【発明の詳細な説明】技術分野本発明は特定量のリン酸モノあるいはジエステルを含む
、耐水変色性の改善されたメタリック塗料組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to metallic coating compositions containing a specific amount of phosphoric acid mono- or diester and having improved water discoloration resistance.
従来技術アルミニウム等の金属粉を含むメタリック塗料に於ては
、温水浸漬などで塗膜が黒変し、係る変色防止機能（耐
水変色性）が問題とされている。Background Art In metallic paints containing metal powders such as aluminum, the paint film turns black when immersed in hot water, and the ability to prevent such discoloration (water discoloration resistance) is a problem.
特に自動車工業などでは近時ウレタンバンパーなどにも
メタリック塗装が行われる傾向にあるが、ウレタン成形
時のアミン触媒により塩基性雰囲気となっており、その
際にはその上に塗装するメタリック塗料の耐水変色性が
特に重大な問題となる。Particularly in the automobile industry, there is a recent trend of applying metallic paint to urethane bumpers, etc., but the amine catalyst created during urethane molding creates a basic atmosphere, and in this case, the water resistance of the metallic paint applied over it is Discoloration is a particularly serious problem.
その解決策として従来シリコン系やアクリル系の添加剤
を加え、アルミニウム等の金属片の周囲にポリマーの保
護層を形成せしめ疎水性の向上がはかられたが耐水変色
性の改善にはあまり効果がなく、また高純度アルミを使
用するとかアルミニウムをポリマーコーティングするこ
とも提案されたが経済性やメタリック感の点で難点があ
ったり、各グレードについて入手の問題があり、これら
の改善が強く求められていた。Conventionally, as a solution to this problem, silicone-based or acrylic-based additives were added to form a protective layer of polymer around metal pieces such as aluminum, which improved hydrophobicity, but this was not effective in improving water resistance to discoloration. In addition, it has been proposed to use high-purity aluminum or coat aluminum with polymers, but there are drawbacks in terms of economy and metallic appearance, and there are problems in obtaining each grade, so improvements in these areas are strongly desired. It was getting worse.
発明が解決しようとする問題点そこでメタリック塗料での有効且つ容易な耐水変色改善
手段ならびに耐水変色性に優れているだけでなく、メタ
リック感を充分発揮しうるメタリック塗料組成物が要望
されており、それに応えるべくなされたのが本発明であ
る。Problems to be Solved by the Invention Therefore, there is a need for an effective and easy means for improving water resistance and discoloration in metallic paints, as well as a metallic paint composition that not only has excellent water discoloration resistance but also can fully exhibit a metallic feel. The present invention has been made to meet this need.
問題点を解決するための手段上記目的は、全固形分に対し０．１〜２０重量％の金属
粉を含み、樹脂、溶媒ならびに塗料用嬌加剤からなるメ
タリック塗料組成物に於て式％式％（式中、Ｒは水素あるいは有機残基、Ｒ′は有機残基）で表わされるリン酸モノまたはジエステルを組成物全固
形分に対し、０．１〜５重量％含有せしめたことを特徴
とする耐水変色性の改善されたメタリック塗料組成物。Means for Solving the Problem The above object is to produce a metallic paint composition containing 0.1 to 20% by weight of metal powder based on the total solid content, and comprising a resin, a solvent, and a paint additive. % (wherein R is hydrogen or an organic residue, and R' is an organic residue) phosphoric acid mono- or diester is contained in an amount of 0.1 to 5% by weight based on the total solid content of the composition. A metallic paint composition with improved water discoloration resistance.
本発明で使用せられる上記式により表わされるリン酸モ
ノあるいはジエステルに於て、Ｒは水素原子であるか有
機残基でＲ′は有機残基である。In the phosphoric acid mono- or diester represented by the above formula used in the present invention, R is a hydrogen atom or an organic residue, and R' is an organic residue.
尚、有機残基としては有機材料と相溶性を有する限り任
意の基であることができ、代表的なものとしてはアルキ
ル、フェニル等のアリール、アラルキル、シクロアルキ
ルなどがあげられ、またポリエーテル、ポリエステル、
アクリル樹脂等塗料用基体樹脂の低分子量体（数分子量
４０００以下）でありうる。これらの多くは既知化合物
であり。The organic residue can be any group as long as it is compatible with the organic material, and typical examples include alkyl, aryl such as phenyl, aralkyl, cycloalkyl, etc. Polyether, polyester,
It may be a low molecular weight substance (number molecular weight of 4000 or less) of a base resin for paint such as acrylic resin. Many of these are known compounds.
また当業者衆知の方法で容易に合成することができる。Moreover, it can be easily synthesized by methods well known to those skilled in the art.
また、それらのいくつかは市場で容易に入手可能であり
、特に界面活性剤として知られる、例えばプライサーフ
Ａ２１２Ｃ，Ａ２０８Ｓ、２０８Ｂ○Ｈなどが好ましく使用せられる。Further, some of them are easily available on the market, and in particular, those known as surfactants, such as Plysurf A212C, A208S, and 208B ○H, are preferably used.
本発明者らはこういったリン酸モノあるいはジエステル
をメタリック塗料に配合すると、リン酸基がメタリック
塗料中の金属粉、例えばアルミニウムと比較的強い結合
をなし有機残基部が塗料の基体樹脂と相溶性を有するた
め、該樹脂に吸着され、結局アルミニウムの保護層が形
成され、これは従来の単にアルミニウムのまわりに樹脂
が保護層を形成する場合に比しはるかに強固に付着され
た保護層をなすこと、またリン酸部分による塩基性雰囲
気の中和効果を有し、本発明のメタリック塗料は塩基性
雰囲気中ですら極めて優れた耐水変色性を示すことが見
出されたのである。リン酸モノあるいはジエステルの添
加量は塗料全固形分に対し０．１〜５重量％の範囲内で
適宜選択せられる。というのはリン酸エステル量が０．
１％未満では効果があまり期待できず、他方５％を越え
ると作業性が悪くなりブリスタ発生の原因となることが
確かめられているからである。The present inventors found that when these phosphoric acid mono- or diesters are blended into metallic paints, the phosphoric acid groups form relatively strong bonds with the metal powder in the metallic paint, such as aluminum, and the organic residues bond with the base resin of the paint. Due to their compatibility, they are adsorbed to the resin and eventually form a protective layer of aluminum, which is much more firmly attached than the conventional case where the resin simply forms a protective layer around aluminum. It was also discovered that the phosphoric acid moiety has the effect of neutralizing a basic atmosphere, and that the metallic paint of the present invention exhibits extremely excellent water discoloration resistance even in a basic atmosphere. The amount of phosphoric acid mono- or diester added is appropriately selected within the range of 0.1 to 5% by weight based on the total solid content of the coating material. This is because the amount of phosphate ester is 0.
This is because it has been confirmed that if it is less than 1%, little effect can be expected, while if it exceeds 5%, workability deteriorates and causes blisters.
本発明のメタリック塗料は、特にウレタンパン１（ＥＪ
ｂ＋＋、、、ｈ＊ら重：Ｉ−ＭしｈｋＪＭＩ＋、−、ｈ
シｈ市；曾＋−＋＋／においてその特徴が顕著に認めら
れる。しかしながら、通常のメタリック塗料に於て優れ
た耐水変色性を示すことは勿論である。The metallic paint of the present invention is particularly suitable for urethane pan 1 (EJ
b++,,,h*ra weight:I-MshihkJMI+,-,h
This characteristic can be clearly seen in Shih City; Zeng+-++/. However, it goes without saying that it exhibits excellent water discoloration resistance in ordinary metallic paints.
以下実施例および比較例により本発明を説明する。特に
ことわりなき限り、部および％は重量による。The present invention will be explained below with reference to Examples and Comparative Examples. Parts and percentages are by weight unless otherwise specified.
実施例１下記組成のアクリルウレタン塗料用メタリック塗料を作
った。Example 1 A metallic paint for acrylic urethane paint having the following composition was prepared.
アルペースト１１ｏＯＮＡ（東洋インキ社製） ９．０部プライサーフＡ
−２１２Ｇ（第一工業製薬社製） ０．３部ヒタロイド４
４−１２７（日立化成社製） ７９．０部トルエン
１０．４部ディスパｏン４２００
−１０（楠本化成社製） １．３部１０凸 ｎ朝アルペーストｌ１００ＮＡに、プライサーフＡ−２１２
Ｃ、ヒタロイド４４−１２７、トルエンを加え室温で３
０分攪拌後ディスパロン４２００−１０を加えさらに３
０分攪拌を続はメタリック塗料を得た。Alpaste 11oONA (manufactured by Toyo Ink Co., Ltd.) 9.0 parts Plysurf A
-212G (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.3 parts Hytaloid 4
4-127 (manufactured by Hitachi Chemical) 79.0 parts toluene
10.4 part dispan on 4200
-10 (manufactured by Kusumoto Kasei Co., Ltd.) 1.3 parts 10 convex n Asaru Paste l100NA, Plysurf A-212
C, Hitaloid 44-127, add toluene and stir at room temperature.
After stirring for 0 minutes, add Disparon 4200-10 and further stir for 3 minutes.
After stirring for 0 minutes, a metallic paint was obtained.
実施例２〜６下記配合により、実施例１と同様の手法でアクリルウレ
タン塗料用メタリック塗料を調製した。Examples 2 to 6 Metallic paints for acrylic urethane paints were prepared in the same manner as in Example 1 using the following formulations.
比較例１〜４実施例１と同様の手法で上記配合のアクリルウレタン塗
料用メタリック塗料を調製した。Comparative Examples 1 to 4 Metallic paints for acrylic urethane paints having the above formulations were prepared in the same manner as in Example 1.
耐温水試験実施例１〜６及び比較例１〜４にスミジュールＮ−７５
（住人バイエル社製）をＯＨ／ＮＣＯ” １ ｅｑ／
ｌ ｅｑで混合し、トルエン／酢酸ブチル＝１／１のシ
ンナーでスプレー粘ｇ （＃４フォードカップ１４秒）
に稀釈した。○Ｔｏ−４８１１グレー（日本ペイント社
製）中塗をほどこした塗板にスプレー後、ウェットオン
ウェットでアクリデイクＡ−８０１（大日本インキ社製
）とスミジュールＮ−７５を○Ｈ／ＮＣ０＝ｌｅｑ／ｌ
ｅｑで混合したクリアー（＃４フォードカップ２０秒に
シンナーで稀釈したもの）をスプレー塗装し１００°Ｃ
で３０分焼き付はメタリック塗膜を形成した。Sumidur N-75 was used in hot water resistance test Examples 1 to 6 and Comparative Examples 1 to 4.
(Manufactured by Resident Bayer) OH/NCO” 1 eq/
Mix with l eq and spray with toluene/butyl acetate = 1/1 thinner (#4 Ford cup 14 seconds)
diluted to ○To-4811 Gray (manufactured by Nippon Paint Co., Ltd.) After spraying on a painted board with intermediate coating, apply Acridique A-801 (manufactured by Dainippon Ink Co., Ltd.) and Sumidur N-75 wet-on-wet at ○H/NC0=leq/l.
Spray paint with clear mixed with eq (#4 Ford Cup diluted with thinner for 20 seconds) and heat at 100°C.
After baking for 30 minutes, a metallic coating was formed.
塗板を４０℃の温水に５日間半没し、塗膜外観及びメタ
リック感を観察した。The coated plate was submerged in warm water at 40°C for 5 and a half days, and the appearance of the coating film and metallic feel were observed.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16938185AJPS6230168A (en) | 1985-07-30 | 1985-07-30 | Metallic coating composition |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16938185AJPS6230168A (en) | 1985-07-30 | 1985-07-30 | Metallic coating composition |
| Publication Number | Publication Date |
|---|---|
| JPS6230168Atrue JPS6230168A (en) | 1987-02-09 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16938185APendingJPS6230168A (en) | 1985-07-30 | 1985-07-30 | Metallic coating composition |
| Country | Link |
|---|---|
| JP (1) | JPS6230168A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61145119A (en)* | 1984-12-19 | 1986-07-02 | Yamanouchi Pharmaceut Co Ltd | Improver and remedy for mental symptoms caused by brain disorder |
| US5990206A (en)* | 1996-02-28 | 1999-11-23 | Kao Corporation | Asphalt modifier composition and asphalt composition |
| JP2010235729A (en)* | 2009-03-31 | 2010-10-21 | Denso Corp | Resin composition and reactor using the same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5544112A (en)* | 1978-09-19 | 1980-03-28 | Ishikawajima Harima Heavy Ind Co Ltd | Vaporizer in reliquefaction system of low temperature liquefied gas tank |
| JPS58168663A (en)* | 1982-03-31 | 1983-10-05 | Asahi Etsukaruto Kk | Powdered metal pigment composition and its preparation |
| JPS58168670A (en)* | 1982-03-31 | 1983-10-05 | Asahi Etsukaruto Kk | Colored metallic coating composition |
| JPS61291662A (en)* | 1985-06-19 | 1986-12-22 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | Aqueous paint composition and pigment composition |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5544112A (en)* | 1978-09-19 | 1980-03-28 | Ishikawajima Harima Heavy Ind Co Ltd | Vaporizer in reliquefaction system of low temperature liquefied gas tank |
| JPS58168663A (en)* | 1982-03-31 | 1983-10-05 | Asahi Etsukaruto Kk | Powdered metal pigment composition and its preparation |
| JPS58168670A (en)* | 1982-03-31 | 1983-10-05 | Asahi Etsukaruto Kk | Colored metallic coating composition |
| JPS61291662A (en)* | 1985-06-19 | 1986-12-22 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | Aqueous paint composition and pigment composition |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61145119A (en)* | 1984-12-19 | 1986-07-02 | Yamanouchi Pharmaceut Co Ltd | Improver and remedy for mental symptoms caused by brain disorder |
| US5990206A (en)* | 1996-02-28 | 1999-11-23 | Kao Corporation | Asphalt modifier composition and asphalt composition |
| JP2010235729A (en)* | 2009-03-31 | 2010-10-21 | Denso Corp | Resin composition and reactor using the same |
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|---|---|---|
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