Emulsion Paint”. This type of paint is commonly referred to as a flat paint. Other matte coatings include thin finish coating materials such as lysine paints, thick finish coating materials such as stucco paints, etc. as defined in JIS A6909, other stone finish finish coating materials, and sandstone finish finish coating materials There are various finishing coating materials for buildings. Such a building finish coating material can be used as a thick film type material capable of forming an uneven pattern.

艶消し塗膜層は、建築物や土木構造物等の基材表面に艶消し塗料を塗付・乾燥することによって形成できる。艶消し塗膜層は、建築物や土木構造物等の基材表面に予め旧塗膜として存在するものであってもよい。
なお、艶消し塗膜層における「艶消し」の程度は、その鏡面光沢度によって規定することができる。艶消し塗膜層の鏡面光沢度(測定角度60度)は通常20以下、好ましくは15以下、さらに好ましくは10以下である。
The matte paint film layer can be formed by applying and drying a matte paint on the surface of a base material such as a building or a civil engineering structure. The matte paint film layer may exist in advance as an old paint film on the surface of a base material such as a building or a civil engineering structure.
The degree of “matte” in the matte coating layer can be defined by its specular gloss. The specular gloss (measuring angle 60 degrees) of the matte coating layer is usually 20 or less, preferably 15 or less, more preferably 10 or less.

本発明の塗膜積層体は、上述の艶消し塗膜層の表面に、被覆層が設けられたものである。この被覆層は、艶消し塗膜層が視認可能な状態で設けられる。すなわち、艶消し塗膜が有する色相、凹凸模様は、被覆層の有無にかかわらずほとんど変化しない。   The coating film laminate of the present invention has a coating layer provided on the surface of the matte coating layer described above. This coating layer is provided in a state where the matte coating layer is visible. That is, the hue and concavo-convex pattern of the matte coating film hardly change regardless of the presence or absence of the coating layer.

本発明における被覆層は、有機質樹脂及びシリカを含む被覆液によって形成されるものである。
このうち、有機質樹脂は、主にシリカを固定化する役割を担う成分である。有機質樹脂としては、例えば、セルロース、ポリビニルアルコール、バイオガム、ガラクトマンナン誘導体、アルギン酸誘導体、酢酸ビニル樹脂、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、アクリルシリコン樹脂、フッ素樹脂等、あるいはこれらの複合系等が挙げられ、これらの1種または2種以上を使用することができる。これらは架橋反応性を有するものであってもよい。有機質樹脂の形態としては、水溶性樹脂及び/または水分散性樹脂(樹脂エマルション)が好適である。
The coating layer in the present invention is formed by a coating solution containing an organic resin and silica.
Of these, the organic resin is a component mainly responsible for immobilizing silica. Examples of the organic resin include cellulose, polyvinyl alcohol, bio gum, galactomannan derivative, alginic acid derivative, vinyl acetate resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, fluorine resin, or a composite thereof. A system etc. are mentioned, These 1 type (s) or 2 or more types can be used. These may have crosslinking reactivity. As the form of the organic resin, a water-soluble resin and / or a water-dispersible resin (resin emulsion) is preferable.

被覆層におけるシリカは、平均一次粒子径1〜200nmのシリカゾルに由来する凝集体である。このようなシリカは、シラノール基等の極性基の作用により耐汚染性を発揮し、さらに凝集体の形成により底艶、濡れ色、干渉ムラ等の発生を抑制し、艶消し塗膜の質感を保持する役割を担う成分である。   Silica in the coating layer is an aggregate derived from silica sol having an average primary particle diameter of 1 to 200 nm. Such silica exhibits stain resistance by the action of polar groups such as silanol groups, and further suppresses the occurrence of bottom gloss, wet color, interference interference, etc. due to the formation of aggregates, and improves the texture of matte coatings. It is a component that plays a role of holding.

シリカゾルの平均一次粒子径は、通常1〜200nm、好ましくは5〜100nmである。この範囲内であれば、平均一次粒子径が異なる複数のシリカゾルを併用することもできる。シリカゾルの平均一次粒子径が200nmよりも大きい場合は、比表面積が小さくなり、シラノール基も減るため耐汚染性が不十分となる。平均一次粒子径が1nmよりも小さい場合は、シリカゾル自体が不安定化するため、実用的でない。なお、ここに言う平均一次粒子径は、光散乱法によって測定される値である。   The average primary particle diameter of the silica sol is usually 1 to 200 nm, preferably 5 to 100 nm. Within this range, a plurality of silica sols having different average primary particle sizes can be used in combination. When the average primary particle diameter of the silica sol is larger than 200 nm, the specific surface area becomes small and silanol groups are reduced, so that the stain resistance is insufficient. When the average primary particle size is smaller than 1 nm, the silica sol itself becomes unstable, so that it is not practical. In addition, the average primary particle diameter said here is a value measured by the light-scattering method.

シリカゾルとしては、pH5.0以上8.5未満(好ましくは6.0以上8.0以下)の水分散性シリカゾルが好適である。このようなpHに調製されたシリカゾルは、その粒子表面の豊富なシラノール基によって、優れた耐汚染効果を発揮することができる。また、水溶性樹脂及び/または水分散性樹脂と水分散性シリカゾルとの組合せにより、有機溶剤をほとんど含まない水性被覆液を得ることができる。   As the silica sol, a water-dispersible silica sol having a pH of 5.0 or more and less than 8.5 (preferably 6.0 or more and 8.0 or less) is suitable. The silica sol prepared at such pH can exhibit an excellent antifouling effect due to abundant silanol groups on the particle surface. Moreover, the aqueous coating liquid which hardly contains an organic solvent can be obtained by the combination of water-soluble resin and / or water-dispersible resin, and water-dispersible silica sol.

このような中性タイプの水分散性シリカゾルは、シリケート化合物を原料として製造することができる。シリケート化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラn−プロポキシシラン、テトライソプロポキシシラン、テトラn−ブトキシシラン、テトライソブトキシシラン、テトラsec−ブトキシシラン、テトラt−ブトキシシラン、テトラフェノキシシラン等、あるいはこれらの縮合物等が挙げられる。この他、上記シリケート化合物以外のアルコキシシラン化合物や、アルコール類、グリコール類、グルコールエーテル類、フッ素アルコール、シランカップリング剤、ポリオキシアルキレン基含有化合物等を併せて使用することもできる。水分散性シリカゾルの媒体としては、水及び/または水溶性溶剤が使用できる。水溶性溶剤としては、例えば、アルコール類、グリコール類、グリコールエーテル類等が挙げられる。   Such a neutral type water-dispersible silica sol can be produced using a silicate compound as a raw material. Examples of the silicate compound include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, tetra t-butoxysilane, tetra Examples thereof include phenoxysilane and the condensates thereof. In addition, alkoxysilane compounds other than the above silicate compounds, alcohols, glycols, glycol ethers, fluorine alcohols, silane coupling agents, polyoxyalkylene group-containing compounds, and the like can also be used. As the medium of the water-dispersible silica sol, water and / or a water-soluble solvent can be used. Examples of the water-soluble solvent include alcohols, glycols, glycol ethers and the like.

被覆層におけるシリカは、このようなシリカゾルの一次粒子が二次凝集したものである。シリカゾルの二次凝集は、被覆層を形成する被覆液の濃度、荷電状態等を適宜調整することにより進行させることができる。例えば、被覆液における固形分濃度を十分に低く設定しておけば、被覆液の乾燥過程においてシリカゾル同士が接近し、その相互作用により二次凝集体が生成される。このような理由から、被覆液の固形分濃度は、通常10重量%以下(好ましくは5重量%以下、より好ましくは3重量%以下)に設定することが望ましい。さらに、被覆液を構成する有機質樹脂として、異なる2種以上の樹脂を併用することも、二次凝集体の生成には有効な手段である。一例としてアクリル樹脂とウレタン樹脂、アクリルシリコン樹脂とウレタン樹脂、アクリル樹脂とエポキシ樹脂、アクリルシリコン樹脂とエポキシ樹脂、アクリル樹脂とバイオガム、アクリルシリコン樹脂とバイオガムの組合せ等が挙げられる。2種の樹脂を組合せて使用する場合は、固形分重量比において、一方の樹脂が他方の樹脂の1/9未満となるように調整すればよい。   The silica in the coating layer is a secondary aggregate of the primary particles of such a silica sol. The secondary flocculation of the silica sol can be advanced by appropriately adjusting the concentration of the coating liquid forming the coating layer, the charged state, and the like. For example, if the solid content concentration in the coating liquid is set sufficiently low, silica sols approach each other in the drying process of the coating liquid, and a secondary aggregate is generated by the interaction. For these reasons, it is desirable that the solid content concentration of the coating liquid is usually set to 10% by weight or less (preferably 5% by weight or less, more preferably 3% by weight or less). Furthermore, using two or more different resins in combination as the organic resin constituting the coating liquid is also an effective means for producing secondary aggregates. Examples include acrylic resin and urethane resin, acrylic silicon resin and urethane resin, acrylic resin and epoxy resin, acrylic silicon resin and epoxy resin, acrylic resin and biogum, and a combination of acrylic silicon resin and biogum. When two types of resins are used in combination, one resin may be adjusted to be less than 1/9 of the other resin in the solid content weight ratio.

被覆層における有機質樹脂とシリカの固形分重量比率は、通常100:50〜100:500(好ましくは100:80〜100:400、より好ましくは100:100〜100:300)とする。このような範囲内であれば、艶消し塗膜の質感を保持しつつ、優れた耐汚染性能を得ることができる。この固形分比率においてシリカが少なすぎる場合は、艶消し塗膜の質感が損われやすく、また耐汚染性の点で十分な効果を得ることができない。シリカが多すぎる場合は、被覆層のシリカが経時的に脱離して耐汚染効果が損なわれるおそれがある。また、被覆層に割れが生じやすくなる。   The solid content weight ratio of the organic resin and silica in the coating layer is usually 100: 50 to 100: 500 (preferably 100: 80 to 100: 400, more preferably 100: 100 to 100: 300). Within such a range, excellent antifouling performance can be obtained while maintaining the texture of the matte coating film. When the amount of silica is too small in this solid content ratio, the texture of the matte coating film is liable to be damaged, and a sufficient effect cannot be obtained in terms of stain resistance. When there is too much silica, the silica of the coating layer may be detached over time, and the anti-staining effect may be impaired. In addition, cracks are likely to occur in the coating layer.

被覆層を形成する被覆液には、有機質樹脂とシリカ以外の成分を適宜混合することができる。このような成分としては、例えば、増粘剤、レベリング剤、湿潤剤、可塑剤、造膜助剤、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、顔料、触媒、架橋剤等が挙げられる。被覆液のpHは、被覆液の安定性の点でpH5.0以上8.5未満(好ましくは6.5以上8.0以下)とすることが望ましい。   Components other than the organic resin and silica can be appropriately mixed in the coating solution for forming the coating layer. Such components include, for example, thickeners, leveling agents, wetting agents, plasticizers, film-forming aids, antifreezing agents, pH adjusting agents, preservatives, antifungal agents, antialgae agents, antibacterial agents, dispersions Agents, antifoaming agents, ultraviolet absorbers, antioxidants, pigments, catalysts, crosslinking agents and the like. The pH of the coating solution is desirably 5.0 to less than 8.5 (preferably 6.5 to 8.0) from the viewpoint of the stability of the coating solution.

被覆層を形成する際には、スプレー塗り、刷毛塗り、ローラー塗り等の塗装手段を適宜採用することができる。
被覆層の塗付量は固形分で0.1〜50g/m(好ましくは0.5〜20g/m)とする。塗付量が0.1g/mよりも少ない場合は耐汚染性向上効果が得られず、50g/mよりも多い場合は、艶消し塗膜表面の微細な凹凸が平坦化してしまい、艶消し塗膜の質感が損われやすくなる。なお、本発明における被覆層は、上記範囲内で塗付量が多少変動しても艶むら等の不具合が生じないため、塗付作業の効率化を図ることができる。
When forming the coating layer, coating means such as spray coating, brush coating, and roller coating can be appropriately employed.
The coating amount of the coating layer is 0.1 to 50 g / m 2 (preferably 0.5 to 20 g / m 2 ) in terms of solid content. When the coating amount is less than 0.1 g / m 2, the effect of improving the stain resistance is not obtained, and when it is more than 50 g / m 2 , the fine unevenness on the matte coating surface is flattened, The texture of the matte paint film is easily damaged. In addition, since the coating layer in the present invention does not cause defects such as uneven gloss even if the coating amount varies slightly within the above range, the efficiency of the coating operation can be improved.

以下に実施例を示し、本発明の特徴をより明確にする。   Examples are given below to clarify the features of the present invention.

(水性被覆液A)
アクリルシリコン樹脂エマルション(固形分50重量%)、水溶性ウレタン樹脂(固形分35重量%)、水分散性シリカゾル(pH7.6、固形分20重量%、平均1次粒子径27nm)を固形分重量比率92:8:125で混合し、これに水を加えて固形分2重量%、pH7.2の水性被覆液Aを作製した。この水性被覆液Aを黒色紙上に塗付量(固形分)が3g/mでスプレー塗装し、標準状態で24時間乾燥させ、その塗膜を走査型電子顕微鏡で観察したところ、シリカゾルの凝集体が確認された。
(Aqueous coating solution A)
Acrylic silicone resin emulsion (solid content 50% by weight), water-soluble urethane resin (solid content 35% by weight), water-dispersible silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm) The mixture was mixed at a ratio of 92: 8: 125, and water was added thereto to prepare an aqueous coating liquid A having a solid content of 2% by weight and a pH of 7.2. This aqueous coating liquid A was spray-coated on black paper at a coating amount (solid content) of 3 g / m 2 , dried in a standard state for 24 hours, and the coating film was observed with a scanning electron microscope. Aggregation was confirmed.

(水性被覆液B)
アクリルシリコン樹脂エマルション(固形分50重量%)、水溶性エポキシ樹脂(固形分100重量%)、水分散性シリカゾル(pH7.6、固形分20重量%、平均1次粒子径27nm)を固形分重量比率92:8:125で混合し、これに水を加えて固形分2重量%、pH7.2の水性被覆液Bを作製した。この水性被覆液Bを黒色紙上に塗付量(固形分)が3g/mでスプレー塗装し、標準状態で24時間乾燥させ、その塗膜を走査型電子顕微鏡で観察したところ、シリカゾルの凝集体が確認された。
(Aqueous coating solution B)
Acrylic silicon resin emulsion (solid content 50% by weight), water-soluble epoxy resin (solid content 100% by weight), water-dispersible silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm) The mixture was mixed at a ratio of 92: 8: 125, and water was added thereto to prepare an aqueous coating solution B having a solid content of 2% by weight and a pH of 7.2. This aqueous coating solution B was spray-coated on black paper at a coating amount (solid content) of 3 g / m 2 , dried in a standard state for 24 hours, and the coating film was observed with a scanning electron microscope. Aggregation was confirmed.

(水性被覆液C)
アクリルシリコン樹脂エマルション(固形分50重量%)、バイオガム(固形分100重量%)、水分散性シリカゾル(pH7.6、固形分20重量%、平均1次粒子径27nm)を固形分重量比率92:8:125で混合し、これに水を加えて固形分2重量%、pH7.2の水性被覆液Cを作製した。この水性被覆液Cを黒色紙上に塗付量(固形分)が3g/mでスプレー塗装し、標準状態で24時間乾燥させ、その塗膜を走査型電子顕微鏡で観察したところ、シリカゾルの凝集体が確認された。
(Aqueous coating solution C)
Acrylic silicone resin emulsion (solid content 50% by weight), bio gum (solid content 100% by weight), water dispersible silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm), solid content weight ratio 92: The mixture was mixed at 8: 125, and water was added thereto to prepare an aqueous coating solution C having a solid content of 2% by weight and a pH of 7.2. The aqueous coating liquid C was spray-coated on black paper at a coating amount (solid content) of 3 g / m 2 , dried in a standard state for 24 hours, and the coating film was observed with a scanning electron microscope. Aggregation was confirmed.

(水性被覆液D)
アクリルシリコン樹脂エマルション(固形分50重量%)、水分散性シリカゾル(pH7.6、固形分20重量%、平均1次粒子径27nm)を固形分重量比率100:125で混合し、これに水を加え、さらに0.1N酢酸水溶液を用いて固形分2重量%、pH6.0の水性被覆液Dを作製した。この水性被覆液Dを黒色紙上に塗付量(固形分)が3g/mでスプレー塗装し、標準状態で24時間乾燥させ、その塗膜を走査型電子顕微鏡で観察したところ、シリカゾルの凝集体が確認された。
(Aqueous coating solution D)
Acrylic silicon resin emulsion (solid content 50% by weight) and water-dispersible silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm) were mixed at a solid content weight ratio of 100: 125, and water was added thereto. In addition, an aqueous coating solution D having a solid content of 2% by weight and a pH of 6.0 was prepared using a 0.1N aqueous acetic acid solution. This aqueous coating liquid D was spray-coated on black paper at a coating amount (solid content) of 3 g / m 2 , dried in a standard state for 24 hours, and the coating film was observed with a scanning electron microscope. Aggregation was confirmed.

(水性被覆液E)
アクリルシリコン樹脂エマルション(固形分50重量%)、水分散性シリカゾル(pH7.6、固形分20重量%、平均1次粒子径27nm)を固形分重量比率100:125で混合し、これに水を加えて固形分2重量%、pH7.2の水性被覆液Eを作製した。この水性被覆液Eを黒色紙上に塗付量(固形分)が3g/mでスプレー塗装し、標準状態で24時間乾燥させ、その塗膜を走査型電子顕微鏡で観察したところ、凝集体の存在は認められなかった。
(Aqueous coating solution E)
Acrylic silicon resin emulsion (solid content 50% by weight) and water-dispersible silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm) were mixed at a solid content weight ratio of 100: 125, and water was added thereto. In addition, an aqueous coating solution E having a solid content of 2% by weight and a pH of 7.2 was prepared. This aqueous coating liquid E was spray-coated on black paper at a coating amount (solid content) of 3 g / m 2 , dried in a standard state for 24 hours, and the coating film was observed with a scanning electron microscope. Existence was not recognized.

(試験例1)
アクリル樹脂エマルション(固形分50重量%)200重量部に対し、酸化チタン分散液(固形分70重量%)40重量部、重質炭酸カルシウム(平均粒子径8μm)160重量部、寒水石(平均粒子径200μm)270重量部、造膜助剤16重量部、増粘剤5重量部、消泡剤5重量部を常法により均一に混合して艶消し塗料を作製した。予めシーラー処理を行ったスレート板に、上記方法にて得られた艶消し塗料を塗付量(固形分)が800g/mとなるように鏝塗りし、標準状態(温度23℃・相対湿度50%)で48時間乾燥させることにより、白色の艶消し塗膜を形成させた。この艶消し塗膜の鏡面光沢度は1.6であった。
また、上記艶消し塗料に対し、カーボンブラック分散液(固形分20重量%)を3重量%添加した後、同様の方法で塗装を行い、灰色の艶消し塗膜を形成させた。この艶消し塗膜の鏡面光沢度は1.9であった。
(Test Example 1)
40 parts by weight of titanium oxide dispersion (solid content 70% by weight), 160 parts by weight of heavy calcium carbonate (average particle size 8 μm), 200 ml by weight of acrylic resin emulsion (solid content 50% by weight) A matte paint was prepared by uniformly mixing 270 parts by weight (diameter 200 μm), 16 parts by weight of a film-forming aid, 5 parts by weight of a thickener, and 5 parts by weight of an antifoaming agent by a conventional method. The matte paint obtained by the above method is applied to a slate plate that has been subjected to a sealer treatment in advance so that the coating amount (solid content) is 800 g / m 2, and the standard state (temperature 23 ° C., relative humidity) (50%) for 48 hours to form a white matte coating. The specular gloss of this matte coating film was 1.6.
Further, after adding 3% by weight of carbon black dispersion (solid content 20% by weight) to the matte paint, coating was performed in the same manner to form a gray matte coating film. The specular gloss of this matte coating film was 1.9.

以上の方法で得られた各艶消し塗膜に対し、前記水性被覆液Aを塗付量(固形分)が3g/mとなるようにスプレー塗装し、標準状態で24時間乾燥させた。このようにして得られた各試験体の仕上状態を確認したところ、艶・色の状態や全体的な質感において艶消し塗膜との差異は認められなかった。
次に白色の試験体を大阪府茨木市にて南向き45度の角度で屋外曝露し、3ヶ月後の外観を確認した。その結果、水性被覆液Aを塗付した試験体における白色度の変化(△L)は−0.8であった。なお、艶消し塗膜のみを形成させた試験体について同様の試験を行ったところ、その△Lは−4.5であった。
Each matte coating film obtained by the above method was spray-coated with the aqueous coating solution A so that the coating amount (solid content) was 3 g / m 2 and dried in a standard state for 24 hours. As a result of confirming the finished state of each specimen thus obtained, no difference from the matte coating was observed in the gloss / color state and overall texture.
Next, the white specimen was exposed outdoors at an angle of 45 degrees southward in Ibaraki City, Osaka Prefecture, and the appearance after 3 months was confirmed. As a result, the change in whiteness (ΔL) in the test body to which the aqueous coating liquid A was applied was −0.8. In addition, when the same test was done about the test body which formed only the matte coating film, that (DELTA) L was -4.5.

(試験例2)
水性被覆液Aに替えて水性被覆液Bを使用した以外は、試験例1と同様の方法で試験体を作製した。その仕上状態を確認したところ、艶・色の状態や全体的な質感において艶消し塗膜との差異は認められなかった。屋外曝露試験における△Lは−0.6であった。
(Test Example 2)
A test specimen was prepared in the same manner as in Test Example 1 except that the aqueous coating liquid B was used instead of the aqueous coating liquid A. When the finished state was confirmed, there was no difference from the matte coating in terms of gloss / color and overall texture. ΔL in the outdoor exposure test was −0.6.

(試験例3)
水性被覆液Aに替えて水性被覆液Cを使用した以外は、試験例1と同様の方法で試験体を作製した。その仕上状態を確認したところ、艶・色の状態や全体的な質感において艶消し塗膜との差異は認められなかった。屋外曝露試験における△Lは−0.6であった。
(Test Example 3)
A test specimen was prepared in the same manner as in Test Example 1 except that the aqueous coating liquid C was used instead of the aqueous coating liquid A. When the finished state was confirmed, there was no difference from the matte coating in terms of gloss / color and overall texture. ΔL in the outdoor exposure test was −0.6.

(試験例4)
水性被覆液Aに替えて水性被覆液Dを使用した以外は、試験例1と同様の方法で試験体を作製した。その仕上状態を確認したところ、艶・色の状態や全体的な質感において艶消し塗膜との差異は認められなかった。屋外曝露試験における△Lは−1.2であった。
(Test Example 4)
A test specimen was prepared in the same manner as in Test Example 1 except that the aqueous coating liquid D was used instead of the aqueous coating liquid A. When the finished state was confirmed, there was no difference from the matte coating in terms of gloss / color and overall texture. ΔL in the outdoor exposure test was −1.2.

(試験例5)
水性被覆液Aに替えて水性被覆液Eを使用した以外は、試験例1と同様の方法で試験体を作製した。その仕上状態を確認したところ、底艶と濡れ色の発生が認められた。屋外曝露試験における△Lは−0.8であった。
(Test Example 5)
A test specimen was prepared in the same manner as in Test Example 1 except that the aqueous coating liquid E was used instead of the aqueous coating liquid A. When the finished state was confirmed, generation of bottom gloss and wet color was observed. ΔL in the outdoor exposure test was −0.8.

Claims (4)

艶消し塗膜層の表面に、該艶消し塗膜層が視認可能な状態で被覆層が設けられ、
前記艶消し層の鏡面光沢度(測定角度60度)が、20以下であり、
前記被覆層は、有機質樹脂及びシリカを固形分重量比率100:80〜100:500で含むものであり、
前記被覆層に含まれるシリカは、平均一次粒子径1〜200nmのシリカゾルに由来する凝集体であり、
前記シリカゾルが、pH5.0以上8.0以下の水分散性シリカゾルであり
前記有機質樹脂が、異なる2種以上の樹脂を併用するものであり、
前記被覆層の塗付量は固形分で0.1〜50g/mであることを特徴とする塗膜積層体。
A coating layer is provided on the surface of the matte coating layer in a state where the matting coating layer is visible,
The matte layer has a specular gloss (measurement angle of 60 degrees) of 20 or less,
The coating layer includes an organic resin and silica in a solid content weight ratio of 100: 80 to 100: 500,
Silica contained in the coating layer is an aggregate derived from silica sol having an average primary particle diameter of 1 to 200 nm,
The silica sol is a water-dispersible silica sol having a pH of 5.0 or more and 8.0 or less ,
The organic resin is a combination of two or more different resins,
The coating amount of the coating layer is 0.1 to 50 g / m 2 in terms of solid content.
前記有機質樹脂が、アクリル樹脂とウレタン樹脂、アクリルシリコン樹脂とウレタン樹脂、アクリル樹脂とエポキシ樹脂、アクリルシリコン樹脂とエポキシ樹脂、アクリル樹脂とバイオガム、及び、アクリルシリコン樹脂とバイオガムの組合せからなる群より選択される少なくとも1種の組み合わせであることを特徴とする請求項1記載の塗膜積層体。 The organic resin is selected from the group consisting of an acrylic resin and a urethane resin, an acrylic silicon resin and a urethane resin, an acrylic resin and an epoxy resin, an acrylic silicon resin and an epoxy resin, an acrylic resin and a biogum, and a combination of an acrylic silicon resin and a biogum. The coating layered product according to claim 1, wherein the coating layered product is at least one kind of combination . 前記被覆層を形成する被覆液の固形分濃度が、10重量%以下であることを特徴とする請求項1又は2に記載の塗膜積層体。The coating film laminate according to claim 1 or 2, wherein the coating liquid forming the coating layer has a solid concentration of 10% by weight or less. 前記有機樹脂が、異なる2種の樹脂を併用する場合において、In the case where the organic resin is used in combination of two different resins,
前記有機樹脂の一方の樹脂の固形分重量比が、他方の樹脂に対して、1/9未満であることを特徴とする請求項1〜3のいずれかに記載の塗膜積層体。The coating film laminate according to any one of claims 1 to 3, wherein a solid content weight ratio of one of the organic resins is less than 1/9 with respect to the other resin.
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