JP2002256220A5

JP2002256220A5 -

Info

Publication number: JP2002256220A5
Application number: JP2001054125A
Authority: JP
Filing date: 2001-02-28
Publication date: 2004-12-09
Anticipated expiration: 2021-02-28

Description

【発明の名称】被覆用硬化性組成物、被覆物品、自動車用外板、および活性エネルギー線硬化性組成物Coating a curable composition [Title of Invention], the covering article, automotive outer panel, and the active energy ray-curable composition

【０００１】
本発明は、新規な組成物に関するものであり、より詳しくは基材表面に、透明性に優れ、かつ耐擦り傷性、耐熱性、耐薬品性、耐候性、および下地塗膜との密着性に優れた上塗り塗膜を形成しうる被覆用硬化性組成物、該組成物の硬化塗膜を有する被覆物品、その被覆物品からなる自動車用外板、および重合硬化前に基材に形成した塗膜がタックフリーになる活性エネルギー線硬化性組成物に関する。[0001]
The present invention relates to a novel composition, and more particularly to a substrate surface having excellent transparency and excellent scratch resistance, heat resistance, chemical resistance, weather resistance, and adhesion to an undercoat film. A curable composition for coating which can form an excellent top coat , a coated article having a cured coating of the composition, an automobile outer plate comprising the coated article, and a coating formed on a substrate before polymerization curing The present invention relates to an active energy ray-curable composition which becomes tack free.

【００１２】
（式中、Ｘはメタクリロイルオキシ基、アクリロイルオキシ基、またはビニルオキシ基を、Ｒ^１は炭素数０〜８の直鎖型または分岐型アルキル基を、Ｒ^２、Ｒ^３は炭素数１〜８の直鎖または分岐アルキル基を、ｎは０〜２の正の整数を示し、ｍ＋ｎは１〜３の正数である。）で示される単量体もしくはその加水分解物（固形分）１０〜６０質量％（但し、(b1)成分と(b2)成分との合計量を１００質量部とする）を加水分解、縮合反応して得られる硬化性シリコン（固形分）２〜６０質量％、および（Ｃ）１分子中に１個以上のアクリロイルオキシ基を有する脂環式化合物群および／または１分子中に１個以上のアクリロイルオキシ基を有するヘテロ環式化合物群５〜５０質量％の合計１００質量部に対して、（Ｄ）ラジカル重合開始剤０．０１〜１０質量部を配合してなる被覆用硬化性組成物、
該被覆用硬化性組成物の硬化塗膜を有する被覆物品、
該被覆物品からなる自動車用外板、
および重合硬化前に基材に形成した塗膜がタックフリーになる活性エネルギー線硬化性組成物にある。[0012]
(Wherein, X is a methacryloyloxy group, an acryloyloxy group, or a vinyloxy group, R ¹ is a linear or branched alkyl group having 0 to 8 carbon atoms, R ² , and R ³ is 1 to 8 carbon atoms A linear or branched alkyl group, n is a positive integer of 0 to 2 and m + n is a positive number of 1 to 3.) a monomer or its hydrolyzate (solid content) 10 to 60 2 to 60 mass% of curable silicon (solid content) obtained by hydrolysis and condensation reaction of mass% (however, the total amount of the components (b1) and (b2) is 100 parts by mass), C) Alicyclic compound group having one or more acryloyloxy groups in one molecule and / or 5 to 50% by mass in total of heterocyclic compound group having one or more acryloyloxy groups in one molecule (D) radical polymerization initiator 0.0 for each part Coating a curable composition obtained by blending 10 parts by weight,
Coated article having a cured coating film of the coating curable composition,
A car outer panel comprising the coated article,
And an active energy ray-curable composition in which the coating formed on the substrate becomes tack-free before polymerization curing .

【００２６】
本発明の被覆用組成物において、（Ｂ）成分を得るために用いるコロイダルシリカ微粒子(b1)とは、一次粒子径が１〜２００ｎｍの範囲の無水ケイ酸の超微粒子を水または有機溶剤の分散媒に分散させた状態のものをいう。[0026]
In the coating composition of the present invention, the colloidal silica fine particles (b1) used to obtain the component (B) is a dispersion of ultrafine particles of silicic anhydride having a primary particle diameter in the range of 1 to 200 nm in water or an organic solvent. In the state of being dispersed in the medium.

【００５４】
本発明において化合物（Ｃ）の使用量は、（Ａ）〜（Ｃ）成分の合計量１００質量部中、５〜５０質量％の範囲、好ましくは１０〜３０質量％の範囲である。化合物（Ｃ）の使用量が５質量％より少ないと得られる硬化塗膜の耐候性および基材との密着性が低下する傾向にあり、一方、５０質量％を超えると硬化塗膜にクラックが発生したり、タックフリー性が低下する傾向にある。[0054]
The amount of the compound (C) in the present invention is (A) in the total amount 100 parts by mass of ~ (C) component in the range of 5 to 50 mass%, the range preferably of 10 to 30 mass%. If the amount of the compound (C) used is less than 5% by mass, the weather resistance of the resulting cured coating film and the adhesion to the substrate tend to decrease, while if it exceeds 50% by mass, the cured coating film has cracks It tends to occur or the tack free property decreases.

【００６８】
次に、本発明の被覆物品について以下詳細に説明する。
本発明の被覆物品とは、前記被覆用組成物の硬化塗膜を有する物品である。 [0068]
Next, the coated article of the present invention will be described in detail below.
The coated article of the present invention is an article having a cured coating of the coating composition.

【００６９】
本発明の被覆物品を得るには、まず前記被覆用組成物を、ハケ塗り法、スプレーコート法、シャワーフローコート法、ディップコート法、カーテンコート法等、公知の方法で基材に塗布すればよい。[0069]
In order to obtain the coated article of the present invention, first, the coating composition is applied to a substrate by a known method such as a brush coating method, a spray coating method, a shower flow coating method, a dip coating method or a curtain coating method. Good.

【００７４】
本発明の被覆物品に用いる基材は、特に限定されるものではなく、化成処理した鋼板にプライマーを電着塗装し、必要に応じて中塗り塗料を塗装した基材、各種プラスチック基材（必要に応じて予めプライマー塗装、中塗り塗装等の表面処理を行ったものでも可）、これらのものが組合わさった複合部材等が挙げられる。[0074]
The base material used for the coated article of the present invention is not particularly limited, and a base material obtained by electrodeposition coating of a primer on a chemically treated steel plate and, if necessary, an intermediate coating, various plastic base materials Depending on the surface treatment such as primer coating, middle coat coating, etc. may be carried out in advance), and composite members in which these components are combined may be mentioned.

【００７６】
また、前記した基材の他、ガラス、金属、木材、紙、布等を基材として用いてもよい。
本発明の物品としては、特に自動車用外板に好適である。[0076]
Moreover, you may use glass, a metal, wood, paper, cloth etc. as a base material besides the above-mentioned base material .
The article of the present invention is particularly suitable for automobile outer plates.

【００８８】
４．耐溶剤性：メチルエチルケトンおよびキシレンを十分に染み込ませたガーゼを５００ｇ荷重で５０往復させた後、硬化塗膜表面の外観を目視で評価した。
○：全く変化なし
△：傷が付く、もしくは硬化塗膜が曇る
×：硬化塗膜が膨潤する、もしくは溶解する[0088]
4. Solvent resistance: The gauze sufficiently impregnated with methyl ethyl ketone and xylene was reciprocated 50 times with a load of 500 g, and then the appearance of the surface of the cured coating was visually evaluated.
:: no change △: scratched or cured film becomes cloudy x: cured film swells or dissolves

【００９１】
７．耐候性：試験板をサンシャインウェザオメーターにて１０００時間試験した後の硬化塗膜表面を目視にて観察した。
○：硬化塗膜面に変化なし
×：クラック、変色、剥離等の異常あり[0091]
7. Weatherability: The surface of the cured coating film after the test plate was tested for 1000 hours with a sunshine weatherometer was visually observed.
○: No change in the cured coating surface ×: Abnormality such as cracking, discoloration, peeling

【０１０５】
比較例４は、本発明における（Ａ）成分が少ない被覆用組成物の例であり、表面タック性に劣る塗膜であり、また耐候性、密着性に劣る硬化塗膜であった。[0105]
Comparative Example 4 is an example of a coating composition containing a small amount of the component (A) in the present invention, which is a coating film inferior in surface tackiness, and a cured coating film inferior in weather resistance and adhesion .

【０１０７】
比較例６は、本発明における（Ｂ）成分が少ない被覆用組成物の例であり、表面タック性に劣る塗膜であり、また耐擦り傷性に劣る硬化塗膜であった。[0107]
Comparative Example 6 is an example of a coating composition containing a small amount of the component (B) in the present invention, and is a coating film inferior in surface tackiness and a cured coating film inferior in abrasion resistance .

【０１０９】
比較例８は、本発明における（Ｃ）成分が多い被覆用組成物の例であり、表面タック性に劣る塗膜であり、また耐候性、密着性に劣る硬化塗膜であった。[0109]
Comparative Example 8 is an example of a coating composition containing a large amount of the component (C) in the present invention, which is a coating film inferior in surface tackiness, and a cured coating film inferior in weather resistance and adhesion.

Claims

(A) 20 to 80 mass% of a polymer compound having an acryloyloxy group in a side chain, (B) (b1) colloidal silica fine particles (solid content) 40 to 90 mass%, (b2) the following general formula (I)

(Wherein, X is a methacryloyloxy group, an acryloyloxy group, or a vinyloxy group, R ¹ is a linear or branched alkyl group having 0 to 8 carbon atoms, R ² , and R ³ is 1 to 8 carbon atoms A linear or branched alkyl group, n is a positive integer of 0 to 2 and m + n is a positive number of 1 to 3.) a monomer or its hydrolyzate (solid content) 10 to 60 2 to 60 mass% of curable silicon (solid content) obtained by hydrolysis and condensation reaction of mass% (however, the total amount of the components (b1) and (b2) is 100 parts by mass), C) Alicyclic compound group having one or more acryloyloxy groups in one molecule and / or 5 to 50% by mass in total of heterocyclic compound group having one or more acryloyloxy groups in one molecule (D) radical polymerization initiator 0.0 for each part Coating a curable composition obtained by blending 10 parts by weight.

The curable composition for coating | cover formed by mix | blending 10-1000 mass parts of organic solvents (E) with respect to 100 mass parts of total amounts of (A)-(C) component.

The curable composition for coating according to claim 1 or 2, wherein the radical polymerization initiator (D) is a compound in which a radical is generated by an active energy ray.

The coated article which has a cured coating film of the curable composition for a coating in any one of Claims 1-3 on a base material.

The coated article of claim 4 wherein the cured coating is a clear top coat film.

The coated article according to claim 5, wherein the film thickness of the clear top coat film is 5 to 80 m .

The coated article according to claim 4, wherein the substrate, the colored base coat film and the clear top coat film of one or more layers are sequentially formed, and the clear top coat film of the outermost layer is the cured coating film according to claim 4. .

The coated article according to claim 7, wherein the colored base coat film is a cured product of a paint composition containing water.

An automobile outer panel comprising the coated article according to any one of claims 4 to 8 .

An active energy ray curable composition in which a coating film comprising the composition according to any one of claims 1 to 3 becomes tack-free before polymerization curing.