JP5208032B2 - Pattern surface forming method - Google Patents
Pattern surface forming method Download PDFInfo
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- JP5208032B2 JP5208032B2 JP2009080700A JP2009080700A JP5208032B2 JP 5208032 B2 JP5208032 B2 JP 5208032B2 JP 2009080700 A JP2009080700 A JP 2009080700A JP 2009080700 A JP2009080700 A JP 2009080700A JP 5208032 B2 JP5208032 B2 JP 5208032B2
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、新規な模様面形成方法に関するものである。 The present invention relates to a novel pattern surface forming method.
従来、建築物の壁面等では、基材の保護、美観性の向上等の目的で、塗装によって種々の凹凸模様を形成することが行われている。このような凹凸模様は、塗装時の器具の種類、使用方法等を適宜設定することで形成することができる。そして、塗装に供する被覆材については、構成成分として粉体成分を比較的多く含むものが用いられている。このような被覆材の使用により、凹凸模様の付与が容易となる。 2. Description of the Related Art Conventionally, on a wall surface of a building or the like, various uneven patterns are formed by painting for the purpose of protecting a base material and improving aesthetics. Such a concavo-convex pattern can be formed by appropriately setting the type of appliance at the time of painting, the method of use, and the like. And about the coating | covering material with which it uses for coating, what contains comparatively many powder components as a structural component is used. By using such a covering material, it becomes easy to provide a concavo-convex pattern.
しかしながら、上述のような被覆材では、粉体成分の含有比率が高くなれば、凹凸付与の点では有利であるが、その反面、塗膜に割れが生じやすくなる。特に形成塗膜の厚みが薄い凹部では、その傾向が強くなる。さらに、基材がシーリング目地部等を有するものである場合は、基材の変位によって塗膜の割れが引き起こされる可能性が高くなる。
また、上述のような被覆材では、形成塗膜の凸部における乾燥硬化が凹部に比べて遅く、耐水性等の塗膜物性発現に時間を要するという問題もある。
However, in the coating material as described above, if the content ratio of the powder component is high, it is advantageous in terms of imparting irregularities, but on the other hand, cracks are likely to occur in the coating film. In particular, the tendency becomes strong in the concave portion where the formed coating film is thin. Furthermore, when a base material has a sealing joint part etc., possibility that the crack of a coating film will be caused by the displacement of a base material becomes high.
In addition, the coating material as described above also has a problem that drying and curing at the convex portion of the formed coating film is slower than that of the concave portion, and it takes time to develop physical properties of the coating film such as water resistance.
凹凸模様を形成する方法として、特公平８−２９３００号公報（特許文献１）には、セメント系素地面に対し、下塗層を形成させた後、不燃可とう形多彩模様塗材をローラーで塗布して凹凸状多彩模様上塗層を形成させることが記載されている。この不燃可とう形多彩模様塗材については、その具体例としてガラス転移温度が０℃以下のアクリル系共重合樹脂エマルション、顔料、及び難燃剤等を含む塗材が記載されている。当該公報の技術では、ガラス転移温度の低いアクリル系共重合樹脂エマルションを採用することで、塗膜の割れ発生を抑制している。 As a method for forming a concavo-convex pattern, Japanese Patent Publication No. 8-29300 (Patent Document 1) discloses that a primer layer is formed on a cementitious substrate, and then a nonflammable flexible pattern coating material is applied with a roller. It is described that it is applied to form a concavo-convex multicolored pattern overcoat layer. As for the incombustible flexible pattern coating material, a coating material containing an acrylic copolymer resin emulsion having a glass transition temperature of 0 ° C. or less, a pigment, a flame retardant and the like is described as a specific example. In the technique of the publication, the occurrence of cracks in the coating film is suppressed by employing an acrylic copolymer resin emulsion having a low glass transition temperature.
しかしながら、上記特許文献のように、樹脂エマルションのガラス転移温度を単に低く設定するのみでは、塗膜表面における汚れ付着を誘発してしまうこととなる。特に凹凸模様面の凹部においては、汚れが溜まりやすく、一旦付着した汚れの除去も難しくなる。また、上記特許文献では、基材の変位に対する割れの問題や、被覆材の乾燥硬化性に起因する塗膜物性の問題について、何ら考慮されていない。 However, simply setting the glass transition temperature of the resin emulsion to be low as in the above-mentioned patent document will induce the adhesion of dirt on the coating film surface. In particular, in the concave portion of the concave / convex pattern surface, dirt tends to accumulate, and it is difficult to remove the dirt once adhered. In the above-mentioned patent documents, no consideration is given to the problem of cracking due to displacement of the substrate and the problem of physical properties of the coating film due to the dry curability of the coating material.
本発明は、上述のような問題点に鑑みなされたもので、基材に被覆材を塗付して凹凸模様面を形成する際、その形成塗膜の耐汚染性、耐割れ性、乾燥硬化性、耐水性等を高めることができる方法を提供す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. When a concavo-convex pattern surface is formed by applying a coating material to a base material, the formed coating film has stain resistance, crack resistance, and dry curing. It aims at providing the method which can improve property, water resistance, etc.
このような課題を解決するために本発明者らは、鋭意検討の結果、特定の合成樹脂エマルション、無機質粉体、及び有機溶剤を含む被覆材を用いて凹凸模様面を形成することに想到し、本発明を完成するに到った。 In order to solve such a problem, the present inventors, as a result of intensive studies, have conceived that a concavo-convex pattern surface is formed using a coating material containing a specific synthetic resin emulsion, an inorganic powder, and an organic solvent. 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．基材に対し、被覆材を塗付して凹凸模様面を形成する模様面形成方法であって、
前記被覆材として、
アルキル基の炭素数が１〜６である（メタ）アクリル酸アルキルエステル５０〜９５重量％、アルキル基の炭素数が７以上である（メタ）アクリル酸アルキルエステル０〜４５重量％、及びシロキサン化合物５〜５０重量％を樹脂構成成分とする合成樹脂エマルション（Ａ）、
平均粒子径５０μｍ以下の無機質粉体（Ｂ）、並びに、
酢酸ブチルを１００としたときの蒸発速度が２〜５０、水への溶解度が２〜８０ｇ／１００ｇである有機溶剤（Ｃ）を含み、
前記合成樹脂エマルション（Ａ）の固形分１００重量部に対し、前記無機質粉体（Ｂ）を２００〜１０００重量部、前記有機溶剤（Ｃ）を１〜５０重量部含む水性被覆材を用いることを特徴とする模様面形成方法。
That is, the present invention has the following characteristics.
1. A pattern surface forming method for forming a concavo-convex pattern surface by applying a coating material to a base material,
As the covering material,
(Meth) acrylic acid alkyl ester having 1 to 6 carbon atoms of alkyl group, 50 to 95% by weight, (meth) acrylic acid alkyl ester having 7 or more carbon atoms in alkyl group, 0 to 45% by weight, and siloxane compound A synthetic resin emulsion (A) containing 5 to 50% by weight of a resin component,
Inorganic powder (B) having an average particle size of 50 μm or less, and
An organic solvent (C) having an evaporation rate of 2 to 50 and a solubility in water of 2 to 80 g / 100 g based on butyl acetate as 100,
Using an aqueous coating material containing 200 to 1000 parts by weight of the inorganic powder (B) and 1 to 50 parts by weight of the organic solvent (C) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (A). A method for forming a patterned surface.
本発明によれば、凹凸模様面における耐汚染性、耐割れ性、乾燥硬化性、耐水性等を高めることができる。 According to the present invention, the stain resistance, crack resistance, dry curability, water resistance, etc. on the concavo-convex pattern surface can be enhanced.
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明は、基材に対し、特定の被覆材を塗付して凹凸模様面を形成する方法に関するものである。
このうち、基材は、建築物、土木構造物等において使用可能なものであればよい。このような基材としては、例えば、コンクリート、モルタル、スレート板、珪酸カルシウム板、ＡＬＣ板、押出成型板、スレート瓦、セメント瓦、新生瓦、磁器タイル、サイディングボード、金属板、合板等が挙げられる。これら基材は、何らかの表面処理（シーラー、サーフェーサー、フィラー、パテ等）が施されたものであってもよく、既存塗膜等を有するものであってもよい。
The present invention relates to a method for forming a concavo-convex pattern surface by applying a specific coating material to a substrate.
Among these, a base material should just be usable in a building, a civil engineering structure, etc. Examples of such a base material include concrete, mortar, slate plate, calcium silicate plate, ALC plate, extruded plate, slate tile, cement tile, new roof tile, porcelain tile, siding board, metal plate, plywood and the like. It is done. These base materials may have been subjected to some surface treatment (sealer, surfacer, filler, putty, etc.), or may have an existing coating film.
本発明では、塗装対象となる基材がシーリング材を有する場合に、特に有利な効果を得ることができる。このような基材は、各種基材によって形成され、その目地部や補修部等にシーリング材が充填された面である。
シーリング材としては、例えば、シリコーン系シーリング材、変性シリコーン系シーリング材、ポリサルファイド系シーリング材、変性ポリサルファイド系シーリング材、アクリルウレタン系シーリング材、ポリウレタン系シーリング材、ＳＢＲ系シーリング材、ブチルゴム系シーリング材等が挙げられる。これらは一成分形、二成分形のいずれであってもよい。
In the present invention, particularly advantageous effects can be obtained when the base material to be coated has a sealing material. Such a base material is a surface that is formed of various base materials, and the joint portion, the repair portion, or the like is filled with a sealing material.
Examples of sealing materials include silicone-based sealing materials, modified silicone-based sealing materials, polysulfide-based sealing materials, modified polysulfide-based sealing materials, acrylic urethane-based sealing materials, polyurethane-based sealing materials, SBR-based sealing materials, and butyl rubber-based sealing materials. Is mentioned. These may be either a one-component form or a two-component form.
本発明における被覆材は、それぞれ特定の合成樹脂エマルション（Ａ）、無機質粉体（Ｂ）、有機溶剤（Ｃ）を必須成分とするものである。
このうち、合成樹脂エマルション（Ａ）は、アルキル基の炭素数が１〜６である（メタ）アクリル酸アルキルエステル５０〜９５重量％、アルキル基の炭素数が７以上である（メタ）アクリル酸アルキルエステル０〜４５重量％、及びシロキサン化合物５〜５０重量％を樹脂構成成分とする合成樹脂エマルション（Ａ）（以下「（Ａ）成分」という）である。本発明では、このような合成樹脂エマルションと、後述の無機質粉体、有機溶剤を組み合わせて用いることにより、凹凸模様を有する塗膜が容易に形成できるとともに、耐汚染性、耐割れ性、乾燥硬化性、耐水性等において優れた効果を発揮することができる。
The covering material in the present invention contains a specific synthetic resin emulsion (A), inorganic powder (B), and organic solvent (C) as essential components.
Of these, the synthetic resin emulsion (A) is a (meth) acrylic acid alkyl ester having 1 to 6 carbon atoms in the alkyl group of 50 to 95% by weight and a (meth) acrylic acid in which the alkyl group has 7 or more carbon atoms. It is a synthetic resin emulsion (A) (hereinafter referred to as “component (A)”) having 0 to 45% by weight of an alkyl ester and 5 to 50% by weight of a siloxane compound as a resin constituent component. In the present invention, by using such a synthetic resin emulsion in combination with an inorganic powder and an organic solvent described later, a coating film having a concavo-convex pattern can be easily formed, as well as stain resistance, crack resistance, and dry curing. The effect which was excellent in property, water resistance, etc. can be exhibited.
アルキル基の炭素数が１〜６である（メタ）アクリル酸アルキルエステル（以下「（ａ−１）成分」という）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、２−エチルブチル（メタ）アクリレート、ｎ−へキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。
本発明では、このような（メタ）アクリル酸アルキルエステルを２種以上組合せて用いることが望ましい。さらには、アルキル基の炭素数が１〜２である（メタ）アクリル酸アルキルエステルの１種以上と、アルキル基の炭素数が３〜６である（メタ）アクリル酸アルキルエステルの１種以上を組合せて用いることが望ましい。なお、本発明では、アクリル酸アルキルエステルとメタクリル酸アルキルエステルを合わせて、（メタ）アクリル酸アルキルエステルと表記する。
（Ａ）成分の樹脂成分中に占める（ａ−１）成分の比率は、通常５０〜９５重量％、好ましくは５５〜８０重量％である。（ａ−１）成分の比率が上記比率よりも低すぎる場合は、耐汚染性、乾燥硬化性、耐水性等において、十分な物性が得られ難くなる。（ａ−１）成分の比率が上記比率よりも高すぎる場合は、耐割れ性の点で不利となる。
Examples of the (meth) acrylic acid alkyl ester having 1 to 6 carbon atoms in the alkyl group (hereinafter referred to as “component (a-1)”) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl. (Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (Meth) acrylate, 2-ethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be mentioned.
In the present invention, it is desirable to use a combination of two or more such (meth) acrylic acid alkyl esters. Furthermore, 1 or more types of the (meth) acrylic acid alkyl ester whose carbon number of an alkyl group is 1-2, and 1 or more types of the (meth) acrylic acid alkyl ester whose carbon number of an alkyl group is 3-6. It is desirable to use in combination. In the present invention, the acrylic acid alkyl ester and the methacrylic acid alkyl ester are collectively referred to as (meth) acrylic acid alkyl ester.
The proportion of the component (a-1) in the resin component (A) is usually 50 to 95% by weight, preferably 55 to 80% by weight. When the ratio of the component (a-1) is too lower than the above ratio, it is difficult to obtain sufficient physical properties in terms of contamination resistance, dry curability, water resistance, and the like. (A-1) When the ratio of a component is too higher than the said ratio, it becomes disadvantageous at the point of crack resistance.
アルキル基の炭素数が７以上である（メタ）アクリル酸アルキルエステル（以下「（ａ−２）成分」という）としては、例えば、ｎ−ヘプチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、ｎ−テトラデシル（メタ）アクリレート、ｎ−ヘキサデシル（メタ）アクリレート、ｎ−オクタデシル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。
（Ａ）成分の樹脂成分中に占める（ａ−２）成分の比率は、通常０〜４５重量％、好ましくは５〜３０重量％である。（ａ−２）成分の比率が上記比率よりも高すぎる場合は、耐汚染性、乾燥硬化性、耐水性等において、十分な物性が得られ難くなる。
Examples of the (meth) acrylic acid alkyl ester (hereinafter referred to as “component (a-2)”) having 7 or more carbon atoms in the alkyl group include n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n- Examples include octadecyl (meth) acrylate and stearyl (meth) acrylate.
The ratio of the component (a-2) in the resin component (A) is usually 0 to 45% by weight, preferably 5 to 30% by weight. When the ratio of the component (a-2) is too higher than the above ratio, it is difficult to obtain sufficient physical properties in terms of contamination resistance, dry curability, water resistance, and the like.
（Ａ）成分におけるシロキサン化合物（以下「（ａ−３）成分」という）は、重合によりシリコーン樹脂を生成するものである。シロキサン化合物としては、例えば一般式ＲｎＳｉＯ（４−ｎ）／２（式中Ｒは炭化水素基、ｎ＝０〜３）で表される構造単位を有するものが挙げられる。このような化合物としては、直鎖状シロキサン化合物、分岐状シロキサン化合物、環状シロキサン化合物等が挙げられ、このうち環状シロキサン化合物が好適である。環状シロキサン化合物としては、例えばヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等が挙げられる。このような環状シロキサン化合物を重合する際には、直鎖状シロキサン化合物、分岐状シロキサン化合物、アルコキシシラン化合物等を用いることもでき、重合用の触媒を適宜用いることもできる。このうち、アルコキシシラン化合物としては、分子中に１個以上のアルコキシル基を有するシラン化合物が使用でき、例えばテトラメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン等の他、ビニルメチルジメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン等のシランカップリング剤等が使用できる。環状シロキサン化合物を重合する際、このようなアルコキシシラン化合物を併用することにより、（Ａ）成分中における（ａ−３）成分の結合が強固となり、耐水性等の塗膜物性向上の点で有利である。
（Ａ）成分の樹脂成分中に占める（ａ−３）成分の比率は、通常５〜５０重量％、好ましくは１５〜４０重量％である。（ａ−３）成分の比率が上記比率よりも低すぎる場合は、耐汚染性、耐割れ性等において、十分な物性が得られ難くなる。（ａ−３）成分が上記比率よりも高すぎる場合は、耐汚染性、乾燥硬化性、耐水性等が不十分となるおそれがある。
The siloxane compound (hereinafter referred to as “component (a-3)”) in component (A) generates a silicone resin by polymerization. Examples of the siloxane compound include those having a structural unit represented by a general formula R n SiO (4-n) / 2 (wherein R is a hydrocarbon group, n = 0 to 3). Examples of such a compound include a linear siloxane compound, a branched siloxane compound, a cyclic siloxane compound, and the like, among which a cyclic siloxane compound is preferable. Examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. When such a cyclic siloxane compound is polymerized, a linear siloxane compound, a branched siloxane compound, an alkoxysilane compound, or the like can be used, and a polymerization catalyst can be appropriately used. Of these, as the alkoxysilane compound, a silane compound having one or more alkoxyl groups in the molecule can be used. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ- Silane coupling agents such as (meth) acryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be used. When the cyclic siloxane compound is polymerized, by using such an alkoxysilane compound in combination, the bond of the component (a-3) in the component (A) is strengthened, which is advantageous in terms of improving the properties of the coating film such as water resistance. It is.
The ratio of the component (a-3) in the resin component (A) is usually 5 to 50% by weight, preferably 15 to 40% by weight. When the ratio of the component (a-3) is too lower than the above ratio, it is difficult to obtain sufficient physical properties in terms of contamination resistance, crack resistance, and the like. (A-3) When a component is too higher than the said ratio, there exists a possibility that stain resistance, dry curability, water resistance, etc. may become inadequate.
（Ａ）成分においては、上記以外のビニル系モノマーを使用することもできる。このようなビニル系モノマーとしては、例えば、カルボキシル基含有モノマー、アミノ基含有モノマー、水酸基含有モノマー、ニトリル基含有モノマー、アミド基含有モノマー、エポキシ基含有モノマー、カルボニル基含有モノマー、アルコキシシリル基含有モノマー、芳香族モノマー、ハロゲン化ビニリデン系モノマー、その他エチレン、プロピレン、イソプレン、ブタジエン、ビニルピロリドン、塩化ビニル、ビニルエーテル、ビニルケトン、ビニルアミド、クロロプレン等が挙げられる。 In the component (A), vinyl monomers other than those described above can also be used. Examples of such vinyl monomers include carboxyl group-containing monomers, amino group-containing monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, and alkoxysilyl group-containing monomers. , Aromatic monomers, vinylidene halide monomers, ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, chloroprene, and the like.
（Ａ）成分の製造方法は特に限定されないが、例えば、乳化重合、ソープフリー乳化重合、分散重合、フィード乳化重合、フィード分散重合、シード乳化重合、シード分散重合等を採用することができる。（Ａ）成分の平均粒子径は、通常０．０５〜０．３μｍ程度である。 Although the manufacturing method of (A) component is not specifically limited, For example, emulsion polymerization, soap free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, seed dispersion polymerization, etc. are employable. (A) The average particle diameter of a component is about 0.05-0.3 micrometer normally.
本発明における（Ｂ）成分は、平均粒子径５０μｍ以下の無機質粉体（Ｂ）（以下「（Ｂ）成分」という）である。（Ｂ）成分としては、平均粒子径が５０μｍ以下の範囲内にあるものであれば、その種類については特に限定されず、各種無機質粉体を使用することができる。（Ｂ）成分としては、例えば、重質炭酸カルシウム、沈降性炭酸カルシウム、カオリン、タルク、クレー、陶土、チャイナクレー、硫酸バリウム、炭酸バリウム、珪砂、珪石、珪藻土、酸化チタン、酸化亜鉛、酸化アルミニウム、酸化鉄等が挙げられ、これらの１種または２種以上を使用することができる。
平均粒子径が５０μｍより大きい場合は、凹凸模様面の仕上り性が低下してしまう。（Ｂ）成分の好適な平均粒子径は０．１〜４０μｍ（より好ましくは０．２〜３０μｍ）である。
The component (B) in the present invention is an inorganic powder (B) (hereinafter referred to as “component (B)”) having an average particle size of 50 μm or less. The component (B) is not particularly limited as long as it has an average particle size in the range of 50 μm or less, and various inorganic powders can be used. Examples of the component (B) include heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, porcelain clay, China clay, barium sulfate, barium carbonate, quartz sand, quartzite, diatomaceous earth, titanium oxide, zinc oxide, and aluminum oxide. Iron oxide and the like, and one or more of these can be used.
When the average particle diameter is larger than 50 μm, the finish of the concavo-convex pattern surface is lowered. The suitable average particle diameter of (B) component is 0.1-40 micrometers (preferably 0.2-30 micrometers).
（Ｂ）成分の混合量は、上記（Ａ）成分の固形分１００重量部に対し、通常２００〜１０００重量部、好ましくは３００〜８００重量部である。このような混合量であれば、凹凸模様面を容易に形成することが可能となる。（Ｂ）成分の混合量が少なすぎる場合は、凹凸模様を付与することが困難となる。また、塗膜の強度が低下するおそれもある。（Ｂ）成分の混合量が多すぎる場合は、耐割れ性、耐水性等が不十分となりやすくなる。 The mixing amount of the component (B) is usually 200 to 1000 parts by weight, preferably 300 to 800 parts by weight with respect to 100 parts by weight of the solid content of the component (A). With such a mixing amount, it is possible to easily form a concavo-convex pattern surface. When the mixing amount of the component (B) is too small, it becomes difficult to provide a concavo-convex pattern. Moreover, there exists a possibility that the intensity | strength of a coating film may fall. When the amount of component (B) is too large, crack resistance, water resistance, etc. tend to be insufficient.
本発明の被覆材では、上記成分に加え、酢酸ブチルを１００としたときの蒸発速度（以下単に「蒸発速度」という）が２〜５０、水への溶解度が２〜８０ｇ／１００ｇである有機溶剤（Ｃ）（以下「（Ｃ）成分」という）を必須成分とする。本発明では、上記成分と（Ｃ）成分を組み合わせて用いることにより、耐汚染性、耐割れ性、乾燥硬化性、耐水性等において優れた効果を得ることができる。このような効果は、（Ｃ）成分が、塗膜形成時において（Ａ）成分の造膜性向上に作用するとともに、塗膜形成後は塗膜内にほとんど残存しないことにより奏されるものと推察される。 In the coating material of the present invention, in addition to the above components, an organic solvent having an evaporation rate (hereinafter simply referred to as “evaporation rate”) of 2 to 50 and a solubility in water of 2 to 80 g / 100 g when butyl acetate is 100 (C) (hereinafter referred to as “component (C)”) is an essential component. In the present invention, by using a combination of the above components and the component (C), excellent effects in stain resistance, crack resistance, dry curability, water resistance and the like can be obtained. Such an effect is achieved by the fact that the component (C) acts to improve the film forming property of the component (A) at the time of coating film formation, and hardly remains in the coating film after the coating film is formed. Inferred.
（Ｃ）成分の蒸発速度は通常２〜５０、好ましくは３〜３０、より好ましくは５〜２０である。（Ｃ）成分の蒸発速度が小さすぎる場合は、耐汚染性、乾燥硬化性、耐水性等において十分な性能が得られにくくなる。（Ｃ）成分の蒸発速度が大きすぎる場合は、造膜性、耐割れ性等が不十分となりやすくなる。なお、本発明の蒸発速度は、酢酸ブチルの蒸発速度を１００としたときの相対値であり、測定温度は２０℃である。 The evaporation rate of the component (C) is usually 2 to 50, preferably 3 to 30, and more preferably 5 to 20. When the evaporation rate of the component (C) is too small, it is difficult to obtain sufficient performance in terms of contamination resistance, dry curability, water resistance, and the like. When the evaporation rate of the component (C) is too high, the film forming property, crack resistance, etc. tend to be insufficient. In addition, the evaporation rate of this invention is a relative value when the evaporation rate of butyl acetate is set to 100, and measurement temperature is 20 degreeC.
（Ｃ）成分の水への溶解度（以下単に「溶解度」ともいう）は、通常２〜８０ｇ／１００ｇ、好ましくは３〜５０ｇ／１００ｇ、より好ましくは４〜３０ｇ／１００ｇである。（Ｃ）成分の溶解度が小さすぎる場合は、耐汚染性、乾燥硬化性、耐水性等において十分な性能が得られにくくなる。（Ｃ）成分の溶解度が大きすぎる場合は、造膜性、耐割れ性等が不十分となりやすくなる。なお、本発明の溶解度は、水１００ｇに対し溶解可能な有機溶剤の質量であり、測定温度は２０℃である。 The solubility of the component (C) in water (hereinafter also simply referred to as “solubility”) is usually 2 to 80 g / 100 g, preferably 3 to 50 g / 100 g, more preferably 4 to 30 g / 100 g. When the solubility of the component (C) is too small, it becomes difficult to obtain sufficient performance in terms of contamination resistance, dry curability, water resistance, and the like. When the solubility of the component (C) is too large, the film forming property, crack resistance, etc. tend to be insufficient. In addition, the solubility of this invention is the mass of the organic solvent which can be melt | dissolved with respect to 100 g of water, and measurement temperature is 20 degreeC.
本発明における（Ｃ）成分としては、例えば、ジプロピレングリコールジメチルエーテル（蒸発速度１６、溶解度５３）、エチレングリコールモノエチルエーテルアセテート（蒸発速度２１、溶解度２３）、プロピレングリコールモノメチルエーテルアセテート（蒸発速度３４、溶解度１６）、メチル−１，３−ブチレングリコールアセテート（蒸発速度３４、溶解度７）、３−メトキシ−３−メチル−１−ブチルアセテート（蒸発速度１０、溶解度７）、プロピレングリコールｎ−ブチルエーテル（蒸発速度９、溶解度６）等が挙げられる。 Examples of the component (C) in the present invention include dipropylene glycol dimethyl ether (evaporation rate 16, solubility 53), ethylene glycol monoethyl ether acetate (evaporation rate 21, solubility 23), propylene glycol monomethyl ether acetate (evaporation rate 34, Solubility 16), methyl-1,3-butylene glycol acetate (evaporation rate 34, solubility 7), 3-methoxy-3-methyl-1-butyl acetate (evaporation rate 10, solubility 7), propylene glycol n-butyl ether (evaporation) Speed 9 and solubility 6).
（Ｃ）成分の混合量は、（Ａ）成分の固形分１００重量部に対し、通常１〜５０重量部、好ましくは２〜４５重量部、より好ましくは５〜４０重量部である。（Ｃ）成分の混合量が少なすぎる場合は、耐割れ性、乾燥硬化性、耐水性等が不十分となるおそれがある。（Ｃ）成分の混合量が多すぎる場合は、被覆材の安定性が阻害されるおそれがあり、実用的ではない。 The mixing amount of the component (C) is usually 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the solid content of the component (A). When the amount of component (C) is too small, crack resistance, dry curability, water resistance and the like may be insufficient. When the amount of component (C) is too large, the stability of the coating material may be impaired, which is not practical.
本発明では、上記成分に加え、水への溶解度が１ｇ／１００ｇ未満である有機溶剤（Ｄ）（以下「（Ｄ）成分」という）を用いることができる。但し、その混合比率は、重量比率において、（Ｄ）成分／（Ｃ）成分が５以下（好ましくは０．１以上３以下、より好ましくは０．２以上２以下）となる範囲内にする。このような範囲内であれば、（Ｃ）成分による作用を活かしつつ、本発明の効果を高めることができる。
（Ｄ）成分としては、例えば、ジエチレングリコールモノ２−エチルヘキシルエーテル、ジエチレングリコールジブチルエーテル、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、２，２，４−トリメチル−１，３−ペンタンジオールジイソブチレート等が挙げられる。
In the present invention, in addition to the above components, an organic solvent (D) having a solubility in water of less than 1 g / 100 g (hereinafter referred to as “component (D)”) can be used. However, the mixing ratio is within the range where the (D) component / (C) component is 5 or less (preferably 0.1 or more and 3 or less, more preferably 0.2 or more and 2 or less) in weight ratio. If it is in such a range, the effect of this invention can be heightened, utilizing the effect | action by (C) component.
Examples of the component (D) include diethylene glycol mono 2-ethylhexyl ether, diethylene glycol dibutyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3. -Pentanediol diisobutyrate and the like.
本発明の被覆材には、上記成分以外に、着色顔料、体質顔料、骨材、可塑剤、凍結防止剤、防腐剤、防黴剤、抗菌剤、消泡剤、顔料分散剤、増粘剤、レベリング剤、湿潤剤、ｐＨ調整剤、繊維類、つや消し剤、紫外線吸収剤、酸化防止剤、光安定剤、吸着剤、触媒、架橋剤等を混合することができ、このような成分を適宜組み合わせて使用することにより、種々の形態の被覆材を設計することができる。本発明の被覆材は、前述の成分に加え、必要に応じこれら成分を常法により均一に混合することで製造できる。 In addition to the above components, the coating material of the present invention includes coloring pigments, extender pigments, aggregates, plasticizers, antifreezing agents, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, pigment dispersants, thickeners. , Leveling agents, wetting agents, pH adjusting agents, fibers, matting agents, UV absorbers, antioxidants, light stabilizers, adsorbents, catalysts, cross-linking agents, etc. By using in combination, various forms of coating materials can be designed. The coating material of the present invention can be produced by uniformly mixing these components by a conventional method, if necessary, in addition to the aforementioned components.
上記被覆材の塗装においては、塗装器具の種類とその使用方法を適宜選定することで、種々の凹凸模様、例えば砂壁状、ゆず肌状、繊維壁状、さざ波状、スタッコ状、凹凸状、月面状、櫛引状、虫喰状等の模様を形成することができる。塗装器具としては、例えば、スプレー、ローラー、コテ等が使用できる。この際、被覆材が乾燥するまでに塗面をデザインローラー、コテ、刷毛、櫛、へら等で処理することで、種々の凹凸模様を形成させることもできる。目地棒や目地型枠等の使用によって、タイル調模様、幾何学的模様等を形成させることもできる。また、色彩の異なる２種以上の塗材を組み合わせて多色模様を形成することも可能である。凹凸模様の高低差は、概ね０．２〜５ｍｍの範囲内で適宜設定すればよい。 In the coating of the above-mentioned coating material, various uneven patterns such as sand wall, yuzu skin, fiber wall, ripple, stucco, uneven, moon Patterns such as a planar shape, a comb-like shape, and an insect-like shape can be formed. For example, a spray, a roller, a trowel, or the like can be used as the coating instrument. At this time, various uneven patterns can be formed by treating the coated surface with a design roller, a trowel, a brush, a comb, a spatula or the like until the coating material is dried. Tile patterns, geometric patterns, etc. can be formed by using joint rods or joint molds. It is also possible to form a multicolor pattern by combining two or more kinds of coating materials having different colors. What is necessary is just to set the height difference of an uneven | corrugated pattern suitably in the range of 0.2-5 mm in general.
上記被覆材の塗付け量は、形成される模様の種類等にもよるが、通常０．１〜４ｋｇ／ｍ２、好ましくは０．２〜３ｋｇ／ｍ２程度である。このような塗付け量の範囲内で、複数回に分けて塗分けることも可能である。塗付時には水等の希釈剤を混合して、塗材の粘性を適宜調製することもできる。希釈割合は、通常０〜１０重量％程度である。
塗装及びその後の乾燥は、通常、常温（０〜４０℃）で行えばよい。
Coating with the amount of the coating material, depending on the kind of pattern to be formed, usually 0.1~4kg / m 2, preferably 0.2~3kg / m 2 approximately. Within such a range of coating amount, it is possible to divide the coating into a plurality of times. At the time of application, a diluent such as water can be mixed to appropriately adjust the viscosity of the coating material. The dilution ratio is usually about 0 to 10% by weight.
The coating and subsequent drying may be usually performed at room temperature (0 to 40 ° C.).
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.
＜被覆材の製造＞
表１に示す配合に従い、常法により各原料を均一に混合して被覆材を製造した。表１において、各原料の混合比率は、重量部にて示した。なお、各被覆材における原料としては、以下に示すものを使用した。
<Manufacture of coating material>
According to the formulation shown in Table 1, each raw material was uniformly mixed by a conventional method to produce a coating material. In Table 1, the mixing ratio of each raw material is shown in parts by weight. In addition, what was shown below was used as a raw material in each coating | covering material.
・合成樹脂エマルション１（固形分：５０重量％、樹脂構成成分：メチルメタクリレート，ｔ−ブチルメタクリレート，ｎ−ブチルアクリレート，２−エチルヘキシルアクリレート，シロキサン化合物（ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン）及びメタクリル酸の乳化重合物（重量比率２５：１６：２０：１５：２１：３））
・合成樹脂エマルション２（固形分：５０重量％、樹脂構成成分：メチルメタクリレート，ｔ−ブチルメタクリレート，ｎ−ブチルアクリレート，２−エチルヘキシルアクリレート，シロキサン化合物（ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン）及びメタクリル酸の乳化重合物（重量比率２５：２０：２４：１８：１０：３））
・合成樹脂エマルション３（固形分：５０重量％、樹脂構成成分：メチルメタクリレート，ｔ−ブチルメタクリレート，ｎ−ブチルアクリレート，２−エチルヘキシルアクリレート，シロキサン化合物（ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン）及びメタクリル酸の乳化重合物（重量比率２５：２０：２：４８：２：３））
・合成樹脂エマルション４（固形分：５０重量％、樹脂構成成分：メチルメタクリレート，ｔ−ブチルメタクリレート，ｎ−ブチルアクリレート，２−エチルヘキシルアクリレート，シロキサン化合物（ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン）及びメタクリル酸の乳化重合物（重量比率３１：２０：２５：１９：２：３））
・合成樹脂エマルション５（固形分：５０重量％、樹脂構成成分：メチルメタクリレート，ｔ−ブチルメタクリレート，ｎ−ブチルアクリレート，２−エチルヘキシルアクリレート，シロキサン化合物（ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン）及びメタクリル酸の乳化重合物（重量比率１８：１１：１２：４６：１０：３））
Synthetic resin emulsion 1 (solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 25: 16: 20: 15: 21: 3))
Synthetic resin emulsion 2 (solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 25: 20: 24: 18: 10: 3))
Synthetic resin emulsion 3 (solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 25: 20: 2: 48: 2: 3))
Synthetic resin emulsion 4 (solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 31: 20: 25: 19: 2: 3))
Synthetic resin emulsion 5 (solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 18: 11: 12: 46: 10: 3))
・無機質粉体１：炭酸カルシウム（平均粒子径２μｍ）
・無機質粉体２：酸化チタン（平均粒子径０．３μｍ）
・有機溶剤１：ジプロピレングリコールジメチルエーテル（蒸発速度１６、溶解度５３）
・有機溶剤２：３−メトキシ−３−メチル−１−ブチルアセテート（蒸発速度１０、溶解度７）
・有機溶剤３：プロピレングリコールｎ−ブチルエーテル（蒸発速度９、溶解度６）
・有機溶剤４：２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート（蒸発速度０．２、溶解度＜１）
・有機溶剤５：エチレングリコールモノブチルエーテル（蒸発速度８、溶解度∞）
・有機溶剤６：ジエチレングリコールモノブチルエーテル（蒸発速度＜１、溶解度∞）
・有機溶剤７：トリプロピレングリコールｎ−ブチルエーテル（蒸発速度＜１、溶解度３）
・増粘剤：ポリウレタン系増粘剤
・消泡剤：シリコーン系消泡剤
・ Inorganic powder 1: Calcium carbonate (average particle size 2μm)
Inorganic powder 2: Titanium oxide (average particle size 0.3 μm)
Organic solvent 1: Dipropylene glycol dimethyl ether (evaporation rate 16, solubility 53)
Organic solvent 2: 3-methoxy-3-methyl-1-butyl acetate (evaporation rate 10, solubility 7)
Organic solvent 3: propylene glycol n-butyl ether (evaporation rate 9, solubility 6)
Organic solvent 4: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (evaporation rate 0.2, solubility <1)
Organic solvent 5: ethylene glycol monobutyl ether (evaporation rate 8, solubility ∞)
Organic solvent 6: Diethylene glycol monobutyl ether (evaporation rate <1, solubility ∞)
Organic solvent 7: tripropylene glycol n-butyl ether (evaporation rate <1, solubility 3)
・ Thickener: Polyurethane thickener ・ Defoamer: Silicone defoamer
＜試験方法＞
（１）耐水性試験
シーラー処理を施したスレート板（縦３００×横１５０×厚さ６ｍｍ）に対し、多孔質ローラーを用いて各被覆材を塗付け量０．８ｋｇ／ｍ２でさざ波状に塗付し、温度５℃、相対湿度５０％の環境下で１２時間乾燥させることにより、試験板を作製した。以上の方法で得られた試験板を、水中に３時間浸漬した後、その表面状態を観察した。評価は、膨れ、剥れ等の異常が認められなかったものを「Ａ」、異常が認められたものを「Ｃ」とする３段階（優Ａ＞Ｂ＞Ｃ劣）にて行った。
<Test method>
(1) Water resistance test On a slate plate (length 300 x width 150 x thickness 6 mm) that has been subjected to a sealer treatment, each coating material is rippled in a coating amount of 0.8 kg / m 2 using a porous roller. The test plate was prepared by applying and drying for 12 hours in an environment of a temperature of 5 ° C. and a relative humidity of 50%. The test plate obtained by the above method was immersed in water for 3 hours, and then its surface state was observed. The evaluation was performed in three stages (excellent A>B> C inferior), with “A” indicating no abnormality such as swelling and peeling, and “C” indicating that abnormality was observed.
（２）耐割れ性試験
シーラー処理を施したスレート板（縦１５０×横７０×厚さ６ｍｍ）の横中央部に切り目を入れたものを試験基材として用いた。この試験基材に対し、多孔質ローラーを用いて各被覆材を塗付け量０．８ｋｇ／ｍ２でさざ波状に塗付し、１４日間養生した。なお、試験板の作製・養生はすべて標準状態（気温２３℃・相対湿度５０％）で行った。また、上下の各端部２０ｍｍは無塗装の状態とした。
以上の方法で得られた試験板について、引張試験機を用いて耐割れ性を評価した。評価は、試験基材を１．５ｍｍ引張ったときに異常が認められなかったものを「Ａ」、試験基材を１．０ｍｍ引張ったときに異常が認められなかったものを「Ｂ」、試験基材を０．５ｍｍ引張ったときにひび割れが認められたものを「Ｃ」として行った。
(2) Crack resistance test A slate plate (vertical 150 × horizontal 70 × thickness 6 mm) subjected to a sealer treatment was used as a test substrate with a notch in the horizontal center. Each coating material was applied to the test base material in a rippled manner at a coating amount of 0.8 kg / m 2 using a porous roller, followed by curing for 14 days. The test plates were all prepared and cured in standard conditions (temperature 23 ° C., relative humidity 50%). The upper and lower end portions 20 mm were not coated.
The test plate obtained by the above method was evaluated for crack resistance using a tensile tester. The evaluation was “A” when no abnormality was observed when the test substrate was pulled 1.5 mm, and “B” when no abnormality was observed when the test substrate was pulled 1.0 mm. The case where cracks were observed when the substrate was pulled 0.5 mm was designated as “C”.
（３）耐汚染性試験
シーラー処理を施したスレート板（縦３００×横１５０×厚さ６ｍｍ）に対し、多孔質ローラーを用いて各被覆材を塗付け量０．８ｋｇ／ｍ２でさざ波状に塗付し、標準状態で１４日間養生した。以上の方法で得られた試験板を、大阪府茨木市で３ヶ月間屋外曝露した後、その表面状態を観察した。評価は、汚れの程度が軽微であったものを「Ａ」、汚れの程度が著しかったものを「Ｃ」とする３段階（優Ａ＞Ｂ＞Ｃ劣）にて行った。
(3) Contamination resistance test A slate plate (length 300 x width 150 x thickness 6 mm) subjected to a sealer treatment was coated in a ripple shape with a coating amount of 0.8 kg / m 2 using a porous roller. And applied for 14 days under standard conditions. The test plate obtained by the above method was exposed outdoors in Ibaraki City, Osaka Prefecture for 3 months, and then its surface condition was observed. The evaluation was performed in three stages (excellent A>B> C inferior), with “A” indicating that the degree of contamination was slight and “C” indicating that the degree of contamination was significant.
＜試験結果＞
試験結果を表１に示す。実施例１〜５では、いずれの試験においても良好な結果を得ることができた。
<Test results>
The test results are shown in Table 1. In Examples 1 to 5, good results could be obtained in any test.
Claims (1)
前記被覆材として、
アルキル基の炭素数が１〜６である（メタ）アクリル酸アルキルエステル５０〜９５重量％、アルキル基の炭素数が７以上である（メタ）アクリル酸アルキルエステル０〜４５重量％、及びシロキサン化合物５〜５０重量％を樹脂構成成分とする合成樹脂エマルション（Ａ）、
平均粒子径５０μｍ以下の無機質粉体（Ｂ）、並びに、
酢酸ブチルを１００としたときの蒸発速度が２〜５０、水への溶解度が２〜８０ｇ／１００ｇである有機溶剤（Ｃ）を含み、
前記合成樹脂エマルション（Ａ）の固形分１００重量部に対し、前記無機質粉体（Ｂ）を２００〜１０００重量部、前記有機溶剤（Ｃ）を１〜５０重量部含む水性被覆材を用いることを特徴とする模様面形成方法。
A pattern surface forming method for forming a concavo-convex pattern surface by applying a coating material to a base material,
As the covering material,
(Meth) acrylic acid alkyl ester having 1 to 6 carbon atoms of alkyl group, 50 to 95% by weight, (meth) acrylic acid alkyl ester having 7 or more carbon atoms in alkyl group, 0 to 45% by weight, and siloxane compound A synthetic resin emulsion (A) containing 5 to 50% by weight of a resin component,
Inorganic powder (B) having an average particle size of 50 μm or less, and
An organic solvent (C) having an evaporation rate of 2 to 50 and a solubility in water of 2 to 80 g / 100 g based on butyl acetate as 100,
Using an aqueous coating material containing 200 to 1000 parts by weight of the inorganic powder (B) and 1 to 50 parts by weight of the organic solvent (C) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (A). A method for forming a patterned surface.
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