JPH01280546A - Black silicon resin coated metallic plate - Google Patents
Black silicon resin coated metallic plateInfo
- Publication number
- JPH01280546A JPH01280546A JP10906588A JP10906588A JPH01280546A JP H01280546 A JPH01280546 A JP H01280546A JP 10906588 A JP10906588 A JP 10906588A JP 10906588 A JP10906588 A JP 10906588A JP H01280546 A JPH01280546 A JP H01280546A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- black
- metallic plate
- formula
- colored pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 title claims abstract description 17
- 229910021418 black silicon Inorganic materials 0.000 title 1
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229920002050 silicone resin Polymers 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 5
- 238000004040 coloring Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 238000003466 welding Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910021383 artificial graphite Inorganic materials 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 229910000680 Aluminized steel Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
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 Fields] When used in environments where heating is applied after molding, such as automobile mufflers, exhaust duct materials and partition plates for hot air heaters, and tension bands for TVs. The present invention relates to a resin-coated metal plate with a black design suitable for use in applications requiring heat resistance, workability, spot weldability, etc., such as when a heating process is included during the molding process.
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）しだ後または、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 to a TV tube, black paint was applied to give it a decorative appearance.
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。Additionally, pre-coated materials with heat resistance, workability, and black design are used to eliminate post-painting operations and reduce costs.
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６ｌ−１７
７２３８）。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 that have heat resistance, processability, and black design properties are already known (Japanese Patent Laid-Open No. 61-17
7238). However, considering the corrosion resistance of these materials,
Although it has a film thickness of about 20 μm and has excellent insulation properties, it has the disadvantage that it is impossible to mold 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。Furthermore, in many cases, molded products cannot be treated before painting, resulting in quality defects such as poor adhesion of the paint film.
本発明は、一般式Ｒｅ（ＣＪｓ）ｂｓｉｏ ４−ａ−ｂ
−ｃ（０１１）ｃ（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りＶ ｔ
’Ｊｒ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 Re(CJs) bsio 4-a-b
-c(011)c (in the formula, R is an unsubstituted or substituted alkyl group or alkenyl group, and a and b are 0.6≦a≦
1.3゜0, 35≦b≦0.95, and 1.4≦a+
C is a positive number satisfying b≦1.7, and C is a ratio of 0.01 to 3.
V t
'Jr is applied to a metal plate to a film thickness of 0.5 to 10 μm and dried.
一般式Ｒ’ ｆｉｓｉ０４．（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３０〜７
０ｍｏ１％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２μｍ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 R' fisi04. (In the formula, R' is generally a phenyl group or a methyl group) The heat-resistant silicone resin has a content of phenyl groups in the total organic groups of 30 to 7.
It is said that those with a content of 0 mo1% and a value of n of 1.2 to 1.8 have excellent heat resistance. However, such a resin requires 30 minutes or more to dry and harden, and if the film thickness is made flexible and less than 2 μm, repellency or uncoated areas will occur, so it has not been possible to reduce the film thickness 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・パーミェーション・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■製ＨＬＣ８０２Ａ 、カラ
ムＴＳＫ−Ｇｒ！Ｌ ＧＭ）１６ 、Ｇ４０００１（＆
、Ｇ２０００１１．２本、計４本、溶媒テトラヒドロフ
ラン、流ｆｔ １．２ ｒａＩｌ／ｎ＋ｉｎ 、圧力５
． Ｏｋｇｆ／ｃｎ＋” 、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
ジキや未嘘布部分が発生しなくなり、かつ一般式Ｒ’
、ＳｉＯ，＝工におけるｎの値を１．４〜１．７、かつ
フェニル基含有率を２５〜５５ｍｏ１％（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３５〜５５ｍｏ
１％（本発明の一般式ではｂが０．４９≦ｂ≦０．９５
）にし、そのフェニル基が（ＣＪｓ）ｚｓｉｏ単位を５
ｍｏ１％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。As a result of various studies, the present inventors found that the polystyrene equivalent molecular weight of silicone resin was measured by gel permeation chromatography (hereinafter abbreviated as GPC) (Measurement conditions: Measuring instrument: Toyo Soda HLC802A, column TSK-Gr!L) GM) 16, G40001 (&
, G200011.2 bottles, total 4 bottles, solvent tetrahydrofuran, flow ft 1.2 raIl/n+in, pressure 5
．． Okgf/cn+”, detector refractive index and UV,
If the following resins are made to have a molecular weight ranging from a low molecular weight of about 103 to a high molecular weight of about 106 under the same conditions (same conditions), the flowability to the plated steel sheet and the cohesive force of the film will increase, resulting in repellency and non-woven areas. and the general formula R'
, when the value of n in SiO, = engineering is 1.4 to 1.7 and the phenyl group content is 25 to 55 mo1% (b in the general formula of the present invention is 0.35≦b≦0.95). It has been found that not only flexibility but also heat resistance and thermal shock resistance are significantly improved. In particular, the phenyl group content is 35 to 55 mo.
1% (in the general formula of the present invention, b is 0.49≦b≦0.95
), and its phenyl group converts (CJs)zsio unit into 5
It has been found that the film containing 1% or more of mo is flexible, has a smooth surface, and exhibits excellent heat resistance and corrosion resistance even when the film thickness is reduced 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１０６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。The resin of the present invention was developed based on this knowledge, and has the general formula shown above, and is an organoplastic resin whose molecular weight ranges from a low molecular weight of about 103 to a high molecular weight of about 106 in polystyrene equivalent molecular weight measured by GPC. Contains polysiloxane resin.
ここで一般式中の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、非置換アルギル基
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。Here, R in the general formula is an unsubstituted or substituted alkyl group or alkenyl group as described above, and examples of the unsubstituted argyl group include methyl, ethyl, and propyl groups, and examples of the unsubstituted alkenyl group include vinyl. group, allyl group, etc.
さらに置換アルキル基としてはクロロメチル基、３．３
．３−１−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。Furthermore, as substituted alkyl groups, chloromethyl group, 3.3
．． Examples include 3-1-lifluoropropyl group. Among these, preferred are alkyl groups, and particularly preferred are methyl groups.
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０．０
１〜０．２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 those whose degree of polymerization is adjusted to have a hydroxyl group content of less than 0.01% by weight have poor adhesion to plated steel sheets, and 3.0% by weight.
Those adjusted to exceed 100 μm have poor curing properties, making it impossible to form a film at high temperatures in a short time, and the degree of polymerization is too low, making it difficult to form a uniform film when made into a thin film of 0.5 to 2.0 μm. This is because it does not form a film. Especially film thickness and adhesion,
To maintain a balance with hardenability, the hydroxyl group content should be 0.2~
2.0% by weight (0.0 of the value of C in the general formula of the present invention)
It is preferable to adjust the degree of polymerization so that the degree of polymerization is approximately 1 to 0.2.
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、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−）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、工業用ガソリン等の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 plate, it is usually used after being dissolved in a solvent. Examples of solvents include aromatic organic solvents such as benzene, toluene, xylene, and ethylbenzene, chlorine-containing organic solvents such as trichlorethylene, 1,1.1-)lychloroethane, carbon tetrachloride, and chloroform, hexane,
It is preferable to use an aliphatic hydrocarbon solvent such as ligroin or industrial gasoline alone or in combination, 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Ｐｈ、ＳｉＣｌ
、 、ＰｈＳｉＣｌ 、 、Ｍｅ、ＳｉＣｌ ２ＭｅＳ
ｉＣ１２３、ＰｈＭｅＳｉＣ１ｚ 、Ｃ，ｌ１６ＳｉＣ
ｌ 、、ｃｏ３ｃｈ□ＣＩｌ□５ｉＣ１ｓ 、ＣＦ３Ｃ
ＩＩ□ＣＩｌ□ＳｔＣｊ！ ３ 、ＳｔＣｊ！ ４、Ｍ
ｅ＝ＳｉＣｆが、またアルコキシシランとしては、（Ｃ
ｚｌｌｓＯ）４ｓｉ、 ＰｈｚＳｉＣＯＭｅ）ｚ 、Ｐ
ｈＳｉ（ＯＭｅ）ｓ、Ｍｅ、Ｓｉ（ＯＭｅ）ｚ 、Ｍｅ
Ｓｉ（ＯＭｅ）ｚ、Ｐｈ２ＭｅＳｉＯＣ，ｌ１５、Ｍｅ
、ＳｉＯＭｅ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ＰｈｔＳｉＣｌ ｚあ
るいはＰｈ ｚＳ ｉ （ＯＭｅ） ｚを５ ｍｏ１％
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 contains 1.4 to 1.0% of the desired organic group per silicon.
7 chlorosilanes alone or as a mixture and/or
Alternatively, it can be obtained by hydrolyzing alkoxysilanes alone or in mixtures in the above-mentioned solvents, and polymerizing if necessary. Examples of chlorosilane include Ph, SiCl
, ,PhSiCl, ,Me,SiCl2MeS
iC123, PhMeSiC1z, C, l16SiC
l,,co3ch□CIl□5iC1s, CF3C
II□CIl□StCj! 3. StCj! 4.M
e=SiCf, and as the alkoxysilane, (C
zllsO)4si, PhzSiCOMe)z, P
hSi(OMe)s, Me, Si(OMe)z, Me
Si(OMe)z, Ph2MeSiOC, l15, Me
, SiOMe, etc. (Me is a methyl group, and pH is a phenyl group). Among these, especially PhtSiCl z or Ph zS i (OMe) z at 5 mo1%
The product obtained by hydrolyzing the silane mixture containing the above has excellent 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ａ＠製）、高配向高純度黒鉛粉（住人アル
ミニウム製ｌｌｌ１製）、高純度人造黒鉛粉（＠ニスイ
ージー製）、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 a @), highly oriented high purity graphite powder (manufactured by Jusumi Aluminum Ill1), high purity artificial graphite powder (manufactured by Niseasy), and carbon black (manufactured by Mitsubishi Chemical products) etc. can be applied.
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杉である。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 blending ratio of black color pigment to silicone resin is
1 to 30 cedars. If it is less than 1%, the coloring properties will be poor, and 30
%, the viscosity of the paint becomes high and it becomes impossible to apply 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 to any metal that does not significantly reduce the adhesion of the silicone resin film after heating, such as an aluminized steel sheet with excellent heat resistance and an alloyed galvanized steel sheet with excellent coating adhesion. etc. are preferable.
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 and may not be applicable depending on the temperature reached during shrink fitting and 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５〜４０■／ Ｉ
ｌｇ含むクロム酸塩系、またはリ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 pre-painting treatment performed in the production of the black silicone resin coated metal plate of the present invention, in order to clean and activate the metal surface, after degreasing, the surface oxide film is removed by mechanical polishing, chemical polishing or electrolytic polishing, It is desirable to apply and dry the resin immediately. In addition, as a chemical conversion coating on the polished surface, chromium in the coating is added to 5 to 40 μ/I.
If a chromate-based or phosphate-chromate-based film containing Lg is formed, then applied and dried, the corrosion resistance of processed parts and cut end surfaces during processing and molding, and secondary adhesion will be further improved. can be done.
板厚０．６１１で、付着量が４０ｇ／ｍ”（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。A hot-dip aluminized steel plate with a thickness of 0.611 and a coating weight of 40 g/m'' (both sides) was degreased with a commercially available degreaser and then washed with water, or treated with phosphate chromate after degreasing and washing with water. It was washed with water and then air-dried or force-dried with hot air.
また、板厚０．８■ｌ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, an alloyed galvanized steel sheet with a thickness of 0.8 l and a coating weight of 60 g/m2 (one side) was degreased with a commercially available degreaser and then washed with water, or after degreasing and washing with water, chromate treatment was performed. , washed with water, and air-dried or force-dried with 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（δ）（ライオンアクゾ■
製：ケソチェンブラックＥＣ−ＤＪ６００）を２％また
は高配向高純度黒鉛粉（ｂ）（住人アルミニウム製錬＠
： 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, conductive carbon black (δ) (Lion Akzo™) was applied to the silicone resin coating prepared as described below.
Manufactured by: Kesochen Black EC-DJ600) 2% or highly oriented high purity graphite powder (b) (resident aluminum smelting @
A paint containing 10% POG-2) was applied to the metal plate by a roll coating method, dried at 300°C for 3 minutes, and then cooled in water or air-dried.
〈樹脂Ａ〉
Ｐｈ、Ｓｉ（／！、 ３０ ｍｏ１％、Ｐｈ５ｉＣ１ｚ
２０ ｍｏ１％、Ｍｅ、５ｉＣｊ！、 ３０ ｍｏ１
％およびＭｅＳｉＣ１＝ ２０ ｍｏ１％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。<Resin A> Ph, Si (/!, 30 mo1%, Ph5iC1z
20 mo1%, Me, 5iCj! , 30 mo1
% and MeSiC1 = 20 mo1% mixture was dissolved in trichlorethylene and hydrolyzed, then trichlorethylene was distilled off and polymerized to prepare a xylene solution with a nonvolatile content of 50%.
この溶液の粘度（２５℃）は５０センチストークスで、
水酸基含有率１．０重量％、平均組成式％式％
％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ＭｅＯ，ＢＰｈｏ、 ７ＳｉＯ＋、 ｚ：＋ｓ （
０１１） ｏ、 ｏｓであった。The viscosity of this solution (at 25°C) is 50 centistokes.
A xylene solution with a non-volatile content of 50% was prepared using a mixture having a hydroxyl group content of 1.0% by weight and an average compositional formula of 1.0% by weight in the same manner as Resin A. The solution viscosity (at 25°C) is 130 centistokes, the hydroxyl group content is 0.5% by weight, and the average compositional formula is MeO, BPho, 7SiO+, z:+s (
011) o, os.
〈樹脂Ｃ〉
ＰｈＭｅＳｉＣｊ２ｚ ３０ ｍｏ１％、Ｐｈ５ｔ（１
！ａ ３０ ｍｏ１％、ＭｅｚＳｉＣｆｆｚ ２０ ｍ
ｏ１％およびＭｅＳｉ（ｕｓ ２ Ｏｎ＋ｏ１％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Ｍｅ
ｏ、 、Ｐｈｏ、 、ｓｉＯ＋、 ｚ３ｓ （０１１）
ｏ、 ｏｓであった。<Resin C> PhMeSiCj2z 30 mo1%, Ph5t (1
! a 30 mo1%, MezSiCffz 20 m
A xylene solution with a non-volatile content of 50% was prepared using a mixture of O1% and MeSi (us2On+O1%) in the same manner as Resin A.The solution viscosity (at 25°C) was 130 centistokes, and the hydroxyl group content was 0.5% by weight. , average composition formula Me
o, , Pho, , siO+, z3s (011)
It was o, os.
〈樹脂Ｄ〉
Ｐｈ２Ｓｉ（１，１６ｍｏ１％、Ｐｈ５ｉ（／！ｘ １
６ ｍｏ１％、Ｍｅ２Ｓｉ（Ｊｚ ２４ ｍｏ１％およ
びＭｅＳｉＣｌ３４４ ｍｏ１％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。<Resin D> Ph2Si (1,16mo1%, Ph5i(/!x 1
A xylene solution with a non-volatile content of 50% was prepared using a mixture of 6 mo1%, Me2Si(Jz24 mo1% and MeSiCl344 mo1%) in the same manner as in Resin A.
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Ｍｅｏ、 ｖｚＰｈ
ｏ、 ５ｓｓｉｏ＋、 ｚＪＯＨ） Ｏ，Ｏ！であった
。The solution viscosity (25°C) is 150 centistokes, the hydroxyl group content is 0.3% by weight, and the average composition formula is Meo, vzPh.
o, 5ssio+, zJOH) O,O! Met.
〈樹脂Ｅ〉
Ｐｈ５ｉＣｊ！ｚ ４０ ｍｏ１％、ＭｅＳｉＣｊ’ｓ
２０ ｍｏ１％および門ｅｚｓｉｃｆｆｚ ４ Ｑ
ｍ０１％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２
０センチストークスで、水酸基含有率５．０重量％、平
均組成式％式％
％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Ｍｃｏ、 ５６Ｐｈｏ、 ｑ、ｓｉｏ＋、 ＋ ｓ
（Ｏｔｌ） ｏ、 ｏｓであった。<Resin E> Ph5iCj! z 40 mo1%, MeSiCj's
20 mo1% and gate ezsicffz 4 Q
A mixture of m01% was made in the same manner as resin A, and the nonvolatile content was 60
% xylene solution was prepared. Solution viscosity (25℃) is 2
A xylene solution having a non-volatile content of 50% was prepared in the same manner as Resin A using a mixture having a hydroxyl group content of 5.0% by weight and an average compositional formula of 0 centistokes. The solution viscosity (at 25°C) is 50 centistokes, the hydroxyl group content is 0.7% by weight, and the average compositional formula is Mco, 56Pho, q, sio+, +s
(Otl) It was o, os.
〈樹脂Ｇ〉
Ｐｈ５ｉＣ１！ｓ ２０ ｍｏ１％、ＭｅｚＳｉ（／！
＝ ３０ ｍｏ１％およびＭｅＳｉＣｌ、 ５０ ｍｏ
１％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％式％０
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。<Resin G> Ph5iC1! s 20 mo1%, MezSi(/!
= 30 mo1% and MeSiCl, 50 mo
A 1% mixture was prepared in the same manner as Resin A to prepare a xylene solution with a non-volatile content of 50%. Solution viscosity (25℃) is 150
centistokes, hydroxyl group content 0.5% by weight, average compositional formula %formula %0 Next, the following tests were carried out on the silicone resin coated metal plate produced as described above.
（１１１８０’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１
８０″曲げ加工（２を曲げ）および板厚の４倍の板をは
さんだ１８０°曲げ加工（４を曲げ）を施し、曲げ加工
部をテープばくり試験に供して皮膜の密着性を評価した
。(11180' bending test A plate twice the thickness of the test piece was sandwiched between the unheated test piece.
80" bending (bending 2) and 180° bending (bending 4) with plates 4 times the thickness of the plate were performed, and the bent portion was subjected to a tape peeling test to evaluate the adhesion of the film. .
（２）１８０°曲げ加工部の耐熱性
試験片に上記（１１項のように１８０”曲げ加工を施し
、電気炉（マツフル炉）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。(2) The heat resistance test piece of the 180° bent part was subjected to 180" bending as described above (Section 11), heated in an electric furnace (Matsufuru furnace), and the material temperature reached 300.
After reaching the temperature, the temperature was maintained for 100 hours.
加熱後、大気中で放冷した後、曲げ加工部をテープばく
り試験に供し、皮膜の密着性を評価した。After heating and cooling in the atmosphere, the bent portion was subjected to a tape peeling test to evaluate the adhesion of the film.
（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、ｔｉチップ径４．５
鶴の条件で行なった。(3) Spot welding test With the resin surfaces of the two test pieces aligned, spot welding was carried out at a pressure of 300 kgf, a welding current of 8 kA, and an energization time of 10 cycles for hot-dip aluminized steel sheets, and an alloyed galvanized steel sheet. 7 cycles for ti tip diameter 4.5
This was done under Tsuru's conditions.
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 the manufacturing conditions, and in order to clarify the effects of the present invention, comparative examples are shown in Table 2.
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。The present invention can be formed by spot welding,
It is a material that exhibits 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。The method of painting after molding requires all manual work and causes a significant increase in cost, but the use of the precoat material of the present invention results in a significant cost reduction.
Claims (1)
＿−＿ｂ＿−＿ｃ＿／＿２（ＯＨ）＿ｃ（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、乾燥してなる黒色シリコーン樹脂被覆金
属板。General formula R_a(C_6H_5)_bSiO_4_-_a
___b_-_c_/_2(OH)_c (wherein R is an unsubstituted or substituted alkyl group or alkenyl group, a,
b is 0.6≦a≦1.3, 0.35≦b≦0.95,
and a positive number satisfying 1.4≦a+b≦1.7, c is a value such that the proportion of hydroxyl groups bonded to silicon atoms in this compound is 0.01 to 3.0% by weight) A black silicone resin-coated metal plate is obtained by coating a metal plate with a paint containing organopolysiloxane resin mixed with a black coloring pigment to a film thickness of 0.5 to 10 μm, and drying the coating.
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 true JPH01280546A (en) | 1989-11-10 |
| JPH0737107B2 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0445181A (en) * | 1990-06-11 | 1992-02-14 | Matsushita Refrig Co Ltd | Composition for water-repellent coating and heat exchanger coated with the same composition |
| JP2013079157A (en) * | 2011-09-30 | 2013-05-02 | Nippon Tungsten Co Ltd | Membranous inorganic material |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (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
Patent Citations (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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0445181A (en) * | 1990-06-11 | 1992-02-14 | Matsushita Refrig Co Ltd | Composition for water-repellent coating and heat exchanger coated with the same composition |
| JP2013079157A (en) * | 2011-09-30 | 2013-05-02 | Nippon Tungsten Co Ltd | Membranous inorganic material |
| 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 |
| 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 |
|---|---|
| JPH0737107B2 (en) | 1995-04-26 |
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