JPH0737107B2 - Black silicone resin coated metal plate - Google Patents
Black silicone resin coated metal plateInfo
- Publication number
- JPH0737107B2 JPH0737107B2 JP63109065A JP10906588A JPH0737107B2 JP H0737107 B2 JPH0737107 B2 JP H0737107B2 JP 63109065 A JP63109065 A JP 63109065A JP 10906588 A JP10906588 A JP 10906588A JP H0737107 B2 JPH0737107 B2 JP H0737107B2
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- Prior art keywords
- resin
- metal plate
- silicone resin
- sicl
- coating
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 自動車マフラーや熱風ヒーターの排気ダクト材や仕切板
のように、成形加工後、加熱が加わる環境で使用される
場合、また、TV用テンションバンドのように成形加工時
に加熱工程を含む場合など、耐熱性、加工性、スポット
溶接性などを要求される用途に使用するのに好適な黒色
の意匠性を付与した樹脂皮膜金属板に関する。[Detailed Description of the Invention] [Industrial application] When used in an environment where heating is applied after molding, such as exhaust duct materials and partition plates for automobile mufflers and hot air heaters, and TV tension bands As described above, the present invention relates to a resin-coated metal plate imparted with a black design suitable for use in applications requiring heat resistance, workability, spot weldability, etc., including a heating step during molding.
金属板をマフラーや、ダクトに成形加工（スポット溶接
を含む）した後または、テンションバンドをテレビのブ
ラウン管に焼ばめした後に、意匠性を付与するため黒色
塗料を塗装していた。After forming a metal plate into a muffler or duct (including spot welding), or after shrink-fitting a tension band into a television CRT, a black paint was applied to give it a design.
また、耐熱性、加工性および黒色の意匠性を付与したプ
レコート材料を使用し、後塗装の作業をなくし、コスト
低減をはかることも行なわれている。Further, it is also attempted to reduce the cost by using a precoat material imparted with heat resistance, workability and black designability, eliminating the work of post-coating.
耐熱性、加工性および黒色の意匠性を付与したプレコー
ト材料は、すでに公知になっている（特開昭61−17723
8）。しかし、これらの材料は、耐食性を考え、20μｍ
程度の膜厚で、絶縁性に優れている反面、絶縁抵抗が高
すぎるためスポット溶接による成形加工が不可能という
欠点を有している。Precoat materials having heat resistance, processability and black design have been already known (Japanese Patent Laid-Open No. 61-17723).
8). However, considering the corrosion resistance, these materials are 20 μm
Although it has a relatively thin film thickness and excellent insulation properties, it has a drawback in that it cannot be molded by spot welding because the insulation resistance is too high.
また、成形品は塗装前処理することができない場合も多
く、塗膜の密着性が劣る品質上の欠点も生じやすい。In many cases, the molded product cannot be subjected to pretreatment before coating, so that the adhesion of the coating film is inferior and a quality defect is likely to occur.
本発明は、一般式 （式中Ｒは、非置換または置換のアルキル基、アルケニ
ル基であり、a,bは、0.6≦ａ≦1.3,0.35≦ｂ≦0.95、か
つ1.4≦ａ＋ｂ≦1.7を満たす正数、ｃは本化合物中にお
けるケイ素原子に結合した水酸基の占める比率が0.01〜
3.0重量％となるような値を示す）で示されるオルガノ
ポリシロキサン樹脂に、黒色着色顔料を配合させた塗料
を皮膜厚0.5〜10μｍになるように金属板に塗布、乾燥
してなる。The present invention has the general formula (Wherein R is an unsubstituted or substituted alkyl group or alkenyl group, a and b are positive numbers satisfying 0.6 ≦ a ≦ 1.3, 0.35 ≦ b ≦ 0.95 and 1.4 ≦ a + b ≦ 1.7, and c is The ratio of hydroxyl groups bonded to silicon atoms in the compound is 0.01 ~
A coating material in which a black coloring pigment is mixed with an organopolysiloxane resin represented by (3) shows a value of 3.0% by weight) is applied to a metal plate to a film thickness of 0.5 to 10 μm, and dried.
一般式 （式中Ｒ′は一般にはフェニル基、またはメチル基）で
示される耐熱性シリコーン樹脂は全有機基に占めるフェ
ニル基の含有率が30〜70mol％で、かつｎの値が1.2〜1.
8のものが耐熱性に優れているとされている。しかしか
かる樹脂は乾燥硬化させるのに30分以上要し、また膜厚
を可撓性を持つμｍ以下にすると、ハジキや未塗布部分
が生じてしまうため、５μｍ以下にできないものであっ
た。General formula The heat-resistant silicone resin represented by the formula (wherein R'is generally a phenyl group or a methyl group) has a phenyl group content of 30 to 70 mol% in all organic groups, and an n value of 1.2 to 1.
8 is said to have excellent heat resistance. However, it takes 30 minutes or more to dry and cure such a resin, and if the film thickness is set to less than μm, which has flexibility, cissing and an uncoated portion are generated, so that the resin cannot be set to less than 5 μm.
そこで本発明者らは種々検討した結果、シリコーン樹脂
をゲル・パーミエーション・クロマトグラフィー（以下
GPCと略す）で測定したポリスチレン換算分子量（測定
条件：測定器 東洋曹達（株）製HLC802A、カラムTSK−
GEL GMH6、G4000H6、G2000H6 2本、計４本、溶媒テトラ
ヒドロフラン、流量1.2ml/min、圧力5.0kgf/cm2、検出
器屈折率およびUV、以下の樹脂においても同一条件）で
103程度の低分子量から106程度の高分子量にわたるもの
にすると、めっき鋼板への流展性と皮膜の凝集力が大き
くなって、ハジキや未塗布部分が発生しなくなり、かつ
一般式 におけるｎの値を1.4〜1.7、かつフェニル基含有率を25
〜55mol％（本発明の一般式中のｂが0.35≦ｂ≦0.95）
にすると、可撓性のみならず耐熱性、熱衝撃性も著しく
向上することを見出した。そして特にフェニル基含有率
を35〜55mol％（本発明の一般式ではｂが0.49≦ｂ≦0.9
5）にし、そのフェニル基が（C6H5）2SiO単位を5mol％
以上含有するものの皮膜は可撓性があり、表面も平滑
で、膜厚を0.5〜２μｍと薄くしても優れた耐熱性、耐
食性を発揮することが判明した。Therefore, as a result of various investigations by the present inventors, the silicone resin was analyzed by gel permeation chromatography (hereinafter
Polystyrene-equivalent molecular weight measured by GPC (Measurement conditions: Measuring instrument Toyo Soda Co., Ltd. HLC802A, column TSK-
GEL GMH 6 , G4000H 6 , G2000H 6 2 pieces, 4 pieces in total, solvent tetrahydrofuran, flow rate 1.2 ml / min, pressure 5.0 kgf / cm 2 , detector refractive index and UV, same conditions for the following resins)
When the molecular weight ranges from low molecular weight of about 10 3 to high molecular weight of about 10 6 , the flowability to the plated steel sheet and the cohesive force of the coating become large, and repelling and uncoated parts do not occur, and the general formula Value of n is 1.4 to 1.7, and the phenyl group content is 25
~ 55 mol% (b in the general formula of the present invention is 0.35 ≤ b ≤ 0.95)
It was found that, when it is set, not only flexibility but also heat resistance and thermal shock resistance are remarkably improved. In particular, the phenyl group content is 35 to 55 mol% (in the general formula of the present invention, b is 0.49≤b≤0.9.
5) and the phenyl group contains 5 mol% of (C 6 H 5 ) 2 SiO units.
It was found that the film containing the above has flexibility, the surface is smooth, and excellent heat resistance and corrosion resistance are exhibited even when the film thickness is thinned to 0.5 to 2 μm.
本発明の樹脂はこのような知見に基づいてなされたもの
で、一般式は前述のように示され、分子量がGPCで測定
したポリスチレン換算分子量で103程度の低分子量から1
06程度の高分子量にわたるオルガノポリシロキサン樹脂
を含有している。ここで一般式のＲは前述のごとく非置
換または置換のアルキル基、アルケニル基であるが、非
置換アルキル基としてはメチル基、エチル基、プロピル
基などを、また非置換アルケニル基としてはビニル基、
アリル基などを挙げることができる。さらに置換アルキ
ル基としてはクロロメチル基、3,3,3−トリフルオロプ
ロピル基などを挙げることができる。これらのうち好ま
しいものはアルキル基、特に好ましいものはメチル基で
ある。The resin of the present invention has been made based on such knowledge, the general formula is shown as described above, the molecular weight is from polystyrene low molecular weight measured by GPC of about 10 3 to low molecular weight 1
It contains an organopolysiloxane resin having a high molecular weight of about 0 6 . Here, R in the general formula is an unsubstituted or substituted alkyl group or alkenyl group as described above, but the unsubstituted alkyl group is a methyl group, an ethyl group, a propyl group or the like, and the unsubstituted alkenyl group is a vinyl group. ,
An allyl group etc. can be mentioned. Furthermore, examples of the substituted alkyl group include a chloromethyl group and a 3,3,3-trifluoropropyl group. Of these, an alkyl group is preferable, and a methyl group is particularly preferable.
本発明の樹脂はケイ素原子に結合した水酸基の占める比
率（本発明の一般式におけるｃ）が0.01〜3.0重量％に
なるように重合度調整したものである。これは水酸基含
有率が0.01重量％未満に重合度を調整したものはめっき
鋼板に対して密着性が乏しく、3.0重量％を越えるよう
に調整したものは硬化性に乏しいため、高温、短時間に
皮膜を形成することができず、また重合度が低すぎて、
0.5〜2.0μｍという薄膜にした場合均一な皮膜とならな
いためである。特に膜厚と密着性、硬化性とのバランス
を保つには水酸基含有率が0.2〜2.0重量％（本発明の一
般式におけるｃの値の0.01〜0.2程度に相当する）にな
るように重合度調整したものが好ましい。The resin of the present invention has a degree of polymerization adjusted such that the ratio of hydroxyl groups bonded to silicon atoms (c in the general formula of the present invention) is 0.01 to 3.0% by weight. This is because if the degree of polymerization is adjusted to less than 0.01% by weight of the hydroxyl group, the adhesion to the plated steel sheet is poor, and if it is adjusted to exceed 3.0% by weight, the curability is poor. A film cannot be formed, and the degree of polymerization is too low,
This is because a thin film of 0.5 to 2.0 μm does not form a uniform film. In particular, in order to maintain the balance between the film thickness, the adhesion and the curability, the degree of polymerization is adjusted so that the hydroxyl group content is 0.2 to 2.0% by weight (corresponding to about 0.01 to 0.2 of the value of c in the general formula of the present invention). The adjusted one is preferable.
本発明の樹脂は鋼板に塗布するときは通常溶剤に溶解さ
せて使用する。溶剤としては、ベンゼン、トルエンン、
キシレン、エチルベンゼン等の芳香族系有機溶剤、トリ
クロルエチレン、1,1,1−トリクロルエタン、四塩化炭
素、クロロホルム等の含塩素系有機溶剤、ヘキサン、リ
グロイン、工業用ガソリン等脂肪族炭化水素の単独もし
くは混合溶剤を使用するのが好ましく、特に塗布作業面
からキシレンが好ましい。When the resin of the present invention is applied to a steel sheet, it is usually dissolved in a solvent before use. Solvents include benzene, toluene,
Aromatic organic solvents such as xylene and ethylbenzene, chlorine-containing organic solvents such as trichloroethylene, 1,1,1-trichloroethane, carbon tetrachloride and chloroform, hexane, ligroin, and aliphatic hydrocarbons such as industrial gasoline Alternatively, it is preferable to use a mixed solvent, and xylene is particularly preferable from the viewpoint of coating work.
この樹脂は目的の有機基をケイ素１個当り1.4〜1.7個有
するクロロシランの単独もしくは混合物および／または
アルコキシシランの単独または混合物を前記のような溶
剤中で加水分解し、必要に応じて重合すれば得られる。
クロロシランとしては、例えばPh2SiCl2、PhSiCl3、Me2
SiCl2、MeSiCl3、PhMeSiCl2、C2H5SiCl3、CH3CH2CH2SiC
l3、CF3CH2CH2SiCl3、SiCl4、Me3SiClが、またアルコキ
シシランとしては、（C2H5O）4Si、Ph2Si（OMe）２、Ph
Si（OMe）３、Me2Si（OMe）２、MeSi（OMe）３、Ph2MeS
iOC2H5、Me3SiOMe等がある（Meはメチル基、Phはフェニ
ル基である）。これらのうち特にPh2SiCl2あるいはPh2S
i（OMe）２を5mol％以上含有するシラン混合物を加水分
解して得たものは前述のごとく耐熱性、可撓性および熱
衝撃性に優れている。This resin is prepared by hydrolyzing a chlorosilane having a desired organic group of 1.4 to 1.7 per silicon, alone or in a mixture, and / or an alkoxysilane in a solvent as described above, and polymerizing it if necessary. can get.
Examples of chlorosilanes include Ph 2 SiCl 2 , PhSiCl 3 , Me 2
SiCl 2 , MeSiCl 3 , PhMeSiCl 2 , C 2 H 5 SiCl 3 , CH 3 CH 2 CH 2 SiC
l 3 , CF 3 CH 2 CH 2 SiCl 3 , SiCl 4 , and Me 3 SiCl, and as alkoxysilane, (C 2 H 5 O) 4 Si, Ph 2 Si (OMe) 2 , Ph
Si (OMe) 3 , Me 2 Si (OMe) 2 , MeSi (OMe) 3 , Ph 2 MeS
iOC 2 H 5 , Me 3 SiOMe, etc. (Me is a methyl group, Ph is a phenyl group). Among these, especially Ph 2 SiCl 2 or Ph 2 S
The product obtained by hydrolyzing a silane mixture containing i (OMe) 2 in an amount of 5 mol% or more is excellent in heat resistance, flexibility and thermal shock resistance as described above.
本発明の黒色着色顔料は、導電性カーボンブラック（ラ
イオンアクゾ（株）製）、高度向高純度黒鉛粉（住友ア
ルミニウム製錬（株）製）、高純度人造黒鉛粉（（株）
エスイーシー製）、カーボンブラック（三菱化成製）な
どが適用できる。The black coloring pigment of the present invention includes conductive carbon black (manufactured by Lion Akzo Co., Ltd.), high-purity graphite powder for advanced use (Sumitomo Aluminum Smelting Co., Ltd.), high-purity artificial graphite powder (Co., Ltd.).
Applicable products are SSC) and carbon black (manufactured by Mitsubishi Kasei).
黒色着色顔料の配合比率は、シリコーン樹脂に対して、
１〜30％である。１％未満では着色性が劣るし、30％を
越えると塗料の粘度が高くなり、薄膜に塗装することが
不可能となる。The mixing ratio of the black color pigment is based on the silicone resin.
1 to 30%. If it is less than 1%, the coloring property will be poor, and if it exceeds 30%, the viscosity of the coating will be high, making it impossible to coat it in a thin film.
本発明の金属材は、加熱後にシリコーン樹脂皮膜の密着
性が著しく低下しない金属であれば適用可能であり、耐
熱性に優れたアルミめっき鋼板や、塗膜密着性に優れた
合金化亜鉛めっき鋼板などが好ましい。The metal material of the present invention can be applied as long as the adhesion of the silicone resin film does not significantly decrease after heating, an aluminum-plated steel sheet having excellent heat resistance, and an alloyed galvanized steel sheet having excellent coating film adhesion. Are preferred.
亜鉛めっき鋼板（合金化亜鉛めっき鋼板を除く）は塗膜
密着性に優れた金属板であるが、めっき層の融点が低
く、焼ばめ時の到達温度、加熱時間により適用不可の場
合がある。Galvanized steel sheets (excluding alloyed galvanized steel sheets) are metal sheets with excellent coating adhesion, but the melting point of the plating layer is low, so they may not be applicable depending on the temperature reached during heating and the heating time. .
本発明の黒色シリコーン樹脂被覆金属板の製造において
行なわれる塗装前処理として、金属表面を清浄かつ活性
化するために脱脂後、機械的研摩、化学研摩または電解
研摩により表面酸化皮膜の除去を行ない、ただちに、樹
脂を塗布・乾燥するのが望ましい。また、研摩表面に化
成処理皮膜として、皮膜中のクロムを５〜40mg/m2含む
クロム酸塩系、またはりン酸クロム酸塩系皮膜を形成さ
せた後、塗布・乾燥させれば、加工成形した際の加工部
・切断端面部の耐食性、および二次密着性をより向上さ
せることができる。As a coating pretreatment performed in the production of the black silicone resin-coated metal plate of the present invention, after degreasing to clean and activate the metal surface, mechanical polishing, chemical polishing or electrolytic polishing to remove the surface oxide film, It is desirable to apply and dry the resin immediately. Also, as a chemical conversion coating on the polished surface, a chromate-based coating containing 5-40 mg / m 2 of chromium in the coating, or a chromate-based phosphonate coating is formed, and then coated and dried to process. It is possible to further improve the corrosion resistance and the secondary adhesion of the processed portion and the cut end surface portion at the time of molding.
板厚0.6mmで、付着量が40g/m2（両面）である溶融アル
ミめっき鋼板を市販の脱脂剤で脱脂後、水洗を施して、
あるいは、脱脂、水洗後にリン酸クロム酸塩処理、水洗
を施して、風乾または、熱風により強制乾燥させた。After degreasing a hot-dip aluminized steel sheet with a plate thickness of 0.6 mm and an adhesion amount of 40 g / m 2 (both sides) with a commercially available degreasing agent, wash it with water,
Alternatively, after degreasing and washing with water, phosphoric acid chromate treatment and washing with water were performed, followed by air drying or forced drying with hot air.
また、板厚0.8mmで、付着量が60g/m2（片面）である合
金化亜鉛めっき鋼板を市販の脱脂剤で脱脂後、水洗を施
して、あるいは、脱脂、水洗後に、クロメート処理、水
洗を施して、風乾または、熱風により強制乾燥させた。In addition, after degreasing the alloyed galvanized steel sheet with a plate thickness of 0.8 mm and the adhesion amount of 60 g / m 2 (one side) with a commercially available degreasing agent and then washing with water, or after degreasing and washing with water, chromate treatment and water washing And dried by air or forcedly by hot air.
次に、下記のようにして調整したシリコーン樹脂被覆剤
に、導電性カーボンブラック（ａ）（ライオンアクゾ
（株）製：ケッチェンブラックEC−DJ600）を２％また
は高配向高純度黒鉛粉（ｂ）（住友アルミニウム製錬
（株）:POG−２）を10％配合した塗料を上記金属板にロ
ールコート法により塗布し、300℃で３分間乾燥し、水
冷または風乾した。Next, 2% of conductive carbon black (a) (Lion Akzo Co., Ltd .: Ketjen Black EC-DJ600) or highly oriented high purity graphite powder (b) was added to the silicone resin coating agent prepared as described below. ) (Sumitomo Aluminum Smelting Co., Ltd .: POG-2) was applied to the above metal plate by a roll coating method, dried at 300 ° C. for 3 minutes, and water-cooled or air-dried.
＜樹脂Ａ＞ Ph2SiCl2 30mol％、PhSiCl3 20mol％、Me2SiCl2 30mol
％およびMeSiCl3 20mol％の混合物をトリクロルエチレ
ンに溶解させ加水分解した後、トリクロルエチレンを留
去、重合して、不揮発分50％のキシレン溶液を調整し
た。この溶液の粘度（25℃）は50センチトークスで、水
酸基含有率1.0重量％、平均組成式Me0.8Ph0.8SiO1.165
（OH）0.07であった。<Resin A> Ph 2 SiCl 2 30mol%, PhSiCl 3 20mol%, Me 2 SiCl 2 30mol
% And 20 mol% of MeSiCl 3 were dissolved in trichlorethylene and hydrolyzed, then trichlorethylene was distilled off and polymerized to prepare a xylene solution having a nonvolatile content of 50%. The viscosity of this solution (25 ° C) is 50 centistokes, the hydroxyl group content is 1.0% by weight, and the average composition formula is Me 0.8 Ph 0.8 SiO 1.165.
(OH) was 0.07 .
＜樹脂Ｂ＞ Ph2SiCl2 20mol％、PhSiCl3 30mol％、Me2SiCl2 30mol
％およびMeSiCl3 20mol％の混合物を樹脂Ａと同様にし
て、不揮発分50％のキシレン溶液を調整した。溶液粘度
（25℃）は130センチストークスで、水酸基含有率0.5重
量％、平均組成式Me0.8Ph0.7SiO1.235（OH）0.03であっ
た。<Resin B> Ph 2 SiCl 2 20mol%, PhSiCl 3 30mol%, Me 2 SiCl 2 30mol
% And MeSiCl 3 20 mol% as in Resin A to prepare a 50% non-volatile xylene solution. The solution viscosity (25 ° C) was 130 centistokes, the hydroxyl group content was 0.5% by weight, and the average composition formula was Me 0.8 Ph 0.7 SiO 1.235 (OH) 0.03 .
＜樹脂Ｃ＞ PhMeSiCl2 30mol％、PhSiCl3 30mol％、Me2SiCl2 20mol
％およびMeSiCl3 20mol％の混合物を樹脂Ａと同様にし
て、不揮発分50％のキシレン溶液を調整した。溶液粘度
（25℃）は130センチトークスで、水酸基含有率0.5重量
％、平均組成式Me0.9Ph0.6SiO1.235（OH）0.03であっ
た。<Resin C> PhMeSiCl 2 30mol%, PhSiCl 3 30mol%, Me 2 SiCl 2 20mol
% And MeSiCl 3 20 mol% as in Resin A to prepare a 50% non-volatile xylene solution. The solution viscosity (25 ° C.) was 130 centistokes, the hydroxyl group content was 0.5% by weight, and the average composition formula was Me 0.9 Ph 0.6 SiO 1.235 (OH) 0.03 .
＜樹脂Ｄ＞ Ph2SiCl2 16mol％、PhSiCl3 16mol％、Me2SiCl2 24mol
％およびMeSiCl3 44mol％の混合物を樹脂Ａと同様にし
て、不揮発分50％のキシレン溶液を調整した。溶液粘度
（25℃）は150センチストークスで、水酸基含有率0.3重
量％、平均組成式Me0.92Ph0.48SiO1.29（OH）0.02であ
った。<Resin D> Ph 2 SiCl 2 16mol%, PhSiCl 3 16mol%, Me 2 SiCl 2 24mol
% And 44 mol% MeSiCl 3 in the same manner as in Resin A to prepare a xylene solution having a nonvolatile content of 50%. The solution viscosity (25 ° C.) was 150 centistokes, the hydroxyl group content was 0.3% by weight, and the average composition formula was Me 0.92 Ph 0.48 SiO 1.29 (OH) 0.02 .
＜樹脂Ｅ＞ PhSiCl3 40mol％、MeSiCl3 20mol％およびMe2SiCl2 40m
ol％の混合物を樹脂Ａと同様にして、不揮発分60％のキ
シレン溶液を調整した。溶液粘度（25℃）は20センチス
トークスで、水酸基含有率5.0重量％、平均組成式Me1.0
Ph0.4SiO1.155（OH）0.29であった。<Resin E> PhSiCl 3 40mol%, MeSiCl 3 20mol% and Me 2 SiCl 2 40m
The ol% mixture was treated in the same manner as for Resin A to prepare a xylene solution having a nonvolatile content of 60%. Solution viscosity (25 ° C) is 20 centistokes, hydroxyl group content 5.0% by weight, average composition formula Me 1.0
It was Ph 0.4 SiO 1.155 (OH) 0.29 .
＜樹脂Ｆ＞ Ph2SiCl2 37mol％、PhSiCl3 25mol％、Me2SiCl2 28mol
％およびMeSiCl3 10mol％の混合物を樹脂Ａと同様にし
て、不揮発分50％のキシレン溶液を調整した。溶液粘度
（25℃）は50センチストークスで、水酸基含有率0.7重
量％、平均組成式Me0.66Ph0.99SiO1.15（OH）0.05であ
った。<Resin F> Ph 2 SiCl 2 37mol%, PhSiCl 3 25mol%, Me 2 SiCl 2 28mol
% And MeSiCl 3 10 mol% were treated in the same manner as in Resin A to prepare a xylene solution having a nonvolatile content of 50%. The solution viscosity (25 ° C.) was 50 centistokes, the hydroxyl group content was 0.7% by weight, and the average composition formula was Me 0.66 Ph 0.99 SiO 1.15 (OH) 0.05 .
＜樹脂Ｇ＞ PhSiCl3 20mol％、Me2SiCl2 30mol％およびMeSiCl3 50m
ol％の混合物を樹脂Ａと同様にして、不揮発分50％のキ
シレン溶液を調整した。溶液粘度（25℃）は150センチ
ストークスで、水酸基含有率0.5重量％、平均組成式Me
1.1Ph0.2SiO1.34（OH）0.02であった。<Resin G> PhSiCl 3 20mol%, Me 2 SiCl 2 30mol% and MeSiCl 3 50m
The ol% mixture was treated in the same manner as in Resin A to prepare a xylene solution having a nonvolatile content of 50%. Solution viscosity (25 ° C) is 150 centistokes, hydroxyl content 0.5% by weight, average composition formula Me
It was 1.1 Ph 0.2 SiO 1.34 (OH) 0.02 .
次に、以上のように製造したシリコーン樹脂被覆金属板
に対して、次のような試験を実施した。Next, the following test was performed on the silicone resin-coated metal plate manufactured as described above.
（１） 180゜曲げ加工試験 未加熱の試験片に、試験片の板厚２倍の板をはさんだ18
0゜曲げ加工（2t曲げ）および板厚の４倍の板をはさん
だ180゜曲げ加工（4t曲げ）を施し、曲げ加工部をテー
プはくり試験に供して皮膜の密着性を評価した。(1) 180 ° bending test A plate with twice the thickness of the test piece was sandwiched between unheated test pieces 18
A 0 ° bending process (2t bending) and a 180 ° bending process (4t bending) sandwiching a plate 4 times the plate thickness were performed, and the bending part was subjected to a tape peeling test to evaluate the adhesion of the coating.
（２） 180゜曲げ加工部の耐熱性 試験片に上記（１）項のように180゜曲げ加工を施し、
電気炉（マッフル炉）中で加熱し、材料温度が300℃に
到達してから100時間保持した。加熱後、大気中で放冷
した後、曲げ加工部をテープはくり試験に供し、皮膜の
密着性を評価した。(2) Heat resistance of 180 ° bent part The test piece was bent 180 ° as described in (1) above,
The material was heated in an electric furnace (muffle furnace) and held for 100 hours after the material temperature reached 300 ° C. After heating and allowing to cool in the atmosphere, the bent portion was subjected to a tape peeling test to evaluate the adhesion of the coating.
（３） スポット溶接試験 ２枚の試験片の樹脂面同志を合わせた状態で、スポット
溶接を、加圧力300kgf、溶接電流8kA、通電時間は溶融
アルミめっき鋼板の場合10サイクル、合金化亜鉛めっき
鋼板の場合７サイクル、電極チップ径4.5mmの条件で行
なった。(3) Spot welding test In the state where the resin surfaces of two test pieces are matched, spot welding is applied with a pressing force of 300 kgf, a welding current of 8 kA, and the energization time is 10 cycles in the case of hot-dip aluminized steel sheet, galvannealed steel sheet. In the case of, the test was carried out for 7 cycles under the condition that the electrode tip diameter was 4.5 mm.
以上の試験結果を、製造条件とともに第１表に示す。ま
た、本発明の効果を明らかにするため、比較例を第２表
に示す。The above test results are shown in Table 1 together with manufacturing conditions. Comparative examples are shown in Table 2 in order to clarify the effect of the present invention.
〔発明の効果〕 本発明は、スポット溶接による成形加工が可能であり、
耐熱性に優れた性能を示す材料である。 EFFECTS OF THE INVENTION The present invention is capable of forming processing by spot welding,
It is a material that has excellent heat resistance.
成形後塗燥する方式は、すべて手作業となり、著しいコ
ストアップの原因になっているが、本発明のプレコート
材料を使用することにより大幅なコストダウンとなる。Although the method of coating and drying after molding is a manual operation and causes a significant increase in cost, the use of the precoat material of the present invention results in a significant cost reduction.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 菅原 広志 千葉県市川市高谷新町７番地の１ 日新製 鋼株式会社新材料研究所内 (72)発明者 増原 憲一 千葉県市川市高谷新町７番地の１ 日新製 鋼株式会社新材料研究所内 審査官 鴨野 研一 (56)参考文献 特開 昭62−132575（ＪＰ，Ａ) 特開 昭61−195831（ＪＰ，Ａ) 特開 昭62−7538（ＪＰ，Ａ) 特公 昭43−8623（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroshi Sugawara, Inventor Hiroshi Sugawara, No. 1, Takatani Shinmachi, Ichikawa City, Chiba Prefecture, Nisshin Steel Co., Ltd. (72) Inventor Kenichi Masuhara 1 Nisshin Steel Co., Ltd. New Material Research Laboratory Examiner Kenichi Kamono (56) Reference JP 62-132575 (JP, A) JP 61-195831 (JP, A) JP 62-7538 (JP , A) Japanese Patent Publication Sho 43-8623 (JP, B1)
Claims (1)
基であり、a,bは、0.6≦ａ≦1.3,0.35≦ｂ≦0.95、かつ
1.4≦ａ＋ｂ≦1.7を満たす正数、ｃは本化合物中におけ
るケイ素原子に結合した水酸基の占める比率が0.01〜3.
0重量％となるような値を示す）で示されるオルガノポ
リシロキサン樹脂に、黒色着色顔料を配合させた塗料を
皮膜厚0.5〜10μｍになるように金属板に塗布、乾燥し
てなる黒色シリコーン樹脂被覆金属板。1. A general formula (In the formula, R is an unsubstituted or substituted alkyl group or alkenyl group, a and b are 0.6 ≦ a ≦ 1.3, 0.35 ≦ b ≦ 0.95, and
A positive number satisfying 1.4 ≦ a + b ≦ 1.7, and c is a ratio of hydroxyl groups bonded to silicon atoms in the compound of 0.01 to 3.
A black silicone resin obtained by applying a coating material in which a black coloring pigment is mixed to an organopolysiloxane resin represented by 0% by weight) to a metal plate to a film thickness of 0.5 to 10 μm and drying. Coated metal plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63109065A JPH0737107B2 (en) | 1988-05-06 | 1988-05-06 | Black silicone resin coated metal plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63109065A JPH0737107B2 (en) | 1988-05-06 | 1988-05-06 | Black silicone resin coated metal plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01280546A JPH01280546A (en) | 1989-11-10 |
| JPH0737107B2 true JPH0737107B2 (en) | 1995-04-26 |
Family
ID=14500707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63109065A Expired - Fee Related JPH0737107B2 (en) | 1988-05-06 | 1988-05-06 | Black silicone resin coated metal plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737107B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015029837A1 (en) * | 2013-08-28 | 2015-03-05 | ディップソール株式会社 | Black coupling member for vehicles, having excellent corrosion resistance and black appearance |
| CN105518182A (en) * | 2013-08-28 | 2016-04-20 | 本田技研工业株式会社 | Black coating film-forming vehicle component and/or fastening component, and manufacturing method therefor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2584109B2 (en) * | 1990-06-11 | 1997-02-19 | 松下冷機株式会社 | Paint for water-repellent coating and heat exchanger coated with the paint |
| JP5967890B2 (en) * | 2011-09-30 | 2016-08-10 | 日本タングステン株式会社 | Film-like inorganic material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61195831A (en) * | 1985-02-25 | 1986-08-30 | 住友金属工業株式会社 | Corrosion-protective coated metallic product |
| JPS627538A (en) * | 1985-07-03 | 1987-01-14 | 住友金属工業株式会社 | Colored steel plate having excellent high temperature-resistant corrosiveness |
| JPS62132575A (en) * | 1985-12-03 | 1987-06-15 | Showa Denko Kk | Painting method |
-
1988
- 1988-05-06 JP JP63109065A patent/JPH0737107B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015029837A1 (en) * | 2013-08-28 | 2015-03-05 | ディップソール株式会社 | Black coupling member for vehicles, having excellent corrosion resistance and black appearance |
| JP2015045061A (en) * | 2013-08-28 | 2015-03-12 | ディップソール株式会社 | Black fastening member for vehicle having high corrosion resistance with excellent black color |
| CN105518182A (en) * | 2013-08-28 | 2016-04-20 | 本田技研工业株式会社 | Black coating film-forming vehicle component and/or fastening component, and manufacturing method therefor |
| CN105579617A (en) * | 2013-08-28 | 2016-05-11 | 迪普索股份公司 | Black coupling member for vehicles, having excellent corrosion resistance and black appearance |
| CN105518182B (en) * | 2013-08-28 | 2018-01-26 | 本田技研工业株式会社 | The vehicle part and/or link part and its manufacture method of black epithelium |
| US10005104B2 (en) | 2013-08-28 | 2018-06-26 | Honda Motor Co., Ltd. | Black coating film-forming vehicle component and/or fastening component, and manufacturing method thereof |
| US10240237B2 (en) | 2013-08-28 | 2019-03-26 | Dipsol Chemicals Co., Ltd. | Black coupling member for vehicles, having excellent corrosion resistance and black appearance |
| CN105579617B (en) * | 2013-08-28 | 2019-05-10 | 迪普索股份公司 | Corrosion resistance and the excellent vehicle black secure component of appearance of black |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01280546A (en) | 1989-11-10 |
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