TWI269805B - Surface coating material - Google Patents
Surface coating material Download PDFInfo
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- TWI269805B TWI269805B TW089112298A TW89112298A TWI269805B TW I269805 B TWI269805 B TW I269805B TW 089112298 A TW089112298 A TW 089112298A TW 89112298 A TW89112298 A TW 89112298A TW I269805 B TWI269805 B TW I269805B
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- emulsion
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Description
1269805 A7 B7 經濟部智慧財產局員工消費合作社印制取 1 五、發明說明() [發明領域] 本發明係有關一種在自己交聯型之水条乳液中混合有 聚矽氧烷条化合物、氟条化合物、聚乙烯条化合物所成 群之潤滑性化合物的水条包覆用組成物、另含有酸性化 合物之該組成物,即使該組成物在60〜300 °C下烘烤所 得的高硬度、良好的耐污染性、常溫與高溫之潤滑性優 異的表面包覆材料。 [先前技術] 稱為乳液、懸浮液、乳膠等之液狀介質分散液,自古 以來廣為利用做為水性塗料、黏接劑、紙塗覆劑、皮革 之素質調整劑、水泥用混合劑、薄膜平滑劑、纖維之黏 接劑等。做為水性塗料塗覆於銅板或樹脂板等以形成塗 膜時,要求具塗膜之耐刮傷性、耐污染性、耐厚性、綱 板或樹脂板間之非黏接住、良好的外觀,最近為省略機 械加工時之塗油需具潤滑性。另外,視其用途亦要求具 耐溶劑性、耐鹼溶出性。 為滿足此等之要求時必須使塗膜變硬、且潤滑性提高 ,惟以習知之水条乳液,不易使塗膜變硬。而且,為提 高潤滑性時考慮在水条乳液中容易混合潤滑劑,惟一般 使用的潤滑劑與水性乳液之混合性不佳、大多於數曰後 或瞬間凝聚一起。此外,連續進行機械加工時,加工機 槭經加熱而成高溫時塗膜無法伴隨具高溫潤滑性、會有 所謂刮痕之問題或必須變更機槭加工條件之問題。 因此目前使具有蜜胺、環氧基、聚胺甲酸酯等之交聯 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -ϋ n I i^i ϋ ϋ .ϋ 一 口、^ ϋ I I (請先閱讀背面之注意事項再填寫本頁) 線一 1269805 A7 經濟部智慧財產局員工消費合作社印製 Β7 2 五、發明說明() 性成份的有機溶劑条塗料在2 〇 0 Ό〜3 0 (TC之高溫下烘烤 ,製得硬且潤滑性佳的塗膜,惟必須回收揮發的有機溶 劑或為得高溫必須使用較大的爐〇 3外,於曰本待開平 11-80485號公報中掲示之發明傺為自己交聯的水条乳液 ,惟該發明之自己交聯性單體之反應性低、在低溫下之 烘烤性不佳,且沒有掲示任何有關潤滑性者。 [發明解決之問題] 本發明之目的傺為解決上述習知技術的缺點,且提供 卽使在完全水条、在低溫下烘烤時可形成具高硬度、良 好的耐污染性及外觀、在常溫及高溫下之潤滑性能優異 的皮膜之包覆用組成物以及以該皮膜被覆的表面包覆材 料。 [解決課題之手段】 為解決上述之問題,本發明僳由下述之構成所成。 換言之,本發明係為使2〜30重量%乙烯聚合性之自己 交聯性單體與其它的共聚合性單體在非聚合性乳化削存 在下共聚合所成的丙烯酸条共聚物之水条乳液,與對上 述水条乳液之固成分而言以2〜10重量:《選自聚矽氧烷条 化合物、氟条化合物、聚乙烯条化合物所成群的潤滑性 化合物為必須成分〇另外,於該組成物中對上逑水条乳 液之固成分而言亦含有0.5〜10重量% —種以上選自磷 酸条化合物、硫酸、硝酸、鹽酸之酸性化合物,且自己 交聯性單體偽為選自Ν-羥基烷基(甲基)丙烯醯胺、Ν-甲 氧基烷基(甲基)丙嫌醯胺、(甲塞)丙烯酸環氧丙酯者。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----------1 — -----Γ (請先閱讀背面之注意事項再填寫本頁) I —訂 ---- ----Ί 線®- 12698〇5 A71269805 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed 1 V. Inventive Note () Field of the Invention The present invention relates to a polyoxonane compound and fluorine mixed in a self-crosslinking type of water-strip emulsion. a composition for coating a water bar of a lubricious compound in which a strip compound or a polyethylene strip compound is contained, and a composition containing an acidic compound, even if the composition is baked at 60 to 300 ° C, and has a high hardness, A surface coating material excellent in stain resistance, excellent in lubricity at normal temperature and high temperature. [Prior Art] A liquid medium dispersion called an emulsion, a suspension, a latex, etc., has been widely used as an aqueous coating, an adhesive, a paper coating agent, a quality adjuster for leather, a cement mixture, and the like since ancient times. Film smoothing agent, fiber bonding agent, and the like. When a water-based paint is applied to a copper plate or a resin plate or the like to form a coating film, scratch resistance, stain resistance, thickness resistance of the coating film, non-sticking between the plates or the resin sheets, and good properties are required. Appearance, recently, it is necessary to lubricate oil for omission of machining. In addition, solvent resistance and alkali-resistant dissolution are required depending on the application. In order to satisfy these requirements, it is necessary to make the coating film hard and to improve the lubricity, but it is difficult to make the coating film hard by the conventional water-strip emulsion. Further, in order to improve the lubricity, it is considered that the lubricant is easily mixed in the water ray emulsion, but the lubricant which is generally used has poor miscibility with the aqueous emulsion, and is often agglomerated after several hours or instantaneously. In addition, when machining is continuously performed, when the processing machine is heated to a high temperature, the coating film cannot be accompanied by high-temperature lubricity, there is a problem of scratching, or it is necessary to change the processing conditions of the maple. Therefore, the cross-linked paper with melamine, epoxy, polyurethane, etc. is currently applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - ϋ n I i^i ϋ ϋ .ϋ One, ^ ϋ II (please read the note on the back and fill out this page) Line 1269805 A7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Β 7 2 V. Invention Description () Organic solvent strip coating for sexual ingredients in 2 〇 0 Ό~3 0 (The TC is baked at a high temperature to obtain a hard and lubricious coating film, but it is necessary to recover the volatile organic solvent or to use a larger furnace 3 for high temperature. The invention shown in the publication No. 11-80485 is a self-crosslinking water-strip emulsion, but the self-crosslinking monomer of the invention has low reactivity, poor baking at low temperatures, and does not indicate any lubrication. [Problem to be Solved by the Invention] The object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a high hardness and good stain resistance when baked at a full water bar and at a low temperature. Appearance, excellent lubrication performance at normal temperature and high temperature The film coating composition and the surface coating material coated with the film. [Means for Solving the Problem] In order to solve the above problems, the present invention is constituted by the following constitution. In other words, the present invention is to make 2 ~30% by weight of ethylene polymerizable self-crosslinkable monomer and other copolymerizable monomers copolymerized in the presence of non-polymeric emulsion, the aqueous strip emulsion of the acrylic strip copolymer, and the above water strip emulsion The solid content is 2 to 10% by weight: "The lubricity compound selected from the group consisting of a polyoxane strip compound, a fluorine strip compound, and a polyethylene strip compound is an essential component. In addition, the composition is in the upper layer. The solid content of the water bar emulsion also contains 0.5 to 10% by weight of an acidic compound selected from the group consisting of a phosphate strip compound, sulfuric acid, nitric acid, and hydrochloric acid, and the self-crosslinkable monomer is pseudo selected from the group consisting of a hydrazine-hydroxyalkyl group ( Methyl) acrylamide, Ν-methoxyalkyl (meth) propyl decylamine, (meth) propylene acrylate. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297) UNI) ----------1 ----- Γ (Please read the Notes on the back to fill out this page) I - set ---- ---- Ί line ®- 12698〇5 A7
經濟部智慧財產局員工消費合作社印製 聚合者即可,沒有特別的限制,以使用一種或一種以上 選自(甲基)丙烯酸酯、苯乙烯、(甲基)丙烯酸、含羥基 之犟體所成的單體較佳。此等其他共聚性單體之總量偽 為除自己交聯性單體之量為70〜9 8重量%。 該(甲基)丙烯酸酯例如有(甲基 > 丙烯酸甲酯、(甲基) 丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙 酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲 基)丙烯酸第2-丁酯、(甲基)丙烯酸第3-丁酯、(甲基) 丙烯酸2 —乙塞已酯等之Ci〜C8之烷酯或(甲基)丙烯 酸環己酯。此等之單體可單獨使用,方可以二種以上之 混合物使用。 上述之含羥基單體傺指在(甲基)丙烯酸烷酯之烷基鏈 中具有一個以上羥基者,該含羥基之單體例如有(甲基) 丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基) 丙烯酸2-羥基丁酯等。此等之含羥基之單體可單獨使用 ,亦可二種以上之混合物使用。 (甲基)丙烯酸酯單體、苯乙烯、(甲基)丙烯酸、含羥 基單體傺如上逑使用70〜98重量%。若小於70重量%時水 条乳液之安定性不佳,而若大於98重量%時所得的皮膜 之鉛筆硬度、耐污染性、耐溶劑性、耐鹺溶出性、高溫 之潤滑性不佳,故無法採用。 使該單體混合物以水条共聚合之本發明乳液,傺於共 聚合時採用非聚合性乳化劑。非聚合性乳化劑傺指本身 之分子量較高、具有與水之相溶性良好的官能基、且不 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -I I I I--I I I I I ___I l· I l· I ^ 0 I I 1.1 (請先閱讀背面之注意事項再填寫本頁) II ί 線一 05 8 96 2 A7 _____B7___— 一 X 5 i、發明說明() 聚乙烯基等之加成聚合性官能基,上逑單體之特歡為無 法進入聚合形成的聚合主鏈中。該非聚合性乳化劑之存 在對下逑本發明組成物之安定性極有效。 非聚合性乳化劑例如有十二苯磺酸鈉、分子量為約2 萬之聚氧化乙烯等之陰離子界面活性劑或非離子界面活 性劑,及聚乙二醇、聚丙烯酸、聚甲基丙烯酸、聚丙燃 醯胺之水溶性保護膠體、或使具羥基、磺酸基、狻基= 犟體聚合之合成物等。此等之非聚合性乳化劑亦可·混合 使用。不使用非聚合性乳化劑時,在聚合階段中於丙^ 酸乳液中會産生凝聚物,結果會使安定性惡化且與水& 乳液混合的聚矽氣烷条化合物、氟条化合物、聚乙嫌& 化合物等的混合安定性惡化,故必須使用該乳化劑。# 用量傺視聚合條件而定,大概對100重量份單體混合物 言為1〜5份。 添加於該水条乳液之潤滑性化合物(以下稱為潤滑_ > 傺為選自聚矽氣烷条化合物、氟条化合物、聚乙烯% # 合物,此等亦可混合使用〇此等之例如聚矽氧烷条化& 物之培困頓51(拉可尼古阿基亞(譯音)(股)製)、KM — 862 (信越聚矽氧烷(股)製),聚乙烯条化合物之肯米β胃 (譯音)700(三井化學工業(股)製)、KSL— 240Α(夫塔巴 法因肯米卡魯(股)製)、梅卡迪克斯HP-5D(明成化學1 業(股)製)、賽里夫(譯音)CL Α — 3(三洋化成工業(股)製) ,氟条化合物之夫魯恩(譯音)AD— 1(旭1C (譯音)製)、 聚氟龍(譯音>LDW4Q(賴睛(譯音)工業(股)製)等。添加 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂· 線 經濟部智慧財產局員工消費合作社印制π 經濟部智慧財產局員工消費合作社印製 1269805 A7 B7 -----6 五、發明說明() 於水条乳液時之潤滑劑形態以例子直徑為1 0 # m以'^之 ®丨間{^態者較佳,添加方法可為在水条乳液攪拌下添加 少許的潤滑劑。 該潤滑劑對水条乳液之固成分而言必須含有2〜1 0重 量:δ。若小於2重量%實在常溫及高溫下潤滑性皆不佳, 而若大於10重量%時組成物中在水条乳液中會産生凝聚 ^,結果使組成物本身之安定性惡化。另外,除本發明 之潤滑劑外之潤滑劑例如使用如硬脂酸条化合物之直鏈 烷酸化合物做為潤滑劑時,即使添加量為2〜1D重量%時 與本發明之水条乳液混合時,組成物在數曰内凝聚。而 且,本發明之被覆用組成物僳上逑之水条乳液與其固成 分之2〜1〇 %之潤滑劑為主要成分,亦可添加防銹劑、增 黏劑、下逑之酸性化合物等之其他成分。 對上逑之水条乳液之固成分而言含有0.5〜10重量%酸 性化合物,促進自己交聯性單體之交聯反應、即使在60 〜1 2 G °C之較低溫下烘烤時,可得具有良好耐溶劑性及 耐鹼溶出性之表面包覆材料。若小於0 · 5重量%時,做為 促進劑之效果弱、結果在低溫下烘烤時表面被覆材料之 耐溶劑性及耐鹼溶出性不佳,若大於10重量%、包覆用 組成物本身之PH會顯著降低、操作安定性不佳。 酸性化合物僳選自磷酸条化合物、硫酸、硝酸、鹽酸 所成群,以具有解離性之氫離子者。磷酸条化合物可使 用礎酸二氫銨、磷酸二氫鈉、磷酸一氬鈉、磷酸三鈉、 焦磷酸鈉、聚磷酸鈉、聚磷酸鈉、甲基磷酸鈉、磷酸二 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ;---·----------4裝----l· (請先閱讀背面之注意事項再填寫本頁) — l· I 訂·----- 線肩 1269805 A7 B7 7 五、發明說明() 氫鎂、磷酸鋁、次亞磷酸、正磷酸、聚隣酸。此等之酸 性化合物可單獨使用、可二種以上之混合物。 (請先閱讀背面之注意事項再填寫本頁) 上逑說明的包覆用組成物之製法沒有待別限制,例不 如下所示。 換言之,使所定量之非聚合性乳化劑與脫離子水置於 反應槽中,使液溫上升至7 0 °C。於其中在2小時同時並 行滴入在所定量之單體混合物中溶解有油溶性聚合啓始 創者、或所定量之單體混合樹與過硫酸鞍水溶液與酸性 亞硫酸鈉水溶液並予以攪拌後,連續在7()°C下搜拌2小 時且進行聚合,可製得水条乳液。然後,例如有可得在 10〜5(TC、約100 r pm之攪拌下之上逑水条乳液中少量添 加濕潤的潤滑劑之組成物的方法。而且,加入酸性化合 物時添加於10〜50。〇、約lOOrpm之攪拌下之上逑組成物 的方法。 經濟部智慧財產局員工消費合作社印製 該發明之組成物的對被覆對象材料而言皮膜之烘烤溫 度為6 0〜3 0 0 °C。若烘烤溫度小於6 G°C時,溶劑之水份 不易除去之問題、共聚物中自己交聯性單體部分之交聯 形成不充分、皮膜之鉛筆硬度、皮膜之外觀、常溫及高 溫下之潤滑性不佳,若大於300 °C時,會有皮膜之分解 徐徐地開始燃燒之問題、或霈龐大的加熱設備,且另需 使處理材料強制冷卻設備,傜不為企求。如此製得之由 本發明組成物所成的皮膜,具有6H以上之鉛筆硬度、良 好的耐污染性、在25 °C之動摩擦像數為0.15以下且在12(TC 之動摩擦偽數為小於25°C時之1· 2倍的優異物性。而且, 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1269805 A7 B7 五、發明說明( 視表面包覆之用途而定,要求耐溶劑性或耐鹸溶出性。 對該要求而言,使用不含酸性化合物之本發明包覆用組 成物時,必須具1 2 (TC以上之烘烤溫度,惟含有酸性化 合物之包覆用組成物卽使在60〜120 °C之烘烤溫度下可 得具優異耐溶劑性(以下述之評估方法為4級以上 >、耐 鹼溶出性(以下逑之評估方法為10%以下)之皮膜。 本發明組成物之包覆對象材料例如有冷延鋼板、鋁板 、鋁合金電鍍鋼板、鋅板、鍍鋅銷板、A BS樹脂板等, 尤其是施用於鋼板時就上逑皮膜通過低、高溫之潤滑性 佳而言,對耐連續壓製加工等之效果亦大。 [實施例] 於下逑中藉由實施例更詳細地說明本發明。而且,實 施例中之各評估傺藉由下逑知方法予以測定及評估。 1 .組成物安定性 將30ml以水条乳液為主之組成物加入50ml玻璃瓶中, 予以密封且在5(TC下靜置1個月。以目視評估1個月 後乳液之狀態β 〇:無凝聚、增黏、沉澱、分離情形、偽佳——合格 會産生凝聚物及沉澱物................不合格 凝膠化..............................不合格 2 .潤滑性(動摩擦偽數) 使以水条乳液為主之組成物錕塗覆於基材後,在熱風 乾燥機内靜置至所定的到達溫度,烘烤塗膜。在冷卻至 常溫之塗膜上於調整至25 °C之室内中以一定速度(10 cm/ 10- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ---I l· I h I 訂 ίιιι---I 1 -The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, can print the aggregator, and there is no particular limitation to use one or more selected from the group consisting of (meth) acrylate, styrene, (meth)acrylic acid, and hydroxyl-containing steroids. The resulting monomer is preferred. The total amount of these other copolymerizable monomers is assumed to be 70 to 98% by weight in addition to the self-crosslinkable monomer. Examples of the (meth) acrylate include (methyl) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate. Butyl ester, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. The alkyl ester or cyclohexyl (meth) acrylate. These monomers may be used singly or in combination of two or more. The above hydroxyl group-containing monomer refers to an alkyl group of (meth) acrylate. If the chain has one or more hydroxyl groups, the hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate or the like. These hydroxyl group-containing monomers may be used singly or in combination of two or more. (Meth) acrylate monomer, styrene, (meth)acrylic acid, hydroxyl group-containing monomer 傺 70~98 as above % by weight. If less than 70% by weight, the stability of the water bar emulsion is not good, and When it is more than 98% by weight, the obtained film has poor pencil hardness, stain resistance, solvent resistance, ytterbium resistance, and high temperature, and therefore cannot be used. The present invention is a copolymer of the water mixture. The emulsion is a non-polymerizable emulsifier used in the copolymerization. The non-polymerizable emulsifier refers to a functional group having a high molecular weight and good compatibility with water, and is not applicable to the Chinese National Standard (CNS). A4 size (210 X 297 mm) -III I--IIIII ___I l· I l· I ^ 0 II 1.1 (Please read the note on the back and fill out this page) II ί Line 1 05 8 96 2 A7 _____B7___— An X 5 i, the invention describes () an addition polymerizable functional group such as a polyvinyl group, and the monomer of the upper oxime monomer is incapable of entering the polymerization main chain formed by polymerization. The presence of the non-polymerizable emulsifier is a sputum The stability of the composition of the invention is extremely effective. The non-polymerizable emulsifier is, for example, an anionic surfactant or a nonionic surfactant such as sodium dodecylsulfonate, a polyoxyethylene having a molecular weight of about 20,000, and a polyethylene glycol. ,Polyacrylic acid, A water-soluble protective colloid of methacrylic acid or polyacrylamide, or a composition obtained by polymerizing a hydroxyl group, a sulfonic acid group, a thiol group, a steroid, etc. These non-polymerizable emulsifiers may also be used in combination. In the case of a non-polymerizable emulsifier, agglomerates are generated in the acrylic acid emulsion in the polymerization stage, and as a result, the stability is deteriorated and the polyxanthene compound, the fluorine-containing compound, and the polyethylene are mixed with the water & emulsion. The mixing stability of the compound and the like is deteriorated, so it is necessary to use the emulsifier. # The amount depends on the polymerization conditions, and is about 1 to 5 parts per 100 parts by weight of the monomer mixture. Lubricity added to the water bar emulsion The compound (hereinafter referred to as lubrication _ > 傺 is selected from the group consisting of a polyxane alkane compound, a fluorine strip compound, a polyethylene % compound, and these may also be used in combination, for example, polyoxyalkylene strips & Pesticide 51 (Lake Niko Agia (trans) (share) system), KM - 862 (Shinjuku polyoxyalkylene (stock) system), polyethylene compound Kemppi beta stomach (transliteration) 700 (Mitsui Chemical Industry Co., Ltd.), KSL-240Α (Futa Fainken Mikaru (share) system, Mercatix HP-5D (Mingcheng Chemical Industry 1 (share) system), Saif (transliteration) CL Α - 3 (Sanyo Chemical Industry Co., Ltd.), Fluorine compound Fruen (transliteration) AD-1 (asahi 1C (transliteration) system), polyfluoron (transliteration > LDW4Q (Lai Jing (transliteration) industry (share) system) and so on. Add this paper scale to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print π Ministry of Economics Property Bureau Staff Consumer Cooperative Printed 1269805 A7 B7 -----6 V. INSTRUCTIONS () The lubricant form in the water strip emulsion is 1 0 # m in the case of '^之丨丨^^ Preferably, the method of addition may be to add a small amount of lubricant under stirring of the water bar emulsion. The lubricant must contain 2 to 10 weights: δ for the solid content of the water bar emulsion. If it is less than 2% by weight, the lubricity is not good at normal temperature and high temperature, and if it is more than 10% by weight, agglomeration occurs in the water-strip emulsion in the composition, and as a result, the stability of the composition itself is deteriorated. Further, when the lubricant other than the lubricant of the present invention is used as a lubricant, for example, a linear alkanoic acid compound such as a stearic acid bar compound, it is mixed with the water slug emulsion of the present invention even when the amount is 2 to 1 D% by weight. At the time, the composition agglomerates within a few turns. Further, the coating composition of the present invention has a lubricant of 2 to 1% by weight of the water-striped emulsion and a solid component thereof, and may be added with a rust inhibitor, a tackifier, an acidic compound of the lower jaw, or the like. Other ingredients. Containing 0.5 to 10% by weight of an acidic compound to the solid component of the water emulsion of the upper layer to promote the crosslinking reaction of the self-crosslinking monomer, even when baking at a lower temperature of 60 to 12 G ° C, A surface coating material having good solvent resistance and alkali dissolution resistance can be obtained. When it is less than 0.5% by weight, the effect as a promoter is weak, and as a result, the solvent resistance and alkali-resistant dissolution property of the surface coating material are poor when baked at a low temperature, and if it is more than 10% by weight, the coating composition is The pH of itself will be significantly reduced and the operation stability will be poor. The acidic compound 僳 is selected from the group consisting of a phosphate strip compound, sulfuric acid, nitric acid, and hydrochloric acid, and has a dissociative hydrogen ion. Phosphate strip compounds can be used in China, such as ammonium dihydrogen phosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium polyphosphate, sodium polyphosphate, sodium methyl phosphate, and phosphoric acid. Standard (CNS) A4 specification (210 X 297 mm) ;---·----------4----l· (Please read the notes on the back and fill out this page) — l· I Book·---- Line shoulder 1269805 A7 B7 7 V. Description of invention () Magnesium hydrogen, aluminum phosphate, hypophosphorous acid, orthophosphoric acid, poly-ortho acid. These acid compounds may be used singly or in combination of two or more. (Please read the precautions on the back and fill out this page.) The method of preparing the coating composition described in the above section is not limited, as shown below. In other words, the quantified non-polymerizable emulsifier and deionized water were placed in a reaction tank to raise the liquid temperature to 70 °C. In which the oil-soluble polymerization initiator, or the monomer mixture tree and the aqueous solution of sodium persulfate and the aqueous sodium sulfite solution are dissolved in the quantitative monomer mixture simultaneously in 2 hours, and stirred continuously. After mixing at 7 () ° C for 2 hours and carrying out polymerization, a water bar emulsion can be obtained. Then, for example, there is a method in which a composition of a wet lubricant is added in a small amount in a water-repellent emulsion of 10 to 5 (TC, about 100 r pm), and added to 10 to 50 when an acidic compound is added. 〇 方法 〇 l l l l l l l l l l l l l l 约 约 约 约 约 约 约 约 约 。 。 。 。 。 。 。 。 。 。 约 。 约 。 约 约 约 约 约 约 约 。 。 。 。 。 约°C. If the baking temperature is less than 6 G °C, the moisture of the solvent is not easily removed, the cross-linking of the self-crosslinking monomer portion in the copolymer is insufficient, the pencil hardness of the film, the appearance of the film, and the room temperature. And the lubricity at high temperatures is not good. If it is more than 300 °C, there will be a problem that the decomposition of the film starts to burn slowly, or a huge heating device, and the processing material is forced to cool the equipment, which is not desirable. The film formed by the composition of the present invention thus obtained has a pencil hardness of 6H or more and good stain resistance, and the number of dynamic friction images at 25 ° C is 0.15 or less and at 12 (the dynamic friction pseudo number of TC is less than 25°). C of 1· 2 Excellent physical properties. Moreover, this paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 V. Invention description (depending on the use of surface coating, solvent resistance or hydrazine resistance is required) Dissolution property. When the coating composition of the present invention containing no acidic compound is used for this requirement, it is necessary to have a baking temperature of 1 2 (TC or higher, but a coating composition containing an acidic compound). At a baking temperature of -120 °C, a film having excellent solvent resistance (four or more levels of evaluation method as described below) and alkali-resistant dissolution (hereinafter, the evaluation method is 10% or less) can be obtained. The material to be coated is, for example, a cold-rolled steel plate, an aluminum plate, an aluminum alloy plated steel plate, a zinc plate, a galvanized pin plate, an ABS resin plate, etc., especially when applied to a steel plate, the low-temperature and high-temperature lubricity of the upper coating film. Preferably, the effect of the continuous press processing or the like is also large. [Embodiment] The present invention will be described in more detail by way of examples in the hem. Moreover, each evaluation in the examples is given by the following method. Determination and evaluation. 1 . Composition stability 30 ml of a water-based emulsion-based composition was added to a 50-ml glass bottle, sealed, and allowed to stand at 5 (TC for 1 month). The state of the emulsion after one month was visually evaluated. β 〇: no condensation , viscosity increase, precipitation, separation, false good - qualified will produce condensate and sediment ................ unqualified gelation ..... ......................Failed 2. Lubricity (dynamic friction pseudo-number) After the composition of the water-striped emulsion is applied to the substrate , let it stand in the hot air dryer to the specified reaching temperature, and bake the coating film. In the room cooled to normal temperature at a certain speed in the room adjusted to 25 °C (10 cm / 10 paper scale applies to China) Standard (CNS) A4 size (210 X 297 mm) (Please read the note on the back and fill out this page) ---I l· I h I Book ίιιι---I 1 -
△ X 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印制π 1269805 A7 B7 9 五、發明說明() 分)使錘滑下,以測定此時摩擦産生的荷重。藉由下式 算出動摩擦係數。而且,有關高溫之潤滑性偽在基材之 下方設置電熱器,且使塗膜預先加熱至120 °C,以上逑 方法測定此時之動摩擦僳數。 (JIS K-7125) 動摩擦像數=錘之重量(g)/因摩擦産生的荷重(gf) 3 .耐污染性 使以水条乳液為主之組成物棍塗覆於基材後,在熱風 乾燥機内靜置至所定的到達溫度,烘烤塗膜ό在冷卻至 常溫之塗膜上滴下2ml、10%之炭黑水分散液,且在81TC 熱風乾燥機内放置24小時。取出試料、以純水流水濕潤 炭黑滴下部分等,以目視判斷塗膜上之碩黑附著狀態。 ® :無附著情形.........合格 〇:稍微可見程度之附著情形.....合格 △:可見程度之附著情形.........不合格 X :明顯地附著情形.............不合格 XX :明顯地附著情形、且擴至周圍——不合格 4 .鉛筆硬度 使以水条乳液為主之組成物棍塗覆於基材後,在熱風 乾燥機内靜置至所定的到達溫度,烘烤塗膜。使冷卻至 常溫之塗膜各以不同硬度之鉛筆搓破,讀取不會使塗膜 破損的鉛筆硬度。 5 .耐溶劑性 使以水条乳液為主之組成物锟塗覆於基材後,在熱風 -11- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --------I — I - I I I l· I l· I · I I —r (請先閱讀背面之注意事項再填寫本頁) 線一 1269805 A7 B7 10 五、發明說明() 乾燥機内靜置至所定的到達溫度,烘烤塗膜。在冷卻至 常溫之塗膜上以染入有乙醇之碎紗等者以約lfcg之荷重 來回擦拭5次。然後以目視觀察塗膜上之外觀變化。 5 (級):無外觀變化 4 (级):藉由目視角度賴確認有變化 3 (級):稍有變化 2 (級):明顯地有變化 、 1 (級):皮膜剝落 6 .耐鹼溶出性 預先測定基材之重量、且使以水条乳液為主之組成物 棍塗覆於鋼板等之上述基材後,在熱風乾燥機内靜置至 所定的到達溫度,烘烤塗膜〇測定在冷卻至常溫下含基 材之塗膜的重量,求得塗膜重量A。然後,將預先調至2 重量%之撒復克里那(譯音)SD280MZ(日本培因頓(譯音) (股)製)之鹼水溶液保持於43°C,於其中使含基材之塗 膜浸漬2分鐘。2分鐘後取出且輕輕地水洗、在50 °C之 熱風乾燥基中乾燥至沒有水份為止。然後,再測定含基 材之塗膜重量,且求取於鹸處理後滯留於基材上之塗膜 重量B ,求得以下式所示之鹸溶出率(% )。 鹼溶出率 U ) = [ 1 - ( B / A ) ] X 1 0 0 7 ·塗覆外觀 使以水条乳液為主之組成物棍塗覆於基材後,在熱風 乾燥機内靜置至所定的到達溫度,烘烤塗膜。藉由目視 評估冷卻至常溫之塗膜表面的外觀。 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -----r--^—訂·---.---Γ-·線一 經濟部智慧財產局員工消費合作社印制农 1269805 A7 B7 11五、發明說明() 〇 :沒有變色 △:稍許變色 X :明顯地變色 實施例1 (非聚合性乳化劑之合成) 將8 9 3份(重量份、以下皆相同 >脱離子水、100份表上 之組成欄所示組成的單體、3份過硫酸銨、4份酸性亞 硫酸鈉置於反應槽内,予以攪拌且使液溫上升至70。0。 再於70°C下攪拌12小時以進行聚合反應,合成滿足本發 明之非聚合性乳化劑a〜c。另外,表1中併記有做為本 發明之非聚合性乳化劑所採用的市售的界面活性劑等d 〜f 0 表1 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 非聚合性 組成 備註 A MAA/ VVS=70/30 B MAA/ SPSS=70/30 C MAA/ VSS/HEA=70/20/10 D PVA-217 (聚乙二醇) 克拉雷股份有 限公司製 E 〇T-7Q(陰離子性界面活性 劑 三洋化成工業股 份有限公司製 F 耶馬魯肯130K(非離子性 界面活性劑) 花王股份有限公 司製△ X Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing π 1269805 A7 B7 9 V. Invention description () points) The hammer is slid down to determine the load generated by friction at this time. The dynamic friction coefficient is calculated by the following formula. Further, regarding the high-temperature lubricity, an electric heater was placed under the substrate, and the coating film was preheated to 120 °C, and the above-described method was used to measure the number of dynamic friction turns. (JIS K-7125) Number of dynamic friction images = weight of hammer (g) / load due to friction (gf) 3. Pollution resistance is caused by applying a stick of water-based emulsion to the substrate, in hot air The inside of the dryer was allowed to stand at a predetermined reaching temperature, and the baking coating film was dropped with 2 ml of a 10% carbon black aqueous dispersion on a film cooled to normal temperature, and left in an 81TC hot air dryer for 24 hours. The sample was taken out, wetted with pure water, and the carbon black was dropped, and the state of the black adhesion on the coating film was visually judged. ® : No adhesion.........Qualified 〇: Adhesive condition with a slight degree of visibility.....Quality △: Visibility of visible degree.........Failed X: Obvious Ground adhesion situation..................Failed XX: Apparently adhered to the situation, and spread to the surrounding - unqualified 4. Pencil hardness is coated with a stick of water-based emulsion After the substrate, it was allowed to stand in a hot air dryer to a predetermined reaching temperature, and the coating film was baked. The coating film cooled to a normal temperature was ruptured with a pencil of different hardness, and the pencil hardness which did not damage the coating film was read. 5. Solvent resistance After applying the composition of the water bar emulsion to the substrate, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to the hot air -11- paper scale --- -----I — I - III l· I l· I · II —r (Please read the notes on the back and fill out this page) Line 1269805 A7 B7 10 V. Invention description () The machine is allowed to stand until The coating temperature is set and the coating film is baked. The film which was cooled to a normal temperature was rubbed back and forth 5 times with a load of about lfcg, or the like, which was dyed with ethanol. Then, the change in appearance on the coating film was visually observed. 5 (level): no appearance change 4 (level): confirmed by visual angle change 3 (level): slight change 2 (level): obviously change, 1 (level): film peeling 6. alkali resistance The elution property is measured by measuring the weight of the substrate in advance, and applying a composition stick mainly composed of a water bar emulsion to the substrate such as a steel sheet, and then standing in a hot air dryer to a predetermined reaching temperature, and measuring the baking coating film. The weight A of the coating film was determined by cooling to the weight of the coating film containing the substrate at normal temperature. Then, the aqueous solution of the base of the Syracuse SD280MZ (manufactured by Peyton, Japan), which was previously adjusted to 2% by weight, was maintained at 43 ° C, and the coating film containing the substrate was placed therein. Dip for 2 minutes. After 2 minutes, it was taken out and gently washed with water, and dried in a hot air drying base at 50 °C until there was no water. Then, the weight of the coating film containing the substrate was measured, and the coating film weight B which was retained on the substrate after the hydrazine treatment was determined, and the 鹸 dissolution rate (%) shown by the following formula was obtained. Alkali dissolution rate U ) = [ 1 - ( B / A ) ] X 1 0 0 7 · The appearance of the coating is applied to the substrate after the composition of the water bar emulsion is applied to the substrate, and then allowed to stand in a hot air dryer to a predetermined temperature. To reach the temperature, bake the film. The appearance of the surface of the coating film cooled to normal temperature was visually evaluated. -12- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) -----r--^-订·--- .---Γ-·Line 1 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printing Agriculture 1269805 A7 B7 11 V. Invention Description () 〇: No discoloration △: slight discoloration X: Significant discoloration Example 1 (non-polymerizable Synthesis of emulsifier) 991 parts by weight (parts by weight, all of the following > deionized water, 100 parts of the monomer shown in the composition column, 3 parts of ammonium persulfate, 4 parts of acidic sodium sulfite are placed in the reaction) The inside of the tank was stirred and the liquid temperature was raised to 70. 0. The polymerization was further carried out by stirring at 70 ° C for 12 hours to synthesize the non-polymerizable emulsifiers a to c satisfying the present invention. As a non-polymerizable emulsifier of the present invention, commercially available surfactants, etc. d ~ f 0 Table 1 (Please read the back note first and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed non- Polymeric composition remarks A MAA/ VVS=70/30 B MAA/ SPSS=70/30 C MAA/ VSS/HEA=70/20/10 D PVA-217 (polyethylene glycol) E 〇T-7Q manufactured by Claret Co., Ltd. (anionic surfactant Sanyo Chemical Industry Co., Ltd. F Yemaruken 130K (nonionic surfactant) Kao shares limited Company system
* MAA : 冰 VSS : * HEA : ^ SPSS 酸鈉羥 嫌酸2-丙磺酸 基烯烯 甲乙丙 酸 磺 烯 乙 苯 對 43 酯 乙 基 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 裝-----„— ^--訂---------,—線^^1 1269805 A7 __B7_____ 五、發明說明(^ ) 實施例2 (水条乳液之合成) 將4 9 5份(重量份、以下皆相同)脱離子水、5份表2所 示之非聚合性乳化劑置於反應槽内且使液溫上升至7 〇 °C 。於其中在2小時内同時滴入97份脱離子水中溶解有300 份表2之其他共聚性單體組成攔中所示組成之單體混合 物、3份過硫酸銨的液體、及在9 6份脫離子水中溶解有4 份酸性亞硫酸鈉之液體後,再於7 (TC下攪拌2小時以進 行聚合反應,合成滿足本發明之水条乳液No. Α〜Ρ。 此外,同樣地以表2所示單體共聚合比例合成除本發 明外之水条乳液N 〇 . Q〜V做為比較例。表2中「乳液安 定性」僳為使此等之水条乳液置於密閉的容器内,且以 目視評估在50 °C下靜置1個月者,0 :無凝聚、增黏、 沉澱、分離倩形、傺佳、△:會産生凝聚物及沉澱物、 X :凝膠化。 (請先閱讀背面之注意事項再填寫本頁) -_ 裝-----^---^1 訂 *---一------線. 經濟部智慧財產局員工消費合作社印制农 4 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1269805 A7 _B7 五、發明說明() 表2 經濟部智慧財產局員工消費合作社印製 水系乳 液名 其他之共聚合性單體組 成 自己交聯 性單體種 類 自己交 聯性單 體% 非聚合 性乳化 劑 乳液安 定性 備註 水系乳 液A i-BMA/n-BA=62/36 N-MAM 2 a 〇 木發明 水系乳 液B MMA/n-BA=51/44 N-MAM 5 · 〇 水系乳 液C MMA/n-BA=49/41 N-MAM 10 b 〇 水系乳 液D MMA/2=19/61 N-MAM 20 a 〇 水系乳 液E MMA/n-BA=38/32 N-MAM 30 e 〇 水系乳 液F MMA/n-BA=53/45 GMA 2 a 〇 水系乳 液G i-BMA/2EHMA=30/65 GMA 5 d 〇 水系乳 液Η CHMA/n-BA=54/36 GMA 10 a 〇 水系乳 液I MMA/n-BA=38/32 GMA 30 f 〇 水系乳 液J MMA/CHMA/n-BA= 29/30/39 N-MMAM 2 c 〇 水系乳 液Κ MMA/n-BA=51/44 N-MMAM 5 d 〇 水系乳 液L MMA/n-BA=49/41 N-MMAM 10 b 〇 水系乳 液Μ MMA/n-BA=38/32 N-MMAM 30 b 〇 水系乳 液Ν St/n-BA/MAA= 35/45/15 N-MMAM 5 e 〇 水系乳 液〇 MMA/n-BA/HEA= 48/37/10 N-MMAM 5 d 〇 水系乳 液Ρ MMA/n-BA/MAA/HEA= 28/42/15/10 N-MMAM 5 f 〇 水系乳 液Q MMA/n-BA=53/46 N-MMAM 1 a 〇 比較例 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) pill— — — — — — — — — · I I (請先閱讀背面之注意事項再填寫本頁) --線· [269805 A7 HB7· 14 五、發明說明( 水系乳 液R MMA/n-BA=35/30 N-MAM 35 a X 水系乳 液S MMA/n-BA=53/46 GMA 1 b 〇 水系乳 液T MMA/n-BA=51/44 N-MAM 5 (SPSS) 0 水系乳1 液U MMA/n-BA=51/44 (DvB) 5 b 〇 水系乳 液V ΜΜΑ/π-ΒΑ=51/44 N-MMAM 5 △ 經濟部智慧財產局員工消費合作社印製 * MMA:甲基丙烯酸甲酯 * n-BA ··丙烯酸正丁酯 * i-BA ··甲基丙烯酸異丁酯 * 2EHMA··甲基丙烯酸2-乙基己酯 * CHMA:甲基丙烯酸環己酯 * St :苯乙烯 * MAA:甲基丙烯酸 * HE A :丙烯酸2 -羥基乙酯 * N-MAM: N -羥甲基丙烯醯胺 * N-MMAM: N-甲氣基甲基丙烯醯胺 * GMA :甲基丙烯酸環氧丙酯 * DvB :二乙烯苯 由表2可知,満足本發明之要件的水条乳液a〜P,聚 合所生成的乳液之安定性優異。S外,自己交聯性單體 過大者為R、不採用非聚合性乳化劑為V ,其乳液本身欠 缺安定性。自己交聯性過小之Q及S、使用聚合性乳化劑 之SPSS之T、使用不具自己交聯性單體之DvB的u,水条 --1 6 - (請先閲讀背面之注音J事項再填寫本頁) 卜 — l·—訂--------1-線 ». 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1269805 A7 B7 15 五、發明說明() 乳液本身之安定性沒有問題·,惟含有下.述之潤滑劑之組 成物時會有缺點。 實施例3〜7及比較例1〜3 使用表2所示之水条乳液C、使4種表3所示之各種 潤滑劑對水条乳液之固成分而言.以表3 <所示之各量混合、 以調整成包覆用組成物(下述中簡稱為組成物),且在鋁 板上使該組成物棍塗覆成烘燎後皮膜之厚度為3# hi後, 製得被覆有烘烤到達溫度為130°C之包覆用組成物皮膜 的表面包覆鋼板〇組成物之安定性與鋼板之表面特性的 評估結果如表3所示。 (請先閱讀背面之注意事項再填寫本頁)* MAA : Ice VSS : * HEA : ^ SPSS Sodium hydroxy acid 2-propane sulfonyl ethene propionate sulfonyl ethylbenzene 43 ester Ethyl paper size applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Pack-----„--------------,-line ^^1 1269805 A7 __B7_____ V. Description of the invention (^) Example 2 (Water strip emulsion Synthesis) 49 parts (parts by weight, all of the same) deionized water, 5 parts of the non-polymerizable emulsifier shown in Table 2 were placed in the reaction tank and the liquid temperature was raised to 7 〇 ° C. Into 97 parts of deionized water, 2 parts of other copolymerizable monomers dissolved in Table 2 were dissolved in 2 hours to form a monomer mixture of the composition shown in the composition, 3 parts of ammonium persulfate, and 96 parts of deionized water. After dissolving 4 parts of the liquid of acidic sodium sulfite, the mixture was stirred at 7 (TC for 2 hours) to carry out polymerization to synthesize the water-strip emulsion No. Α~Ρ satisfying the present invention. Polymerization ratio synthesis In addition to the present invention, the water strip emulsion N 〇. Q~V is used as a comparative example. The "emulsion stability" in Table 2 is used to make these water emulsions In a closed container, and visually evaluated to stand at 50 °C for 1 month, 0: no aggregation, adhesion, precipitation, separation, shape, 傺, △: will produce aggregates and precipitates, X : Gelation. (Please read the notes on the back and fill out this page) -_ Install-----^---^1 Order*---一------Line. Ministry of Economics Intellectual Property Bureau employee consumption cooperatives printed agriculture 4 paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 _B7 V. Invention description () Table 2 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing water emulsion Other co-polymerizable monomers constitute self-crosslinking monomer species self-crosslinking monomer% Non-polymeric emulsifier emulsion stability remarks water emulsion A i-BMA/n-BA=62/36 N-MAM 2 a eucalyptus invention water emulsion B MMA/n-BA=51/44 N-MAM 5 · hydrazine emulsion C MMA/n-BA=49/41 N-MAM 10 b hydrazine emulsion D MMA/2=19/61 N-MAM 20 a Hydrazine emulsion E MMA/n-BA=38/32 N-MAM 30 e Hydrazine emulsion F MMA/n-BA=53/45 GMA 2 a Hydrazine emulsion G i-BMA/2EHMA=30 /65 GMA 5 d 〇 Water emulsion Η CHMA/n-BA=54/36 GMA 10 a Hydrazine emulsion I MMA/n-BA=38/32 GMA 30 f Hydrazine emulsion J MMA/CHMA/n-BA= 29/30/39 N- MMAM 2 c 〇水 emulsion Κ MMA/n-BA=51/44 N-MMAM 5 d 〇Water emulsion L MMA/n-BA=49/41 N-MMAM 10 b 〇水 emulsion Μ MMA/n-BA=38 /32 N-MMAM 30 b Water-based emulsion Ν St/n-BA/MAA= 35/45/15 N-MMAM 5 e Water-based emulsion 〇MMA/n-BA/HEA= 48/37/10 N-MMAM 5 d 〇Water emulsion Ρ MMA/n-BA/MAA/HEA= 28/42/15/10 N-MMAM 5 f Hydrazine emulsion Q MMA/n-BA=53/46 N-MMAM 1 a 〇Comparative example paper The scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) pill — — — — — — — — II (Please read the note on the back and fill out this page) --Line · [269805 A7 HB7 · 14 V. INSTRUCTIONS (aqueous emulsion R MMA/n-BA=35/30 N-MAM 35 a X water emulsion S MMA/n-BA=53/46 GMA 1 b hydrophobic emulsion T MMA/n-BA= 51/44 N-MAM 5 (SPSS) 0 Water emulsion 1 liquid U MMA/n-BA=51/44 (DvB) 5 b Hydrophobic emulsion V ΜΜΑ/π-ΒΑ=51/44 N-MMAM 5 △ Ministry of Economic Affairs wisdom Produced by the staff of the production bureau * MMA: methyl methacrylate * n-BA · n-butyl acrylate * i-BA · isobutyl methacrylate * 2EHMA · 2-ethylhexyl methacrylate * CHMA: cyclohexyl methacrylate * St : styrene * MAA: methacrylic acid * HE A : 2-hydroxyethyl acrylate * N-MAM: N - hydroxymethyl acrylamide * N-MMAM: N- Methyl methacrylamide amide * GMA : glycidyl methacrylate * DvB : divinyl benzene As shown in Table 2, the water bar emulsion a to P which meets the requirements of the present invention, the stability of the emulsion formed by polymerization Excellent. In addition to S, the self-crosslinking monomer is R, and the non-polymerizable emulsifier is not V, and the emulsion itself lacks stability. Q and S which are too small in cross-linking, T of SPSS using a polymeric emulsifier, u which uses DvB which does not have a cross-linking monomer, water strip--1 6 - (Please read the note on the back of the J first. Fill in this page) 卜 — l·—订--------1-线». This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 15 V. Invention Description () There is no problem with the stability of the emulsion itself. However, there are disadvantages when it contains the composition of the lubricant described below. Examples 3 to 7 and Comparative Examples 1 to 3 using the water bar emulsion C shown in Table 2, and various lubricants shown in Table 3 for the solid content of the water bar emulsion, as shown in Table 3 < The respective amounts were mixed to adjust to a coating composition (hereinafter simply referred to as a composition), and the composition was coated on an aluminum plate to form a coating having a thickness of 3 # hi, and then a coating was obtained. Table 3 shows the evaluation results of the stability of the surface coated steel sheet composition and the surface characteristics of the steel sheet having the coating composition film having a baking reaching temperature of 130 °C. (Please read the notes on the back and fill out this page)
經濟部智慧財產局員工消費合作社印製 表3 潤滑劑 mm 潤滑 劑重 量% 組成 物安 定性 塗覆 外觀 動摩擦係數 120°C /25〇C 動摩 擦係 數比 i污 染性 鉛筆 硬度 耐溶 劑性 鹼溶 出率 % 25〇C 120°C 實施 培因塔 2 〇 〇 0.080 0.095 1.188 ◎ 7H 5 0 例3 頓51 實施 培因塔 5 〇 〇 0.049 0.057 1.163 ◎ 7H 5 0 例4 頓51 實施 培因塔 10 〇 〇 0.049 0.056 1.143 ◎ 7H 5 0 例5 頓51 實施 聚氟龍 5 〇 〇 0.055 0.063 1.145 ◎ 7H 5 0 例6 LDW40 - 實施 賽里伏 5 〇 〇 0.057 0.067 1.175 ◎ 7H 5 · 0 例7 CLA3 比較 培因塔 1 〇 〇 0.160 0.195 1.218 ◎ 6H 5 0 例1 頓51 比較 培因塔 12 Δ 例2 頓51 比較 硬脂酸 5 X 例3 系化合 物 丨 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -17- 丨訂· --線· 1269805 A7 B7 16 五、發明說明() 由表3可知,滿足本發明之要件的實施例3〜7具有優 摩鹼 動耐 下及 溫性 高劑 及溶 溫耐 常的 、異 性優 染有 污具 耐亦 / i. 度外 硬此 義 ο 鉛性 、滑 性潤 覆之 塗數 的傺 異擦 用缺 使欠 、身 較物 ί成 ^ Μ 大3, 過例 量較 合比 混的 之劑 劑滑 滑潤 潤之 ,物 外合 另化 〇 条 性酸 出指 溶硬 性例 定較 安比 覆 塗 之 板 鋼 對 成 完 法 無 之 少 過 量 合 混 劑 滑 潤 題 問 有 沒 性 定 安 之 身 本 物 成 組 溫 常 缺 欠 rn ti 成 固 之 液 乳 条 水 對 整 調 以 / 液 乳 J4N糸 例K 較水 eb®之 性sb一7K 滑 2 所 潤-22 之 CO 表 溫例用 高施使 及實 - 之混 )5物烤冑5 $ 合 有 务吏被 ^-hf得 氧«製 矽鋼, { 種 m 5 各Λί 頓ΤΓ3 因‘所為 培 4 度 份表厚 量在之 重且膜 5 ,皮 有物後 合成烤 混組烘 言用成 而覆覆 分包塗 板所 鋼I 覆 包 面 表 的 膜 皮 物 成 組 用 覆 包 之 °c (請先閱讀背面之注意事項再填寫本頁) :#裝----III· — 表 如 I 身 結 估 評 的 性 特 面 表 之 板 鋼 與 性 13定 為安 度之 溫物 達成 C 到組示 訂 I---.-----線- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1269805 A7 B7 五、發明說明(/?) 表4 經濟部智慧財產局員工消費合作社印製 水系 乳液 組成 物安 定性 原料 塗覆 外觀 動摩擦係數 動摩 擦係 數比 耐污 染性 鉛筆 硬度 耐溶 劑性 鹼溶 出率 % 25〇C 120°C 實施 例8 水系 乳液 A 〇 原料1 〇 0.071 0.084 1.183 〇 6H 4 0 實施 例9 水系 乳液 B 〇 原料1 〇 0.055 0.065 1.182 〇 7H 4 0 實施 例4 水系 乳液 C 〇 原料1 〇 0.049 0.057 1.163 ◎ 7H 5 0 實施 例10 水系 乳液 D 〇 原料1 〇 0.048 0.056 1.167 ◎ 8H 5 0 實施 例11 水系 乳液 E 〇 原料1 〇 0.050 0.057 1.140 ◎ 8H 5 0 實施 例12 水系 乳液 F 〇 原料1 〇 0.068 0.079 1.162 〇 6H 4 0 實施 例η 水系 乳液 G 〇 原料1 〇 0.061 0.072 1.180 〇 6H 4 0 實施 例14 水系 乳液 Η 〇 原料1 〇 0.058 0.068 1.172 〇 6H 5 0 實施 例15 水系 乳液I 〇 原料1 〇 0.055 0.063 1.145 ◎ 7H 5 0 實施 例16 水系 乳液J 〇 原料2 〇 0.069 0.079 1.145 〇 6H 4 0 實施 例17 水系 乳液 Κ 〇 原料2 〇 0.060 0.070 1.167 〇 7H 4 0 實施 例18 水系 乳液 L 〇 原料2 〇 0.057 0.066 1.158 ◎ 7H 5 0 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -19- ---------------裝--- (請先閱讀背面之注意事項再填寫本頁) ---訂- 1269805 A7 B7 五、發明說明 經濟部智慧財產局員工消費合作社印製Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 3 Lubricant mm Lubricant Weight % Composition Stability Coating Appearance Dynamic Friction Coefficient 120°C /25〇C Dynamic Friction Coefficient I Pollution Word Hardness Solvent Alkali Dissolution Rate % 25〇C 120°C Implementation of Pein Tower 2 〇〇0.080 0.095 1.188 ◎ 7H 5 0 Example 3 51 51 Implementation of Pein Tower 5 〇〇 0.049 0.057 1.163 ◎ 7H 5 0 Example 4 51 51 Implementation of Pein Tower 10 〇〇 0.049 0.056 1.143 ◎ 7H 5 0 Example 5 顿 51 Implementation of PTFE 5 〇〇 0.055 0.063 1.145 ◎ 7H 5 0 Example 6 LDW40 - Implementation of 赛里伏 5 〇〇 0.057 0.067 1.175 ◎ 7H 5 · 0 Example 7 CLA3 Comparison of Peinta 1 〇〇0.160 0.195 1.218 ◎ 6H 5 0 Example 1 51 51 Comparison of Pein Tower 12 Δ Example 2 51 51 Comparison of stearic acid 5 X Example 3 series of compounds 丨 This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -17- 丨定· --Line · 1269805 A7 B7 16 V. Illustrative () It can be seen from Table 3 that Examples 3 to 7 satisfying the requirements of the present invention have a high-alkali resistance and a high temperature agent and a temperature-difference resistance, and a heterogeneous excellent dyeing and staining resistance/i. It is hard to use this. The difference between the number of coatings for lead and slipperiness is less than that of the body. , the external matter of the addition of the sulphate acid refers to the hardening of the slab. The slab is better than the slab of the slab. The slab of the slab is less than the smear of the smear. Ti solidified milk bar water to adjust to / liquid milk J4N 糸 case K is more than water eb® sex sb-7K slip 2 -22 CO of the surface temperature example with high application and real - mixed 5 things Baked 胄 5 $ 合 吏 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The group is used to cover the cover of the steel coated sheet of the coated coated board. °c (please read the note on the back and then fill out this page): #装----III· — Table such as the body profile of the evaluation of the plate and the sex 13 is set to the temperature of the degree Material reached C to group display I---------Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 V. INSTRUCTIONS (/?) Table 4 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing Water System Emulsion Composition Stability Raw Material Coating Appearance Dynamic Friction Coefficient Dynamic Friction Coefficient Corrosion Resistance Pencil Hardness Solvent-Resistant Alkali Dissolution Rate 25〇 C 120 ° C Example 8 Aqueous emulsion A 〇 Raw material 1 〇 0.071 0.084 1.183 〇 6H 4 0 Example 9 Water emulsion B 〇 Raw material 1 〇 0.055 0.065 1.182 〇 7H 4 0 Example 4 Water emulsion C 〇 Raw material 1 〇 0.049 0.057 1.163 ◎ 7H 5 0 Example 10 Water emulsion D 〇 Raw material 1 〇 0.048 0.056 1.167 ◎ 8H 5 0 Example 11 Water emulsion E 〇 Raw material 1 〇 0.050 0.057 1.140 ◎ 8H 5 0 Example 12 Water emulsion F 〇 Raw material 1 〇 0.068 0.079 1.162 〇6H 4 0 Example η Water emulsion G 〇 Raw material 1 〇 0.061 0.072 1.180 〇6H 4 0 Example 14 Water emulsion 〇 Raw material 1 〇0.058 0.068 1.172 〇6H 5 0 Example 15 Water system Emulsion I 〇 Raw material 1 〇 0.055 0.063 1.145 ◎ 7H 5 0 Example 16 Water emulsion J 〇 Raw material 2 〇 0.069 0.079 1.145 〇6H 4 0 Example 17 Water emulsion 〇 Raw material 2 〇 0.060 0.070 1.167 〇7H 4 0 Example 18 Water emulsion L 〇 raw material 2 〇0.057 0.066 1.158 ◎ 7H 5 0 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -19- -------------- - Packing--- (Please read the notes on the back and fill out this page) --- Order - 1269805 A7 B7 V. Invention Description Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing
實施 例19 水系 乳液 Μ 〇 原料1 〇 0.053 0.061 1.151 ◎ 8Η 5 0 實施 例20 水系 乳液 Ν 〇 原料1 〇 0.058 0.067 1.155 〇 711 5 82.4 實施 例21 水系 乳液 〇 〇 原料1 〇 0.052 0.061 1.173 〇 7Η 4 0 實施 例22 水系 乳液 Ρ 〇 原料1 〇 0.055 0.062 1.127 〇 7Η 5 100 比較 例4 水系 乳液 Q 〇 原料1 〇 0.120 0.165 1.375 Δ 4Η 3 0 比較 例5 水系 乳液 S 〇 原料1 〇 0.145 0.195 1.345 X 4Η 3 0 比較 例6 水系 乳液 U 〇 原料1 〇 0.155 0.198 1.277 X 4Η 2 0 比較 例7 水系 乳液 V X 比較 例8 水系 乳液 Τ X ※原料1 ※原料2 鋁板 電氣鍍鋅鋼板 —20— 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂 A7 1269805 ___B7___ 五、發明說明() 由表4可知,滿足本發明之要件的實施例8〜22具有 優異的塗覆性、鉛筆硬度、耐污染性、常溫及高溫下動 摩擦係數之潤滑性。此外,除實施例2 ϋ及2 2外亦具有優 異的耐溶劑性及耐鹸溶出性。實施例20及22之而鹸溶出 性不佳。此僳含有過多ΜΑΑ之故,惟對只要求其他性能 優異而不要求耐鹼溶出性之用途偽十分實用。潤滑劑混 合量過少之比較例4及5、使用不具自己交聯性單體之 DvB的比較例6,組成物本身之安定性沒有問題、惟欠缺 耐污染性、鉛筆硬度、常溫及高溫之潤滑性,而不使用 非聚合性乳化劑之比較例7及8則欠缺與潤滑劑混合的 組成物安定性。 實施例2 3〜3 2及比較例9〜1 1 使用表2所示之水条乳液C、以調整對水条乳液之固 成分而言混合有5重量份培因頓51(聚矽氣烷条化合物) 之包覆用組成物,且在鋁板上使該組成物棍塗覆成烘烤 後皮膜之厚度為3# m後,製得被覆有烘烤到達溫度如表 5所示之包覆用組成物皮膜的表面包覆銷板。組成物之 安定性與銷板之表面特性的評估結果如表5所示。 (請先閱讀背面之注意事項再填寫本頁) --訂. .線一 經濟部智慧財產局員工消費合作社印製 -21- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1269805 A7 B7 五、發明說明(2〇 ) 表5 經濟部智慧財產局員工消費合作社印製 酸性化合 物 組成 物安 定性 烘烤 溫度 °C 塗覆 外觀 動摩擦係數 120°C /25〇C _摩 擦係 數比 耐污 染性 * 鉛筆 硬度 耐溶 劑性 鹼溶 出率 % 操作 性 種類 添加 量% 25〇C 120°C 實施 例23 - - 〇 60 〇 0.085 0.095 1.118 〇 6H 3 26.5 〇 實施 例24 - - 〇 80 〇 0.067 0.078 1.164 ◎ 7H 3 20.4 〇 實施 例25 硫酸 0.2 〇 80 〇 0.047 0.055 1.170 ◎ 7H 3 10.8 〇 實施 例26 正磷 酸 0.5 〇 80 〇 0.047 0.054 1.149 ◎ 7H 4 0 〇 實施 例27 硫酸 1 〇 80 〇 0.045 0.053 1.178 ◎ 7H 4 0 〇 實施 例28 正磷 酸 2 〇 80 〇 0.046 0.053 1.152 ◎ 7H 5 0 〇 實施 例29 硫酸 5 〇 80 〇 0.044 0.051 1.159 ◎ 7H 5 0 〇 實施 例30 正磷 酸 10 〇 80 〇 0.045 0.052 1.156 ◎ 7H 5 0 〇 實施 例31 - - 〇 120 〇 0.055 0.065 1.182 ◎ 7H 4 5.5 〇 實施 例4 - - 〇 130 〇 0.049 0.057 1.163 ◎ 7H 5 0 〇 實施 例32 - - 〇 270 〇 0.043 0.051 1.186 ◎ 8H 5 0 〇 比較 例9 - - 〇 50 Δ 0.110 0.145 1.318 X 5H 2 29 X 比較 例10 - - 〇 320 X - 比較 例11 正磷 酸 12 〇 80 Δ 0.043 0.050 1.163 ◎ 7H 5 0 X -22- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1269805 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(21) 由表5可知,滿足本發明之要件的實施例23〜3 2具有 優異的塗覆性、鉛筆硬度、耐污染性、常溫及高溫下動 摩擦傺數之潤滑性。此外,烘烤溫度為1 2 0 °C以上之實 施例4、31、32具有優異的耐溶劑性、耐鹸溶出性,混 合有酸性化合物之實施例2 6〜3 G ,即使在8 (TC之較低溫 範圍之烘烤溫度下仍具良好的耐溶劑性、耐鹼溶出性。 而且,實施例23〜2 5之而溶劑性、耐鹸溶出性稭微不佳 ,惟對只要求其他性能優異而不要求耐鹼溶出性之用途 俗十分實用〇另外,烘烤溫度過低之比較例9 ,無法得 到令人滿足的皮膜硬度、耐污染性不佳〇烘烤溫度過高 之比較例1 G ,表面包覆材料與潤滑劑會分解、且無法完 成塗膜評估。使用酸性化合物之混合量過大的比較例11 ,烘烤後之塗覆外觀不佳、且會顯著地降低組成物之pH 值、故操作之安全性顯著不佳。 [發明之效果] 本發明可提供一種以安全性及環境而言優異的水条乳 液為基底,賦予高硬度與低溫至高溫之潤滑性安定 膜之包覆用組成物以及以該皮膜被覆的表面色覆材胃。 本組成物例如施用於綱板等時,該銷板不會有習知 高溫下會使潤滑性降低的問題、可連續進行鑽孔加X ^ -23- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)Example 19 Water-based emulsion 〇 〇 Raw material 1 〇 0.053 0.061 1.151 ◎ 8 Η 5 0 Example 20 Water-based emulsion 〇 Raw material 1 〇 0.058 0.067 1.155 〇 711 5 82.4 Example 21 Water-based emulsion 〇〇 Raw material 1 〇 0.052 0.061 1.173 〇 7 Η 4 0 Example 22 Water-based emulsion 〇 Raw material 1 〇 0.055 0.062 1.127 〇7Η 5 100 Comparative Example 4 Water-based emulsion Q 〇 Raw material 1 〇 0.120 0.165 1.375 Δ 4Η 3 0 Comparative Example 5 Water-based emulsion S 〇 Raw material 1 〇 0.145 0.195 1.345 X 4Η 3 0 Comparative Example 6 Water-based emulsion U 〇 Raw material 1 〇 0.155 0.198 1.277 X 4 Η 2 0 Comparative Example 7 Water-based emulsion VX Comparative Example 8 Water-based emulsion Τ X ※ Raw material 1 ※ Raw material 2 Aluminum plate galvanized steel plate - 20 - This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) Order A7 1269805 ___B7___ V. Invention Description () From Table 4, the implementation of the requirements of the present invention is satisfied. Examples 8 to 22 have excellent coatability, pencil hardness, stain resistance, and lubricity of dynamic friction coefficient at normal temperature and high temperature. . Further, in addition to Examples 2 and 2, it also has excellent solvent resistance and mash resistance. In Examples 20 and 22, the dissolution was poor. This cockroach contains too much cockroaches, but it is practical to use only other applications that are excellent in performance and do not require alkali-resistant dissolution. In Comparative Examples 4 and 5 in which the lubricant amount was too small, and Comparative Example 6 in which DvB having no self-crosslinkable monomer was used, the stability of the composition itself was not problematic, but the lubrication resistance, pencil hardness, normal temperature and high temperature lubrication were lacking. Comparative Examples 7 and 8 which did not use a non-polymeric emulsifier lacked the stability of the composition mixed with the lubricant. Example 2 3 to 3 2 and Comparative Examples 9 to 1 1 Using the water bar emulsion C shown in Table 2, to adjust the solid content of the water bar emulsion, 5 parts by weight of a Peinton 51 (polyoxane gas) was mixed. a coating composition for the strip compound), and coating the composition stick on the aluminum plate to a thickness of 3 # m after baking, and then coating the coated baking temperature as shown in Table 5 The pin plate is covered with the surface of the composition film. The evaluation results of the stability of the composition and the surface characteristics of the pin plate are shown in Table 5. (Please read the notes on the back and then fill out this page) --Border. Line 1 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed - 21 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) 1269805 A7 B7 V. INSTRUCTIONS (2〇) Table 5 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printing Acid Compound Composition Stability Bake Temperature °C Coating Appearance Dynamic Friction Coefficient 120°C /25〇C _ Friction Coefficient ratio pollution resistance* Pencil hardness Solvent-resistant alkali dissolution rate % Operational type addition amount % 25〇C 120°C Example 23 - - 〇60 〇0.085 0.095 1.118 〇6H 3 26.5 〇Example 24 - - 〇80 〇0.067 0.078 1.164 ◎ 7H 3 20.4 〇Example 25 Sulfuric acid 0.2 〇80 〇0.047 0.055 1.170 ◎ 7H 3 10.8 〇Example 26 Orthophosphoric acid 0.5 〇80 〇0.047 0.054 1.149 ◎ 7H 4 0 〇Example 27 Sulfuric acid 1 〇80 〇 0.045 0.053 1.178 ◎ 7H 4 0 〇 Example 28 orthophosphoric acid 2 〇 80 〇 0.046 0.053 1.152 ◎ 7H 5 0 〇 Example 29 Sulfuric acid 5 〇 80 〇 0.044 0.051 1.159 ◎ 7H 5 0 Example 30: orthophosphoric acid 10 〇 80 〇 0.045 0.052 1.156 ◎ 7H 5 0 〇 Example 31 - - 〇 120 〇 0.055 0.065 1.182 ◎ 7H 4 5.5 〇 Example 4 - - 〇130 〇 0.049 0.057 1.163 ◎ 7H 5 0 〇 Example 32 - - 〇270 〇0.043 0.051 1.186 ◎ 8H 5 0 〇Comparative Example 9 - - 〇50 Δ 0.110 0.145 1.318 X 5H 2 29 X Comparative Example 10 - - 〇320 X - Comparative Example 11 orthophosphoric acid 12 〇80 Δ 0.043 0.050 1.163 ◎ 7H 5 0 X -22- (Please read the note on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing 5, invention description (21) It can be seen from Table 5 that Examples 23 to 32 satisfying the requirements of the present invention have excellent coating properties, pencil hardness, stain resistance, dynamic friction at normal temperature and high temperature. The lubricity of the number. Further, Examples 4, 31, and 32 in which the baking temperature was 120 ° C or more had excellent solvent resistance and ytterbium resistance, and Example 2 6 to 3 G in which an acidic compound was mixed, even at 8 (TC) It has good solvent resistance and alkali-resistant dissolution at the baking temperature in the lower temperature range. Moreover, the solvent and leaching-resistance straws of Examples 23 to 25 are not good, but only other properties are required. The use of excellent and not required alkali-resistant dissolution is very practical. In addition, in Comparative Example 9 in which the baking temperature is too low, satisfactory film hardness, poor stain resistance, and high baking temperature are not obtained. G, the surface coating material and the lubricant may decompose and the coating film evaluation may not be completed. In Comparative Example 11 in which the mixing amount of the acidic compound is too large, the coating appearance after baking is not good, and the pH of the composition is remarkably lowered. The safety of the operation is remarkably poor. [Effect of the Invention] The present invention can provide a package of a lubricity stabilizer film which is high in hardness and low temperature to high temperature, which is excellent in safety and environment. Overlying the composition and the skin Membrane-coated surface color covering material stomach. When the composition is applied to a plate or the like, for example, the pin plate does not have a problem that the lubricity is lowered at a high temperature, and the drilling can be continuously performed by adding X ^ -23 - The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page)
中 文 表面包覆材料 (93年12月27日修正) 發明 新型 名稱 英 文Chinese Surface Coating Material (Revised on December 27, 1993) Invented New Name English
SURFACE COATING MATERIAL 姓 名 國 籍 .福川元康 •高橋智二 1, 日本 2. 日本 裝 發明 創作 人 住、居所 1. 岡山縣岡山市海吉959番地5號 2. 岡山縣岡山市金岡東町3 丁目1番11號 if 姓 名 (名稱) 東洋紡績股份有限公司 (東洋紡績株式會社) 線 經濟部智慧財邊锜g (工消費合作社印製 國 籍 日本 三、申讀人 住、居所 (事務所) 代表人 姓 名 大阪市北區堂島浜2 丁目2番8號 津村準二 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 1269805 五、發明說明(3) 而且,本發明係包含以使該組成物在60°C〜300°C下烘烤 所成、具有6H以上之鉛筆硬度、良好的耐污染性、25°C之 動摩擦係數爲0.15以下且120°C之動摩擦係數爲25°C時之 1.2倍以下之皮膜被覆的表面包覆材料。 [實施發明之形態] 如上述之自己交聯性單體係以選自N-羥基烷基(甲基)丙 烯醯胺、N-甲氧基烷基(甲基)丙烯醯胺、(甲基)丙烯酸環 氧丙酯較佳。而且,本發明之自己交聯性單體係指具有N- 1羥基烷基醯胺基、N-甲氧基烷基醯胺基、環氧基之官會g 费基,且以在該官能基之間或該官能基與本發明共聚合中所 κι _採用的其他共聚合性單體即(甲基)丙烯酸之羧基或含羥基 7Τ: :的單體之羥基所反應之物,上述之化合物群爲其代表。具 本 _ 案體而言例如有Ν-羥基甲基(甲基)丙烯醯胺、Ν-羥基乙基(甲 修 至基)丙烯醯胺、Ν-羥基丙基(甲基)丙烯醯胺、Ν-羥基丁基SURFACE COATING MATERIAL Name Nationality. Fukugawa Yukang • Takahashi Chiji 2, Japan 2. Japanese Inventor Creation and Residence 1. Okayama City, Okayama 959, No. 5, Okayama, Okayama, Okayama, Okayama, Okayama, Okayama, Okayama If the name (name) Toyobo Co., Ltd. (Toyobo Co., Ltd.) The Ministry of Finance of the Ministry of Finance and Finance 锜g (The Ministry of Industry and Commerce Co., Ltd. prints the nationality of Japan III. The applicant's residence, residence (office) Representative name Osaka City North District Island 浜 2 Chome 2 Fan No. 8 Tsumura Bimoto This paper scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1269805 V. Invention Description (3) Moreover, the present invention is included so that the composition is at 60° It is prepared by baking at C~300 °C, has a pencil hardness of 6H or more, and has good stain resistance. The dynamic friction coefficient at 25 ° C is 0.15 or less and the dynamic friction coefficient at 120 ° C is 1.2 times or less at 25 ° C. The surface coating material coated with the film. [Form of the invention] The self-crosslinking single system as described above is selected from N-hydroxyalkyl (meth) acrylamide, N-methoxyalkyl (methyl) Acrylamide and glycidyl (meth)acrylate are preferred. Moreover, the self-crosslinking single system of the present invention has N- 1 hydroxyalkylguanamine, N-methoxyalkylguanamine. The epoxy group is a valer group, and the carboxyl group or the (meth)acrylic acid of the other copolymerizable monomer used in the copolymerization of the functional group or the functional group in the copolymer of the present invention. The group of the above-mentioned compound is represented by a hydroxyl group of a hydroxyl group:: a compound group of the above-mentioned compound, for example, a hydrazine-hydroxymethyl (meth) acrylamide, a hydrazine-hydroxyethyl group (for example) A modified to amide, acrylamide, hydrazine-hydroxypropyl (meth) acrylamide, hydrazine-hydroxybutyl
jcX 甲基)丙烯醯胺、N -甲氧基甲基(甲基)丙烯醯胺、N -甲氧 Μ基乙基(甲基)丙烯醯胺、N -甲氧基丙基(甲基)丙烯醯胺、 甲氧基丁基(甲基)丙烯醯胺等烷基爲(^〜〇4者。此等之 |自己交聯性單體可單獨使用,亦可二種以上之混合物使 ^用。而且,以(甲基)丙嫌酸〜表示者係表示甲基丙儲酸〜 或丙烯酸〜(以下皆同)。 自己交聯性單體係使用形成乳液之單體總量的2〜30重 量%。若小於2重量%時鉛筆硬度、耐污染性、常溫及高溫 下之潤滑性不佳,而若大於3 0重量%時水系乳液之安定性 不佳,故無法採用。 其他共聚性單體只要是可與上述之自己交聯性單體共jcX methyl) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyindolyl (meth) acrylamide, N-methoxypropyl (methyl) The alkyl group such as acrylamide or methoxybutyl (meth) acrylamide is (^~〇4. These | self-crosslinkable monomers may be used singly or in combination of two or more. Moreover, the (meth) propylene sulphuric acid ~ indicates that the methyl propyl storage acid ~ or acrylic acid ~ (the same below). Self-crosslinking single system using the total amount of monomers forming the emulsion 2 ~ 30% by weight. If less than 2% by weight, pencil hardness, stain resistance, lubricity at normal temperature and high temperature are not good, and if it is more than 30% by weight, the stability of the aqueous emulsion is not good, so it cannot be used. As long as the monomer is compatible with the above-mentioned self-crosslinking monomer
Claims (1)
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KR200449228Y1 (en) * | 2007-12-21 | 2010-06-24 | 한국동서발전(주) | Electrode detector |
CN106047090B (en) * | 2016-05-28 | 2019-03-26 | 晟通科技集团有限公司 | Compound UV photocureable coating of perfluoropolyether acrylate and preparation method thereof |
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US5726244A (en) * | 1995-08-10 | 1998-03-10 | Basf Corporation | Aqueous coating compositions for environmental etch resistant coatings |
KR0128134B1 (en) * | 1994-12-28 | 1998-04-01 | 김만제 | Resin solution for steel plate coating |
US5902851A (en) * | 1996-12-24 | 1999-05-11 | Matsushita Electric Works, Ltd. | Resinous composition for foul releasing coat and coating articles |
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