JP2001316603A5

JP2001316603A5 -

Info

Publication number: JP2001316603A5
Application number: JP2001054124A
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、および自動車用外板Patent application title: CURABLE COMPOSITIONS FOR COATINGS, COATED ARTICLES, AND AUTOMOBILE SHELLS

【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、および自動車用外板に関する。[0001]
The present invention relates to a novel composition, and more specifically, the substrate surface is excellent in transparency and scratch resistance, heat resistance, chemical resistance, weather resistance, and adhesion to an undercoat film. coating a curable composition capable of forming an excellent topcoat coating film, coated article having a cured coating of the composition, and to automotive outer panels.

【００１３】
（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分子中に少なくとも２個以上の（メタ）アクリロイルオキシ基を有するエチレン性不飽和化合物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、
基材上に前記被覆用硬化性組成物の硬化塗膜を有する被覆物品、
および前記被覆物品からなる自動車用外板にある。[0013]
(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) (D) Radical polymerization initiator 0.01 to 10 per 100 parts by mass in total of 5 to 50% by mass of the ethylenically unsaturated compound having at least two or more (meth) acryloyloxy groups in one molecule A curable composition for coating, which comprises a mass part,
Coated articles having a cured coating of the curable composition for coating on a substrate,
And an automobile skin consisting of the coated article .

【００３０】
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。[0030]
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.

【００６０】
（Ｄ）成分について
本発明の被覆用組成物には、ラジカル重合開始剤（Ｄ）を配合する。このラジカル重合開始剤（Ｄ）はラジカルを発生させるものであればよく、活性エネルギー線によりラジカルが発生する化合物でも熱によりラジカルが発生する化合物でもよい。[0060]
Component (D) The coating composition of the present invention contains a radical polymerization initiator (D). The radical polymerization initiator (D) may be any compound that generates radicals, and may be a compound that generates radicals by active energy rays or a compound that generates radicals by heat.

【００７０】
本発明において有機溶剤（Ｅ）を使用する場合には、（Ａ）〜（Ｃ）成分の合計量１００質量部に対して、好ましくは１０〜１０００質量部の範囲、特に好ましくは５０〜８００質量部の範囲である。
有機溶剤（Ｅ）の使用量が１０００質量部を超えると、溶剤揮発に長時間を要したり、塗装時にたれが発生しやすくなるといった作業性の低下を引き起こす可能性がある。[0070]
When the organic solvent (E) is used in the present invention, it is preferably in the range of 10 to 1000 parts by mass, particularly preferably 50 to 800 parts by mass, per 100 parts by mass of the total amount of components (A) to (C). The scope of the department.
When the amount of use of the organic solvent (E) exceeds 1000 parts by mass, the solvent volatilization may take a long time, and the workability may be deteriorated such that the coating tends to be dripped.

【００７２】
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、基材上に前記組成物の硬化塗膜を有する物品である。 [0072]
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 composition on a substrate.

【００７３】
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。[0073]
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.

【００７８】
本発明の被覆物品に用いる基材としては、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。[0078]
The substrate used for the coated article of the present invention is not particularly limited, and a substrate obtained by electrodeposition coating of a primer on a chemically treated steel plate and, if necessary, an intermediate coating, various plastic substrates ( If necessary, those subjected to surface treatment such as primer coating and middle coat coating in advance may be used), and composite members in which these members are combined, etc. may be mentioned.

【００８０】
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。[0080]
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.

【００９１】
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[0091]
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

【００９４】
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[0094]
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

【０１０６】
実施例１
〈被覆用組成物の調整〉
（Ａ）成分として高分子化合物（A1）を含む溶液１０２質量部（固形分４９質量％）、（Ｂ）成分として硬化性シリコン（B1）３３質量部（固形分６０質量％）、（Ｃ）成分としてイソシアヌレート酸ＥＯ変性トリアクリレート（商品名：Ｍ−３１５、東亜合成社製）(C1)３０質量部、（Ｄ）成分として１−ヒドロキシシクロヘキシルフェニルケトン（D1）（商品名：イルガキュア１８４、チバスペシャリティーケミカルズ社製）２質量部とメチルフェニルグリオキシレート（D2）（商品名：バイキュア５５、ストーファー社製）１質量部を攪拌混合して、被覆用組成物を調整した。[0106]
Example 1
<Preparation of Coating Composition>
102 parts by mass (solid content: 49% by mass) containing the polymer compound (A1) as component (A); 33 parts by mass (solid content: 60% by mass) of curable silicone (B1) as component (B) (C) 30 parts by mass of isocyanurate acid EO modified triacrylate (trade name: M-315, manufactured by Toagosei Co., Ltd.) (C1), 1-hydroxycyclohexyl phenyl ketone (D1) as the component (D) (trade name: Irgacure 184, A coating composition was prepared by stirring and mixing 2 parts by mass of Ciba Specialty Chemicals and 1 part by mass of methylphenylglyoxylate (D2) (trade name: VICURE 55, manufactured by Stoffer).

【０１１１】
さらに、表中の略記号は、以下の化合物を表す。
（Ａ）成分
（A1）：合成例１で重合した高分子化合物（固形分）
（A2）：合成例２で重合した高分子化合物（固形分）
（A3）：合成例３で重合した高分子化合物（固形分）
（Ｂ）成分
（B1）：合成例４で合成した光硬化性有機シリコン（固形分）
（Ｃ）成分
（C1）：イソシアヌレート酸ＥＯ変性トリアクリレート（商品名：Ｍ−３１５、東亜合成社製）
（C2）：４−ヒドロキシブチルアクリレート
（C3）：アクリル酸テトラヒドロフルフリル[0111]
Furthermore, the abbreviations in the table represent the following compounds.
(A) Component (A1): Polymer compound polymerized in Synthesis Example 1 (solid content)
(A2): Polymer compound (solid content) polymerized in Synthesis Example 2
(A3): Polymer compound (solid content) polymerized in Synthesis Example 3
(B) Component (B1): Photocurable organic silicon (solid content) synthesized in Synthesis Example 4
(C) Component (C1): isocyanurate EO modified triacrylate (trade name: M-315, manufactured by Toa Gosei Co., Ltd.)
(C2): 4-hydroxybutyl acrylate (C3): tetrahydrofurfuryl acrylate

【０１１４】
比較例２は、本発明における（Ａ）成分以外の高分子化合物を含む被覆用組成物であるため、塗膜の表面タック性や硬化塗膜の外観はよいものの、耐硫酸性、耐溶剤性、耐擦り傷性に劣る硬化塗膜であった。[0114]
Comparative Example 2 is a coating composition containing a polymer compound other than the component (A) in the present invention, so the surface tackiness of the coating film and the appearance of the cured coating film are good, but sulfuric acid resistance and solvent resistance It was a cured coating film inferior in abrasion resistance.

【０１１７】
比較例５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った。[0117]
Comparative Example 5 is an example of a coating composition containing a small amount of the component (A) in the present invention, and was a coating film inferior in surface tackiness.

【０１２０】
比較例８は、本発明における（Ｂ）成分が多い被覆用組成物の例であり、すべての評価結果において劣る塗膜および硬化塗膜であった。[0120]
Comparative Example 8 is an example of a coating composition containing a large amount of the component (B) in the present invention, and was a coating film and a cured coating film inferior in all the evaluation results.

【０１２１】
比較例９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と、外観に劣る硬化塗膜であった。[0121]
Comparative Example 9 is an example of a coating composition containing a large amount of the component (C) in the present invention, and is a coating film inferior in surface tackiness and a cured coating film inferior in appearance.

Claims

(A) 20 to 80 mass% of a polymer compound having a side chain having at least one carbon-carbon unsaturated double bond, (B) (b1) colloidal silica fine particles (solid content) 40 to 90 mass% And (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) (D) Radical polymerization initiator 0.01 to 10 per 100 parts by mass in total of 5 to 50% by mass of the ethylenically unsaturated compound having at least two or more (meth) acryloyloxy groups in one molecule The curable composition for coating | cover formed by mix | blending a mass part.

The curable composition for coating | cover of Claim 1 which mix | blends 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 5, wherein the substrate, the colored base coat film and the clear top coat film are laminated in this order.

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.