JP4174314B2 - Painted body - Google Patents
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- JP4174314B2 JP4174314B2 JP2002370689A JP2002370689A JP4174314B2 JP 4174314 B2 JP4174314 B2 JP 4174314B2 JP 2002370689 A JP2002370689 A JP 2002370689A JP 2002370689 A JP2002370689 A JP 2002370689A JP 4174314 B2 JP4174314 B2 JP 4174314B2
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- Prior art keywords
- coating film
- paint
- base material
- inorganic
- organic coating
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- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Description
【0001】
【発明の属する技術分野】
この出願の発明は塗装体に関するものである。さらに詳しくは、この出願の発明は、建材等として有用な無機質窯業系基材の表面に塗装を施した塗装体において、長期耐久性、外観性が良好であるとともに塗膜密着性に優れた新しい塗装体に関するものである。
【0002】
【従来の技術】
従来、屋根瓦や外装材、あるいは内装材等の建築材等においては、窯業系基材や樹脂系基材等の表面に塗料を塗布して塗装品とする場合には、塗料としては一般的に有機系のものが用いられてきている。
【0003】
しかしながら、有機質の塗料では、光や雨水による劣化等の理由から耐候性や耐腐食性等の面で充分な性能が得られないことから、近年では、無機質のコーティング剤が開発されている。
【0004】
しかしながら基材としてセメント系無機質板のような窯業系の基材を用いる場合には、基材との密着性や意匠性等の観点から、あらかじめ有機塗膜を形成した後に、その上に無機質コーティング剤を塗布して無機質塗膜を配設することが好ましい場合が少なくないが、このような下地層としての有機塗膜を配設する場合、有機塗膜と無機質塗膜との層間の密着性を向上させることが重要な課題になっていた。
【0005】
このような課題への対策として、有機塗膜層をオルガノシロキサンユニット含有の特有のブロックポリマーを含有する有機塗料で形成し、その上にシランカップリング剤含有の無機塗料を塗布することが提案されている(特許文献1)。
【0006】
しかし、この対策でも層間密着性の改善効果は充分ではない。
【0007】
【特許文献1】
特開平10−193499号公報
【0008】
【発明が解決しようとする課題】
そこで、この出願の発明は、以上のとおりの従来の問題点を解消し、窯業系基材に無機質塗装膜とその下地層として有機塗膜層を配設した塗装体において、無機質塗膜層と有機塗膜層との層間密着性を向上させることのできる新しい塗装体を提供することを課題としている。
【0009】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、第1には、窯業系基材の表面に有機塗装膜とその上の無機質塗装膜を配設した塗装体であって、有機塗装膜は、コアシェル型のアクリルエマルジョン塗料でそのシェル部分のアクリル酸モノマー含有量が5〜15重量%の範囲にある塗料を、樹脂固形分量として50〜200g/m 2 の割合となるように窯業系基材の表面に塗布することにより形成されたものであり、無機質塗装膜は、
(a)一般式R1 nSiX4-n(式中、R1は同一または異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、nは0〜3の整数、Xは加水分解性基を示す。)で表される加水分解性オルガノシラン、
(b)平均組成R2 aSi(OH)bO(4-a-b)/2(式中、R2は同一または異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、a及びbはそれぞれ0.2≦a≦2、0.0001≦b≦3、a+b<4の関係を満たす数である。)で表されるポリオルガノシロキサン、
(c)硬化触媒
の(a)(b)(c)の3成分を必須成分として含有するケイ素アルコキシシラン系塗料の塗布により形成されたものであることを特徴とする塗装体を提供する。
【0011】
【発明の実施の形態】
この出願の発明は上記のとおりの特徴をもつものであるが、以下にその実施の形態について説明する。
【0012】
この出願の発明の塗装体は、
(A)セメント系無機質板のような窯業系基材
(B)下地層としての有機塗装膜
(C)有機塗装膜の上に配設した無機質塗装膜
とによって基本的に構成されている。
【0013】
このうちの(A)窯業系基材については、たとえばセメントを主とする固形成分の水性スラリーの抄造により得られた湿潤シートを脱水プレス成形し、乾燥、養生硬化させたものや、前記固形成分の水性混練物の押し出し成形、あるいは注型成形等により得られた成形体を硬化させたもの等の、従来より公知の組成のものをはじめとして各種のものであってよい。
【0014】
セメントに配合する固形成分についても、たとえば珪石粉、フライアッシュ、高炉スラグ等の無機質粒子や、パルプ等の補強繊維、さらには無機顔料等の各種のものが考慮されてよい。たとえば固形分の組成としては、セメント25〜65重量部、無機質粒子15〜50重量部、補強繊維2〜10重量部、顔料2〜10重量部の範囲のものが例示される。
【0015】
このような(A)窯業系基材の表面には、(B)下地層として有機塗装膜が配設される。そして、この出願の発明では、この有機塗装膜を、コアシェル型のアクリルエマルジョン塗料であって、そのシェル部分のアクリル酸モノマー含有量が5〜15重量%の範囲にある塗料の塗布によって形成することを必須の要件とし、大きな特徴としている。
【0016】
ここで、コアシェル型のアクリルエマルジョンとは、核粒子としてのシードエマルジョンの存在下に、アクリルアミドを主成分とする単量体成分を共重合させて得られる共重合体エマルジョンである。シードエマルジョンとしては、たとえばアクリルエステル系、スチレン/アクリル酸エステル系、アクリロニトリル系、スチレン−ブタジエン系、アクリロニトリル−ブタジエン系、アクリル酸エステル−ブタジエン系、塩化ビニル系、酢酸ビニル系等の一般的な高分子エマルジョンを用いることができ、それら単独であるいは二種類以上併用して使用することもできる。また、単量体成分中には、アクリルアミドと共重合可能な不飽和単量体が含有される。この不飽和単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸2−エチルヘキシル、アクリル酸2−ヒドロキシエチル、アクリル酸2−ヒドロキシプロピル、アクリル酸2−アミノエチル、アクリル酸2−(N−メチルアミノ)エチル、アクリル酸2−(N,N−ジメチルアミノ)エチル、アクリル酸グリシジル等のアクリル酸エステル類、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、アクリロニトリル等のニトリル基含有単量体類、アクリル酸、無水マレイン酸、フマール酸、イタコン酸、クロトン酸等の不飽和カルボン酸類、スチレン、α−メチルスチレン、ジビニルベンゼン等の芳香族ビニル単量体類、N−メチロールアクリルアミド等のN−置換不飽和カルボン酸アミド等が選択できる。特にこれらの内でも、カルボキシル基、水酸基、アミノ基、メチロール基、グリシジル基等の官能基を有する不飽和単量体を用いることが好ましい。このコアシェル構造のアクリルエマルジョンは、上述の材料とともに重合開始剤および連鎖移動剤などを用いて公知の重合技術により製造される。
【0017】
このようなコアシェル型のアクリルエマルジョンは、これまでにも知られている各種のものがあり(たとえば特開2000−204285を参照)、市販品を利用することもできる。
【0018】
この出願の発明では、このようなコアシェル型アクリルエマルジョンを用いた塗料のうちのシェル部分のアクリル酸モノマー含有量が5〜15重量%の範囲のものを用いることになる。そして、コアシェル型アクリルエマルジョンの塗料としては適宜な顔料成分を含有してもよいことは言うまでもない。
【0019】
コアシェル型アクリルエマルジョン塗料は、前記の基材表面に対して、樹脂固形分量として、50〜200g/m2の割合となるように塗布される。塗布後には、80℃〜120℃程度の温度で加熱乾燥して硬化させる。
【0020】
この出願の発明では、コアシェル型アクリルエマルジョン塗料におけるシェル部分のアクリル酸モノマー含有量は前記のとおり5〜15重量%とするか、5重量%未満の場合には、無機質塗装膜との層間密着強度の向上は期待できない。また、15重量%を超える場合も同様である。
【0021】
コアシェル型アクリルエマルジョン塗料によって形成した有機塗装膜の上には、(C)無機質塗装膜を配設するが、この場合の塗料については、塗装体としての長期耐久性や外観意匠性とともに、層間密着性を良好にするものとして、アルコキシシラン系塗料の塗布により形成されたものが考慮される。
アルコキシシラン系塗料としては、この出願の出願人が提案し、実際に開発してきた次の組成のもの、すなわち、
(a)一般式 R 1 n SiX 4-n (式中、 R 1 は同一または異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、 n は0〜3の整数、 X は加水分解性基を示す。)で表される加水分解性オルガノシラン、
(b)平均組成 R 2 a Si(OH) b O (4-a-b)/2 (式中、 R 2 は同一または異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、 a 及び b はそれぞれ0.2≦ a ≦2、0.0001≦ b ≦3、 a + b <4の関係を満たす数である。)で表されるポリオルガノシロキサン、
(c)硬化触媒
の(a)(b)(c)の3成分を必須成分として含有するケイ素アルコキシシラン系塗料(特開平5−117590、特開平9−119198)が使用される。
【0023】
アルコキシシラン系無機質塗料については、その固形分の塗布量が、たとえば2〜15g/m2程度となるように塗布し、100℃〜150℃程度の温度において加熱乾燥する。
【0024】
これによって、模様層あるいはクリアー層としての無機質塗装膜が形成され、このものの下地層としての前記の有機塗装膜との層間密着性は極めて良好なものとなる。
【0025】
なお、有機塗装膜および無機質塗装膜のいずれの場合の塗料の塗布方法には特に限定はない。ロール塗布、ブレード塗布、スプレー塗布、あるいは浸漬法による塗布等の各種の手段が適宜に採用されることになる。
【0026】
そこで以下に実施例を示し、さらに詳しく説明する。もちろん、以下の例によって発明が限定されることはない。
【0027】
【実施例】
表1に示したように、有機塗装膜の形成のためのコアシェル型アクリルエマルジョン塗料を用い、そのシェル部のアクリル酸モノマー含有量を変更しつつ、無機質塗装膜との積層塗装体を作成した。
【0028】
基材としては、セメントを固形分量の45重量%とした、窯業系基材を用いた。
【0029】
コアシェル型アクリルエマルジョン塗料は関西ペイント製のものを用い、また、無機質のケイ素アルコキシシラン系の塗料として出願人により製造されているものを用いた。
【0030】
得られた塗装体について、層間の密着性(2次密着性)を評価した。表1には、その結果も示した。
【0031】
【表1】
【0032】
この出願の発明の実施例1〜3によって優れた層間密着性が得られることが確認された。
【0033】
【発明の効果】
以上詳しく説明したとおり、この出願の発明によって、窯業系基材に無機質塗装膜とその下地層として有機塗膜層を配設した塗装体において、無機質塗膜層と有機塗膜層との層間密着性を向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a coated body. More specifically, the invention of this application is a new product that has long-term durability, good appearance, and excellent coating film adhesion in a coated body in which the surface of an inorganic ceramic base material useful as a building material is applied. It relates to a painted body.
[0002]
[Prior art]
Conventionally, in the case of building materials such as roof tiles, exterior materials, or interior materials, when paint is applied to the surface of ceramic base materials or resin base materials, it is common as a paint Organic materials have been used.
[0003]
However, since organic paints cannot provide sufficient performance in terms of weather resistance, corrosion resistance, and the like due to deterioration due to light and rainwater, inorganic coating agents have been developed in recent years.
[0004]
However, when a ceramic base material such as a cement-based inorganic board is used as the base material, from the viewpoint of adhesion to the base material and design properties, an organic coating film is formed in advance, and then an inorganic coating is formed thereon. In many cases, it is preferable to dispose an inorganic coating film by applying an agent, but in the case of disposing an organic coating film as such a base layer, the adhesion between the organic coating film and the inorganic coating film It has become an important issue to improve.
[0005]
As countermeasures against such problems, it has been proposed to form an organic coating layer with an organic paint containing a specific block polymer containing an organosiloxane unit, and to apply an inorganic paint containing a silane coupling agent thereon. (Patent Document 1).
[0006]
However, even with this measure, the effect of improving interlayer adhesion is not sufficient.
[0007]
[Patent Document 1]
JP-A-10-193499 gazette
[Problems to be solved by the invention]
Therefore, the invention of this application eliminates the conventional problems as described above, and in a coated body in which an inorganic coating film and an organic coating layer as an underlayer are disposed on a ceramic base material, an inorganic coating layer and It is an object to provide a new coated body that can improve interlayer adhesion with an organic coating layer.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention of this application is, firstly, a coated body in which an organic coating film and an inorganic coating film thereon are disposed on the surface of a ceramic base material, and the organic coating film Is a core-shell type acrylic emulsion paint, and the ceramic base content of the resin is such that the content of acrylic acid monomer in the shell portion is in the range of 5 to 15% by weight as the resin solid content is 50 to 200 g / m 2. It is formed by applying to the surface of the material , the inorganic coating film is
(A) General formula R 1 n SiX 4-n (wherein R 1 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0 to 3; X represents a hydrolyzable group.) Hydrolyzable organosilane represented by
(B) Average composition R 2 a Si (OH) b O (4-ab) / 2 (wherein R 2 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , A and b are numbers satisfying the relations 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3 and a + b <4, respectively)
(C) Provided is a coated body formed by applying a silicon alkoxysilane-based paint containing the three components (a), (b) and (c) of the curing catalyst as essential components.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The invention of this application has the features as described above, and an embodiment thereof will be described below.
[0012]
The coated body of the invention of this application is
(A) Ceramic base material such as cement-based inorganic plate (B) Organic coating film as base layer (C) Inorganic coating film disposed on organic coating film
[0013]
Of these, (A) ceramic base materials, for example, those obtained by dehydrating press-molding a wet sheet obtained by making an aqueous slurry of a solid component mainly composed of cement, drying, curing and curing, and the solid component Various types including those of conventionally known compositions such as those obtained by curing a molded body obtained by extrusion molding or casting molding of the aqueous kneaded product may be used.
[0014]
As for the solid component to be blended in the cement, for example, inorganic particles such as silica powder, fly ash and blast furnace slag, reinforcing fibers such as pulp, and inorganic pigments may be considered. For example, the composition of the solid content is exemplified by cement in the range of 25 to 65 parts by weight, inorganic particles 15 to 50 parts by weight, reinforcing fibers 2 to 10 parts by weight, and pigments 2 to 10 parts by weight.
[0015]
On the surface of the (A) ceramic base material, an organic coating film is disposed as a base layer (B). In the invention of this application, the organic coating film is formed by coating a core-shell type acrylic emulsion paint, in which the acrylic acid monomer content in the shell portion is in the range of 5 to 15% by weight. Is an essential requirement and a major feature.
[0016]
Here, the core-shell type acrylic emulsion is a copolymer emulsion obtained by copolymerizing a monomer component mainly composed of acrylamide in the presence of a seed emulsion as a core particle. As seed emulsions, for example, acrylic ester, styrene / acrylate ester, acrylonitrile, styrene-butadiene, acrylonitrile-butadiene, acrylate-butadiene, vinyl chloride, vinyl acetate, etc. Molecular emulsions can be used, and they can be used alone or in combination of two or more. Further, during the monomer component, acrylamide and copolymerizable unsaturated monomer is contained. As this unsaturated monomer, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-aminoethyl acrylate, acrylic acid 2- (N-methylamino) ethyl, 2- (N, N-dimethylamino) ethyl acrylate, acrylic esters such as glycidyl acrylate, vinyl esters such as vinyl acetate and vinyl propionate, and nitriles such as acrylonitrile Group-containing monomers, unsaturated carboxylic acids such as acrylic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, aromatic vinyl monomers such as styrene, α-methylstyrene, divinylbenzene, N- N-substituted unsaturated carboxylic acid amides such as methylolacrylamide can be selected. That. Among these, it is preferable to use an unsaturated monomer having a functional group such as a carboxyl group, a hydroxyl group, an amino group, a methylol group, or a glycidyl group. This core-shell structure acrylic emulsion is produced by a known polymerization technique using a polymerization initiator and a chain transfer agent together with the above-mentioned materials.
[0017]
There are various core-shell acrylic emulsions known so far (see, for example, JP-A-2000-204285), and commercially available products can also be used.
[0018]
In the invention of this application, an acrylic acid monomer content in the shell portion of the paint using the core-shell type acrylic emulsion is in the range of 5 to 15% by weight. Needless to say, an appropriate pigment component may be contained in the coating of the core-shell type acrylic emulsion.
[0019]
Core-shell acrylic emulsion paint, to the surface of the base material as a resin solid content, is coated to a proportion of 50 to 200 g / m 2. After the application, it is dried by heating at a temperature of about 80 ° C. to 120 ° C. and cured.
[0020]
In the invention of this application, when the content of acrylic acid monomer in the shell part in the core-shell type acrylic emulsion paint is 5 to 15% by weight or less than 5% by weight as described above, the interlayer adhesion strength with the inorganic coating film The improvement cannot be expected. The same applies to the case where it exceeds 15% by weight.
[0021]
On the organic coating film formed by core-shell acrylic emulsion paint, but to arrange the (C) inorganic coating film, the coating material in this case, together with the long-term durability and appearance design of the coated body, interlayer adhesion As those for improving the properties, those formed by application of an alkoxysilane-based paint are considered.
As the alkoxysilane-based paint, the applicant has proposed and actually developed the following composition, that is,
(A) General formula R 1 n SiX 4-n (wherein R 1 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0 to 3; X represents a hydrolyzable group.) Hydrolyzable organosilane represented by
(B) Average composition R 2 a Si (OH) b O (4-ab) / 2 (wherein R 2 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , the polyorganosiloxane expressed by a and b is a number satisfying 0.2 ≦ a ≦ 2,0.0001 ≦ b ≦ 3, a + b <4 relation, respectively.)
(C) Curing catalyst
A silicon alkoxysilane-based paint (JP-A-5-117590, JP-A-9-119198) containing the three components (a), (b) and (c) as essential components is used.
[0023]
About an alkoxysilane type inorganic coating material, it apply | coats so that the application quantity of the solid content may be about 2-15 g / m < 2 >, for example, and it heat-drys at the temperature of about 100 to 150 degreeC.
[0024]
As a result, an inorganic coating film as a pattern layer or a clear layer is formed, and the interlaminar adhesion with the organic coating film as an undercoat layer is very good.
[0025]
In addition, there is no limitation in particular in the application method of the coating material in any case of an organic coating film and an inorganic coating film. Various means such as roll coating, blade coating, spray coating, or coating by dipping are appropriately employed.
[0026]
Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.
[0027]
【Example】
As shown in Table 1, a core-shell type acrylic emulsion paint for forming an organic paint film was used, and a laminated paint body with an inorganic paint film was prepared while changing the acrylic acid monomer content in the shell portion.
[0028]
As the base material, a ceramic base material in which cement was 45% by weight of the solid content was used.
[0029]
The core-shell type acrylic emulsion paint used was made by Kansai Paint, and the one manufactured by the applicant as an inorganic silicon alkoxysilane paint was used.
[0030]
About the obtained coating body, the adhesiveness (secondary adhesiveness) between layers was evaluated. Table 1 also shows the results.
[0031]
[Table 1]
[0032]
It was confirmed that excellent interlayer adhesion was obtained by Examples 1 to 3 of the invention of this application.
[0033]
【The invention's effect】
As described above in detail, according to the invention of this application, in a coated body in which an inorganic coating film and an organic coating layer as an underlayer are disposed on a ceramic base material, interlayer adhesion between the inorganic coating layer and the organic coating layer Can be improved.
Claims (1)
(a)一般式R1 nSiX4-n(式中、R1は同一または異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、nは0〜3の整数、Xは加水分解性基を示す。)で表される加水分解性オルガノシラン、
(b)平均組成R2 aSi(OH)bO(4-a-b)/2(式中、R2は同一または異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、a及びbはそれぞれ0.2≦a≦2、0.0001≦b≦3、a+b<4の関係を満たす数である。)で表されるポリオルガノシロキサン、
(c)硬化触媒
の(a)(b)(c)の3成分を必須成分として含有するケイ素アルコキシシラン系塗料の塗布により形成されたものであることを特徴とする塗装体。A coated body in which an organic coating film and an inorganic coating film thereon are disposed on the surface of a ceramic base material, and the organic coating film is a core-shell type acrylic emulsion paint, and the acrylic acid monomer content in the shell portion is 5 It is formed by applying a paint in the range of ˜15 % by weight to the surface of the ceramic base material so as to have a resin solid content of 50 to 200 g / m 2 .
(A) General formula R 1 n SiX 4-n (wherein R 1 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0 to 3; X represents a hydrolyzable group.) Hydrolyzable organosilane represented by
(B) Average composition R 2 a Si (OH) b O (4-ab) / 2 (wherein R 2 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , A and b are numbers satisfying the relations 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3 and a + b <4, respectively)
(C) A coated body formed by applying a silicon alkoxysilane-based paint containing the three components (a), (b) and (c) of the curing catalyst as essential components.
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007168137A (en) * | 2005-12-19 | 2007-07-05 | Kubota Matsushitadenko Exterior Works Ltd | Coated object |
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JP2007167718A (en) * | 2005-12-19 | 2007-07-05 | Kubota Matsushitadenko Exterior Works Ltd | Coating body |
JP2007168136A (en) * | 2005-12-19 | 2007-07-05 | Kubota Matsushitadenko Exterior Works Ltd | Coated object |
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