TW201217468A - Contamination resistant coating composition having excellent durability - Google Patents

Contamination resistant coating composition having excellent durability Download PDF

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TW201217468A
TW201217468A TW100133182A TW100133182A TW201217468A TW 201217468 A TW201217468 A TW 201217468A TW 100133182 A TW100133182 A TW 100133182A TW 100133182 A TW100133182 A TW 100133182A TW 201217468 A TW201217468 A TW 201217468A
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Taiwan
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component
acid
group
resin
coating composition
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TW100133182A
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Chinese (zh)
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TWI525160B (en
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Hideki Matsuda
Takeshi Uchida
Masato Nakamizu
Masahiro Hayashi
Yuya Miyoshi
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Kansai Paint Co Ltd
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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention addresses the problem of providing a contamination resistant coating composition that can form a coating layer having excellent retention of corrosion resistance and contamination resistance with respect to rainwater and the like, in particular, a contamination resistant coating composition that is suitable for overcoat film formation on a coated metal sheet having a glossiness that is no greater than a medium gloss. The coating composition includes a specific organosilicate and/or a condensate component thereof and a fluorine-atom-containing non-aqueous dispersion resin component in a resin binder containing: a polyester resin component that contains a hydroxyl-group-containing polyester resin; and a melamine resin component that contains a butyl ether melamine resin.

Description

201217468 六、發明說明： 【發明所屬之技彳标領诚】 技術領域 本發明係有關於-種主要對雨水等長期耐污染性之保 持性優異_污㈣料、喊物，特別是適於形成塗裳金屬 板的表塗塗膜之耐污染塗料組成物、使用該耐污染塗料組 成物之财雨水汗染性優異塗膜的形成方法、及形成有由該 耐污染塗料組成物所構成之硬化塗膜的塗裝金屬板。 c先前技術】 背景技術 迄今，將耐候性優異之室外用塗料以裝飾或保護為目 的塗裝於室外的基材(例如建築物、展示物、柵攔、器具、 機械等）。作為室外用而受到使用之塗料可例示如含聚胺酿 樹脂的塗料、含氣樹脂的塗料、含珍氧樹脂的塗料、含丙 烯酸樹脂的塗料、含聚酯的塗料等；然而該等的塗裝物因 於室外曝曬’因沙塵'鐵粉、雨（s_'太陽光線等的影響， 使塗裝物表面容易弄辦，而有塗膜美觀程度降低等缺點。 本申咕人為了解決邊問題點，提出一種耐污染性優異 之表塗塗料組成物（參考專利文獻丨國際公開w〇9娜87〇 號公報），該耐污染性優異之表塗塗料乡且成物係由將四烧基 石夕酸鹽及/或聽合物摻混於含有含經基之譲脂及胺基 樹脂交聯劑作為反應硬化型有機樹脂之有機溶劑系塗料組 成物⑴、或含有由含減的氟制及/或含祕的丙稀酸樹 脂與（錢化）聚異氰編旨化合物交咖作為反應硬化型有 201217468 機樹脂之含有機溶劑的塗料組成物（2)_成之塗料組成 物；其特徵在於，相對於酸處理後之塗膜表面的水之接觸 角為70度以下。 然而’專利文獻1之表塗塗料組成物在室外使用時，對 雨跡污痕等、雨水等的耐污染性之保持性不充足，又，即 便是在室外❹之初期階段，對雨水等的耐污染性亦不足。 又，提案有一制污染性塗料組成物作為可抑制屬污 染原因之物_著m隨之耐污染性塗肺成物（參 照專利文獻2)’該对污染性塗料組成物係以⑷聚賴脂、 (b)交聯劑、⑷含絲或羧基之聚自旨改質聚料化合物、及 /或具有經基或叛基之聚驗改質聚石夕氧化合物與⑷氣樹脂 粒子為主成分者。然而，藉由併用屬耐污染性賦予成分之 聚石夕氧化合物、及I樹脂粒子所產生之耐污染性提高效果 娘不充足’故從酬污染性塗料組成物所獲得之塗膜的財 汚染性不足。 又，作為對雨痕污染之耐污染性' 加工性、塗膜外觀 優異之«鋼板用塗料組成物係提案有—種熱硬化性樹脂 組成物，其係由（Α)羥值5〜300、數平均分子量5〇〇〜2〇〇〇〇之 多元醇樹脂、⑻胺基樹脂、（C)石夕氧烧化合物、（d)硬化觸 媒所構成。（參照專利文獻3)然而，對由該熱硬化性樹脂組 成物所獲得的塗膜之歷時性長期的雨痕污染之耐污染性， 雖然在有光澤之塗膜的情況下為Mf，在添加消光劑等 而形成半光以下之光澤⑽光澤在5〇左右以巧的塗膜的情 況下，耐污染性及耐姓性的保持性不足。201217468 VI. Description of the Invention: [Technical Fields of the Invention] Technical Field The present invention relates to an excellent retention of long-term pollution resistance such as rainwater, smudges, materials, and particularly suitable for formation. a stain-resistant coating composition of a surface coating film of a coating metal plate, a method for forming a coating film excellent in rainwater staining using the pollution-resistant coating composition, and a hardening method comprising the composition of the pollution-resistant coating The coated metal plate of the coating film. C. Prior Art [Background Art] Conventionally, an outdoor paint having excellent weather resistance is applied to an outdoor substrate (for example, a building, a display, a barrier, an appliance, a machine, etc.) for the purpose of decoration or protection. The coating material to be used for outdoor use may, for example, be a coating containing a polyamine-dying resin, a coating containing a gas resin, a coating containing an oxygen-containing resin, a coating containing an acrylic resin, a coating containing a polyester, etc.; however, such coating Due to the outdoor exposure, due to the influence of dust, iron powder, rain (s_'sunlight, etc., the surface of the coated object is easy to handle, and the appearance of the coating film is reduced, etc.) In view of the problem, a surface coating composition having excellent stain resistance is proposed (refer to the patent document 丨 International Publication No. 娜 娜 〇 87〇), which is excellent in stain resistance and is formed by the four-burning The skeletal acid salt and/or the conjugate compound is blended in an organic solvent-based coating composition (1) containing a rhodium-containing sulfonate and an amine-based resin crosslinking agent as a reaction-curing organic resin, or contains a fluorine-containing compound. And/or a secret acrylic resin and a (poly) polyisocyanide-based compound as a reaction-hardening type of coating composition having an organic solvent of 201217468 resin (2)_forming coating composition; Characterized by the acid The water contact angle of the surface of the coating film is not more than 70 degrees. However, when the surface coating composition of Patent Document 1 is used outdoors, the stain resistance such as rain stains and rain, and the like are not sufficient, and Even in the early stage of outdoor rafting, the pollution resistance to rainwater and the like is insufficient. In addition, it is proposed to have a pollutant coating composition as a substance that can suppress the cause of pollution. (Refer to Patent Document 2) 'The contaminating coating composition is characterized by (4) polylysate, (b) a crosslinking agent, (4) a filament- or carboxyl group-containing modified meta-polymer compound, and/or a warp group or The rebel group is a combination of a modified polysulfide compound and (4) a gas resin particle as a main component. However, the contamination resistance caused by the combination of the polysulfide compound and the I resin particle which are components imparted to the pollution resistance is used. The improvement of the effect is not sufficient. Therefore, the coating film obtained from the composition of the contaminated paint is insufficient in pollution. As a result of the pollution resistance to rain stains, the processability and the appearance of the coating film are excellent. The system proposal has a kind of hot The resin composition is a polyol resin having a (hydroxy) value of 5 to 300, a number average molecular weight of 5 Å to 2 Å, (8) an amine resin, (C) a oxy-oxygen compound, (d) (Conditional Patent Document 3) However, the coating film obtained from the thermosetting resin composition has a long-term rain stain contamination resistance to the coating film, although it is in a glossy coating film. In the case of Mf, when a matting agent or the like is added to form a gloss of a half-light or less (10), a gloss of about 5 Å is applied, and the stain resistance and the resistance to the surname are insufficient.

S 4 201217468 【專利文獻1】：國際公開WQ9德謂號公報 【專利文獻2】：日本特開平⑼-似⑷ 【專利文獻3】：日本特開平1〇-67945號公報 C 日月】 發明概要 發明欲解決之課題 本發明係提供一種耐污然塗料組成物，其係 雨水等_污染性及耐純之保持性優異之塗膜^成對 塗料組成物’特別是適用於形成半光以下光澤之 板的表塗塗膜者。 1裝金屬 以解決課題之手段 本發明者等為了解決習知之上述問題點而專 覆研究的結果，發現有—難料㈣物可形成(軸= 光以下之光澤(6〇。光澤為50左右以下）之塗膜中 = 的财污染性之保持性優異之塗膜，而完成了本發明；前述 塗料組成物係於含有特㈣含減聚賴脂之聚_月^成 分、與含有T基ϋ化三聚氰贿脂之三聚氰胺樹脂成分之 樹脂黏結劑中，包含特定的有機㈣鹽及/或其縮合物成 分、及含氣原子之非水性分散㈣樹脂成分者。 即，本發明係包含以下的發明： 第1項一種耐污染塗料組成物，其含有： (Α)聚酯樹脂成分’其含有5〇至1〇〇質量％之數平均分子量為 5000至30000、經值為n〇〇mgK〇H/g之含經基聚酿樹脂 (A1)作為固體成分’且該含羥基聚酯樹脂(A1)係藉由 5 201217468 (ai)多元酸成分，及 (a2)醇成分 之反應所獲得之聚酯樹脂成分； (B) 二聚氰胺樹脂成分，其含有30至1〇〇質量％之丁基驗化三 聚氰胺樹脂(B1)作為固體成分； (C) 由下述通式所表示之有機砂酸鹽及/或其縮合物成分： 通式：（Ι^)η-8ί-(ΟΙ12)4-η [式中’ R1係亦可由環氧基或疏基取代之碳數1至18的貌基 或本基，R2為碳數1至6的燒基，η為〇或1。];及 (D) 含有氟原子的非水性分散液型樹脂； 且該耐污染塗料組成物之特徵在於： 以(Α)成分及(Β)成分之固體成分總量為基準，作為固體成分， (C) 成分之含量為1至20質量0/〇 ; (D) 成分之含量為5至30質量％。 第2項如第1項之耐污染塗料組成物，其中含有氟原子 的非水性分散液型樹脂(D)為可藉由在含有氟原子之分散 穩定劑(Dla)與有機溶劑(Dlb)之混合液中，使聚合性不飽和 单體共聚合並在該混1合液中形成不溶的聚合物粒子(D1 c) 來調製之非水性分散液型樹脂。 第3項如第2項之耐污染塗料組成物，其中含有說原子 的分散穩定劑(Dla)係藉由將包含具有氟烷基之（甲基）丙稀 酸酯、及/或含氟烯煙之聚合性不飽和單體進行共聚人所辦 得之聚合物。 第4項如第1項之耐污染塗料組成物，其中在獲得含# 201217468 基聚酯樹脂(A 1)的反應中，多元酸成分(a 1)中的脂環族多元 酸(al-Ι)之合計含量以多元酸成分(al)之總量為基準，係在 50至lOOmol%之範圍内。 第5項如第1至3項中任一項之耐污染塗料組成物，其 中以聚酯樹脂成分（A)及三聚氰胺樹脂成分(B)之固體成分 總量作為基準，含有作為固體成分之50至90質量％的聚酯 樹脂成分(A)，及作為固體成分之10至50質量％的三聚氰胺 樹脂成分(B)。 第6項如第1至4項中任一項之耐污染塗料組成物，係 進一步含有消光劑(E)。 第7項一種塗膜形成方法，其特徵在於包含以下步驟： 於金屬板上之單面或兩面上，形成由無鉻底漆塗料 所形成之底漆塗膜的步驟；及 在底漆塗膜之至少一者上，形成由如第1項之耐污 染塗料組成物所形成之表塗塗膜的步驟，。 第8項一種塗裝金屬板的製造方法，其特徵在於包含 以下步驟： 在金屬板上之單面或兩面上，形成由無鉻底漆塗料 所形成之底漆塗膜的步驟；及 在底漆塗膜之至少一者上，形成由如第1項之耐污 染塗料組成物所形成之表塗塗膜的步驟。 第9項一種塗裝金屬板，係藉由如申請專利範圍第7或 8項之方法所獲得。 發明效果 201217468 本發明之耐污染塗料組成物係在含有特定的含羥基聚 酯樹脂之聚酯樹脂成分、與含有丁基醚化三聚氰胺樹脂之 三聚氰胺樹脂成分的樹脂黏結劑中，含有特定的有機矽酸 鹽及/或其縮合物成分、及含氟原子之非水性分散液型樹脂 成分之塗料組成物；藉由本塗料組成物，可形成特別是在 半光以下之光澤（60°光澤為50左右以下）之塗膜中，對雨水 等的耐污染性之保持性優異的塗膜。 由本發明之耐污染塗料組成物所形成之塗膜，特別是 在作為半光以下光澤之塗膜時，可形成對雨水等的耐污染 性之保持性優異的塗膜之理由雖然尚未明確，但認為係如 下所述。 以提高耐污染性為目的，迄今雖已大量提案有併用含 有氟原子的聚合物及矽酸鹽化合物（矽氧化合物）所獲得之 耐污染性塗料組成物，以獲得氟原子特性所造成之撥水 性、撥油性及所生成的矽醇所造成之親水化的相乘作用， 但藉由併用所獲得之耐污染性提高效果並不充足。一般認 為是因為含有氟原子的成分及矽酸鹽成分皆非均勻地存在 於塗膜表層之故。 本發明之耐污染塗料組成物中耐污染性賦予成分為有 機矽酸鹽及/或其縮合物成分、及含有氟原子的非水性分散 液型樹脂成分，係併用含有氟原子的聚合物及矽酸鹽化合 物者。 一般認為是因為在本發明之塗料組成物中，該含有氟 原子的非水性分散液型樹脂成分係在含有分散穩定劑之有 201217468 機溶劑中，以不溶狀態分散之形態的聚合物粒子，因此與 迄今之併用含有氟原子的聚合物及矽酸鹽化合物（矽氧化 合物）之耐污染性塗料組成物相比，含有氟原子的成分及石夕 酸鹽成分兩者係均勻地存在於塗膜表面，而可獲得兩者較 緻密且良好的分布狀態之故。 藉由消光劑等而形成半光以下之光澤的塗膜，相較於 有光澤的塗膜，其表面形狀凹凸，水的濡溼性佳，且關於 而于加水分解性係處於較嚴苛的狀況下之故，在使用習知之 聚酯塗料系時，會加速塗裝表面的劣化（阻流等），而容易呈 現不好看的外觀狀態。 由本發明之耐污染塗料組成物所獲得之塗膜，因為可 充分地發揮氟原子特性所產生之撥水性、撥油性及所生成 之石夕醇產生之親水化的相乘作用，故财污染性非常地優 異，因此在與迄今之聚酯塗料系相比之下，一般認為係可 發揮優異外觀及耐污染性之保持性者。 c實方包方式j 用以實施發明之最佳形態 耐污染塗料組成物 本發明之耐污染塗料組成物係含有：下述聚酯樹脂成 分(A)、三聚氰胺樹脂成分(B)、有機矽酸鹽及/或其縮合物 成分(C)、及含有氟原子的非水性分散液型樹脂成分(D)的塗 料組成物。 (A)聚S旨樹脂成分 本發明之塗料組成物中，聚酯樹脂成分(A)相對於聚酯 201217468 樹脂成分(A)之固體成分總量，係含有50〜100質量％之下述 含羥基聚酯樹脂(A1)作為固體成分。 (A1)含羥基聚酯樹脂 聚酯樹脂成分(A)的必需成分之含羥基聚酯樹脂 (A1)，係通常可藉由下述多元酸成分(al)與醇成分(a2)之酯 化反應或酯交換反應來製造。 上述多元酸成分(al)係可使用在製造聚酯樹脂時通常 用來作為多元酸成分使用的化合物。多元酸成分(al)例如可 使用脂環族多元酸(al-Ι)、脂肪族多元酸(al-2)、芳香族多 元酸(al-3)等。 脂環族多元酸(al-Ι)—般為在1分子中具有1個以上的 脂環族的構造（例如：4〜6員環)與2個以上的羧基之化合物、 該化合物的酸酐及該化合物的酯化物。作為該脂環族多元 酸(al-Ι)係可舉例如：1,2-環己烷二羧酸、1,3-環己烷二羧 酸、1,4-環己烷二羧酸、4-環己烯-1,2-二羧酸、3-曱基-1，2-環己烷二羧酸、4-曱基-1,2-環己烷二羧酸、1,2,4-環己烷三 羧酸、1,3,5-環己烷三羧酸等的脂環族多價羧酸；該等脂環 族多價羧酸的酸酐；該等脂環族多價羧酸的低級烷酯化物 (此處，在本說明書中「低級烷」係指例如碳數1〜5左右的烷 基。）等。脂環族多元酸(al-Ι)可單獨或組合2種以上來使用。 作為脂環族多元酸(al-Ι)，特別是可適宜地使用1,2-環己 烷二羧酸、1,2-環己烷二羧酸酐、1,3-環己烷二羧酸、1,4-環 己烷二羧酸、4-環己烯-1，2-二羧酸、4-環己烯-1,2-二羧酸酐。 上述之中，從耐加水分解性的觀點看來，可特別適宜 10 201217468 地使用1,2-環己烷二羧酸、1,2-環己烷二羧酸酐。 在獲得上述含羥基聚酯樹脂(A1)的反應中，脂環族多 元酸(al-Ι)的合計含量計，從耐加水分解性及耐污染性的觀 點看來，以多元酸成分(al)的總量為基準，係以50〜lOOmol% 為佳，特別是以70〜lOOmol%為佳，更特別是以80〜lOOmol% 之範圍内為佳。 脂肪族多元酸(al-2)—般係於1分子中含有2個以上的 羧基之脂肪族化合物、該脂肪族化合物的酸酐、該脂肪族 化合物的酯化物等。具體而言，可舉例如：丁二酸、戊二 酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、-J—烧 二酸、十二烧二酸、十三烧二酸、十八烧二酸、檸檬酸等 脂肪族多價羧酸；該等脂肪族多價羧酸的酸酐；該等脂肪 族多價羧酸的低級烷酯化物等。脂肪族多元酸(al-2)可單獨 或組合2種以上來使用。 作為脂肪族多元酸(al-2)，宜使用具有碳數4〜18之烷基 鏈的二羧酸。上述具有碳數4〜18之烷基鏈的二羧酸係可舉 例如：己二酸、庚二酸、辛二酸、壬二酸、癸二酸、— 烧二酸、十二烷二酸、十三烷二酸、十八烧二酸等，其中 尤其是可適宜地使用己二酸。 芳香族多元酸(al-3)—般而言係於1分子中具有2個以 上羧基的芳香族化合物、該芳香族化合物的酸酐、該芳香 族化合物的酯化物等。具體而言，例如鄰苯二甲酸、異酞 酸、對酞酸、萘二羧酸、4,4'-聯苯二羧酸、1,2,4-苯三甲酸、 1,2,4,5-苯四甲酸等芳香族多價羧酸；該等芳香族多價羧酸 201217468 的酸酐；該等芳香族多價羧酸的低級烷酯化物等。芳香族 多元酸(al-3)可單獨或組合2種以上來使用。 在上述多元酸(a 1)以外，作為酸成分可舉例如：椰子油 脂肪酸、棉子油脂肪酸、大麻籽油脂肪酸、米糠油脂肪酸、 魚油脂肪酸、松油脂肪酸、大豆油脂肪酸、亞麻仁油脂肪 酸、桐油脂肪酸、菜籽油脂肪酸、乾麻油脂肪酸、脫水蓖 麻油脂肪酸、紅花油脂肪酸等脂肪酸；十二酸、十四酸、 十六酸、十八酸 '十八稀酸、十八碳二烯酸、十八碳三烯 酸、苯曱酸、對-第三丁基苯甲酸、環己烷酸、10_苯基硬脂 酸等單羧基酸；乳酸、檸檬酸、3-羥基丁酸、3-羥基-4-乙 氧苯曱酸等羥基羧酸等。上述多元酸(al)以外的酸成分可單 獨或組合2種以上來使用。 在上述多元酸(al)以外的酸成分之中，可適宜地使用脂 肪酸(a3)。脂肪酸(a3)係直鏈烴之1價的羧酸，可舉例如： 椰子油脂肪酸、棉子油脂肪酸、大麻籽油脂肪酸' 米糠油 脂肪酸、魚油脂肪酸、松油脂肪酸、大豆油脂肪酸、亞麻 仁油脂肪酸、桐油脂肪酸、菜籽油脂肪酸、蓖麻油脂肪酸、 脫水蓖麻油脂肪酸、紅花油脂肪酸等脂肪酸；十二酸、十 四酸、十六酸、十八酸、十八烯酸、十八碳二烯酸、十八 碳三烯酸等。上述脂肪酸可單獨或組合2種以上使用。 該等之中，從耐候性的觀點看來，可適宜地使用不飽 和度低者，具體而言，碘價在20以下，特別是在1〇以下者。 碘價係作為表示化合物之不飽和度的指標之數值，以1〇〇g 樣本所吸收之碘的克數來表示。測定可依照jIS κ 5421之標 12 201217468 準來進行。 從上述不飽和度的觀點看來，作為脂肪酸(a3)係可適宜 地使用椰子油脂肪酸、十二酸、十四酸、十六酸、十八酸， 特別是椰子油脂肪酸。 醇成分（a2)係可適宜地使用在1分子中具有2個以上羥 基之多元醇。上述多元醇係可舉例如：脂環族二醇(a2_i)、 脂肪族二醇(a2·2)、芳香族二醇(a2-3)等。 脂環族二醇(a2-l)—般而言係於丨分子中具有1個以上 的脂環族構造(例如，4〜6員環)與2個羥基的化合物。作為該 脂環族二醇(a2-l)係可舉例如：l，4-環己烷二甲醇 '三環癸 烷二曱醇、氫化雙酚A、氫化雙酚F等二羥基醇；對該等二 經基醇加成ε-己内自旨等内醋化合物而得之聚内醋二醇等； 該等可單獨或組合2種以上來使用。 脂肪族二醇(a2-2) —般而言係於1分子中具有2個經基 的脂肪族化合物。作為該脂肪族二醇(a2-2)係可舉例如：乙 一 if·、丙·一》酵、一乙一酵、1,3-丙二醇、三縮四乙二醇、三 伸甘醇、二丙二醇、1，4-丁二醇、1，3-丁二醇、2,3-丁二醇、 1，2-丁一醉、3-曱基-1，2-丁一醇 ' 2-丁 基-2-乙基-1，3-丙烧二 醇、1，2-戊烧二醇、1,5-戊烧二醇、1，4-戍烧二醇、2,4-戊院 二醇、2,3-二甲基-1,3-丙二醇、四曱基乙二醇、3 -甲基_i，5_ 戊烧二醇、2,2,4-二甲基-1，3-戊院二醇、1，6-己烧二醇、ι，5_ 己烧·一酵、1，4-己烧二酵、2,5-己院二酵、1,9-壬貌二醇、 1，10-癸烷二醇、1,12-十二烷二醇、新戊二醇等；該等係可 單獨或組合2種以上來使用。 13 201217468 芳香族二醇（a2-3)—般而言係於1分子中具有2個羥基 的芳香族化合物。作為該芳香族二醇(a2-3)係可舉例如：對 酞酸雙（羥乙基）酯等酯二醇化合物；雙酚A的環氧烷加成物 等；該等係可單獨或組合2種以上來使用。 作為前述脂環族二醇（a2-l)、脂肪族二醇（a2-2)及芳香 族二醇(a2-3)以外的多元醇係可舉例如：聚乙二醇、聚丙二 醇、聚丁二醇等聚醚二醇化合物；甘油、三（羥甲）乙烷、 三（經曱）丙烧、二甘油、三甘油、1,2,6-己烧三醇、新戊四 醇、二新戊四醇、三聚異氰酸三（2-羥乙基）酯、山梨醇、甘 露糖醇等3價以上醇；ε-己内酯等内酯化合物對該等3價以 上的醇進行加成所獲得之聚内酯多元醇化合物等。 上述之中，從高分子量化及提高在使用脂肪酸(a3)時與 脂肪酸(a3)之改質反應的反應性之觀點看來，可適宜地使用 3價以上的醇。 作為上述3價以上的多元醇係可舉例如：三（羥曱）乙 烧、三（經甲）丙院、二甘油、三甘油、1,2,6-己烧三醇、新 戊四醇、二新戊四醇、山梨醇、甘露糖醇等3價以上的醇； 使ε -己内酯等内酯化合物對該等3價以上的醇進行加成所 獲得之聚内酯多元醇化合物；三聚異氰酸三（2-羥乙基）S旨、 三聚異氰酸三（2-羥丙基）酯、三聚異氰酸三(2-羥丁基）酯等 三聚異氰酸三（羥烷基）酯等。該等之中，特別是以三（羥曱） 丙烧為佳。 在使用3價以上的多元醇時，醇成分(a2)中之3價以上多 元醇的合計含量係以醇成分（a2)的總量為基準，而以在 14 201217468 10〜70mol%，特別是在20〜65m〇i% ’更特別是在3〇〜6〇m〇1% 之範圍内為佳。 又，作為上述上述多元醇以外的醇成分(a2)亦可視需要 使用例如曱醇、乙醇、丙基醇、丁基醇、十八醇、2_苯氧 基乙醇等單元醇；使環氧丙烷、環氧丁烷、合成高度分支 飽和脂肪酸的環氧丙基酯（商品名「CarduraEl〇」HEXION Specialty Chemicals公司製）等的單環氧化合物與酸進行反 應所獲得之醇化合物等。 含羥基聚酯樹脂（A1)之製造無特別限定，可依照一般 的方法來進行。例如，可藉由將以前述多元酸成分(al)作為 必需成分之酸成分與醇成分(a2)在氮氣流中，在15〇〜250°C 下反應5〜10小時，進行酯化反應或酯交換反應來製造。 在上述酯化反應或酯交換反應中，上述酸成分及醇成分 (a2)可一次添加，亦可分成數次添加。又，在開始合成含羧 基之聚酯樹脂後，亦可使用上述醇成分(a2)將該含羧基之聚 酯樹脂中的一部分羧基酯化。進一步，在開始合成含羥基聚 酯樹脂後，亦可使酸酐反應，將含羥基聚酯樹脂半酯化。 在進行前述酯化或酯交換反應時，為了促進反應，亦 可使用觸媒。作為觸媒係可使用二丁基錫氧化物、三氧化 二銻、醋酸鋅、醋酸錳、醋酸鈷、醋酸鈣、醋酸鉛、鈦酸 四丁醋、鈦酸四異丙酯等已知的觸媒。 又’含羥基聚酯樹脂(A1)係可在該樹脂的調製中、醋 化反應後或者酯交換反應後，以脂肪酸、單環氧化合物、 聚異氰酸酯化合物等進行改質。 15 201217468 作為上述脂肪酸係可舉例如：椰子油脂肪酸、棉子油 脂肺酸、大麻籽油脂肪酸、米糠油脂肪酸、魚油脂肪酸、 松油脂肪酸、大豆油脂肪酸、亞麻仁油脂肪酸、桐油脂肪 酸、菜籽油脂肪酸、蓖麻油脂肪酸、脫水蓖麻油脂肪酸、 紅花油脂肪酸等。S 4 201217468 [Patent Document 1]: International Publications WQ9 German-Japanese Standard [Patent Document 2]: Japanese Patent Publication (9)-like (4) [Patent Document 3]: Japanese Patent Laid-Open No. Hei-67945 DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention provides a composition for stain-resistant coating which is excellent in the retention of rainwater and the like, and which is excellent in the retention of stain resistance and purity, and is particularly suitable for forming a gloss of half light or less. The surface of the board is coated with a film. In the inventors of the present invention, in order to solve the above problems, the inventors of the present invention have found that it is difficult to produce (four) materials (axis = light below the light (6 〇. gloss is about 50) The present invention has been completed in the coating film of the following coating film which is excellent in retaining property of the contaminant, and the coating composition is contained in the poly(M) containing polycondensation lysate and the T-containing group. The resin binder of the melamine resin component of the phthalocyanine resin contains a specific organic (tetra) salt and/or a condensate component thereof, and a non-aqueous dispersion (four) resin component containing a gas atom. The invention of the first aspect is the pollution-resistant coating composition of the first aspect, which comprises: (Α) a polyester resin component having a number average molecular weight of from 5,000 to 30,000 and a value of n 〇〇 from 5 〇 to 1 〇〇 by mass. mgK〇H/g contains a base polymer resin (A1) as a solid component' and the hydroxyl group-containing polyester resin (A1) is a reaction product of 5 201217468 (ai) polybasic acid component and (a2) alcohol component a polyester resin component obtained; (B) a melamine resin component, 30 to 1% by mass of a butyl melamine resin (B1) as a solid component; (C) an organic sulphate represented by the following formula and/or a condensate thereof: Formula: (Ι ^)η-8ί-(ΟΙ12)4-η [In the formula, R1 is a group or a base having a carbon number of 1 to 18 which may be substituted by an epoxy group or a sulfhydryl group, and R2 is a carbon group having 1 to 6 carbon atoms. , η is 〇 or 1..; and (D) a non-aqueous dispersion type resin containing a fluorine atom; and the pollution-resistant coating composition is characterized by: the total solid content of the (Α) component and the (Β) component As a basis, as a solid component, the content of the component (C) is 1 to 20 mass%/〇; and the content of the component (D) is 5 to 30 mass%. The second item is the pollution-resistant coating composition of the first item, wherein The non-aqueous dispersion type resin (D) containing a fluorine atom is obtained by copolymerizing a polymerizable unsaturated monomer in a mixed solution of a dispersion stabilizer (Dla) containing a fluorine atom and an organic solvent (Dlb). A non-aqueous dispersion type resin prepared by forming insoluble polymer particles (D1 c) in the mixed liquid mixture. Item 3 is a pollution-resistant coating composition according to item 2, which contains said atom. The dispersion stabilizer (Dla) is a polymer obtained by copolymerizing a polymerizable unsaturated monomer containing a (meth) acrylate having a fluoroalkyl group and/or a fluorine-containing olefin. Item 4 is the pollution-resistant coating composition of item 1, wherein in the reaction for obtaining the #201217468-based polyester resin (A1), the alicyclic polybasic acid (al-Ι) in the polybasic acid component (a1) The total content of the polybasic acid component (al) is in the range of 50 to 100 mol%. The pollution-resistant coating composition according to any one of items 1 to 3, wherein The polyester resin component (A) as a solid component is contained in an amount of 50 to 90% by mass, and 10 to 50% by mass as a solid component, based on the total amount of the solid content of the ester resin component (A) and the melamine resin component (B). Melamine resin component (B). The pollution-resistant coating composition according to any one of items 1 to 4, further comprising a matting agent (E). Item 7 is a method for forming a coating film, comprising the steps of: forming a primer coating film formed of a chrome-free primer coating on one or both sides of a metal plate; and coating the primer film on the one side or both sides of the metal plate; In at least one of the steps of forming a surface coating film formed of the pollution-resistant coating composition of the first item. Item 8 is a method of manufacturing a coated metal sheet, comprising the steps of: forming a primer coating film formed of a chromium-free primer coating on one or both sides of a metal sheet; and A step of forming a surface coating film formed of the pollution-resistant coating composition of the first item on at least one of the paint coating films. Item 9 A coated metal sheet obtained by the method of claim 7 or 8. EFFECTS OF THE INVENTION 201217468 The stain-resistant coating composition of the present invention contains a specific organic oxime in a resin binder containing a specific polyester resin component containing a hydroxyl group-containing polyester resin and a melamine resin component containing a butyl etherified melamine resin. a coating composition of an acid salt and/or a condensate component thereof and a non-aqueous dispersion liquid resin component containing a fluorine atom; and the coating composition can form a gloss of at least half light (60° gloss is about 50) In the coating film of the following), the coating film which is excellent in the retention of the stain resistance of rainwater or the like. The reason why the coating film formed of the composition of the antifouling paint of the present invention is particularly excellent in the ability to form a coating film which is excellent in the stain resistance of rainwater or the like is not clear, but it is not clear. It is considered as follows. In order to improve the stain resistance, a large number of proposals have been made so far for the use of a fluorine-containing polymer and a phthalate compound (oxygen compound) to obtain a stain-resistant coating composition to obtain the characteristics of the fluorine atom. Water-based, oil-repellent, and the synergistic effect of hydrophilization caused by the produced sterol, but the effect of improving the stain resistance obtained by the combination is not sufficient. It is generally considered that the fluorine atom-containing component and the citrate component are non-uniformly present on the surface of the coating film. In the pollution-resistant coating composition of the present invention, the contamination-imparting component is an organic citrate and/or a condensate component thereof, and a non-aqueous dispersion-type resin component containing a fluorine atom, and a fluorine atom-containing polymer and hydrazine are used in combination. Acid compound. It is considered that the non-aqueous dispersion-type resin component containing a fluorine atom in the coating composition of the present invention is a polymer particle in a form of being dispersed in an insoluble state in a solvent containing a dispersion stabilizer in 201217468. The fluorine atom-containing component and the oxalate component are uniformly present in the coating film as compared with the contamination-resistant coating composition of a polymer containing a fluorine atom and a phthalate compound (oxygen compound). The surface is obtained, and the dense and good distribution of the two is obtained. A coating film having a gloss of a half-light or less by a matting agent or the like has a surface unevenness as compared with a glossy coating film, and the water has a good wettability, and the hydrolyzable system is in a relatively severe state. In the case of using a conventional polyester coating system, deterioration of the coating surface (flow resistance, etc.) is accelerated, and an unsightly appearance state is easily exhibited. The coating film obtained from the composition of the pollution-resistant coating material of the present invention can sufficiently exhibit the water repellency, the oil repellency, and the hydrophilization of the generated sulphuric acid produced by the characteristics of the fluorine atom, so that the pollution is rich. It is very excellent, and therefore it is generally considered to be superior to the polyester coating system of the prior art in that it can exhibit excellent appearance and stain resistance. c solid package method j The best form of the antifouling paint composition for carrying out the invention The antifouling paint composition of the present invention contains: the following polyester resin component (A), melamine resin component (B), organic tannic acid A coating composition of a salt and/or a condensate component (C) thereof and a non-aqueous dispersion-type resin component (D) containing a fluorine atom. (A) Polys-based resin component In the coating composition of the present invention, the polyester resin component (A) is contained in an amount of 50 to 100% by mass based on the total amount of the solid content of the resin component (A) of the polyester 201217468. The hydroxy polyester resin (A1) is used as a solid component. (A1) The hydroxyl group-containing polyester resin (A1) which is an essential component of the hydroxyl group-containing polyester resin polyester resin component (A), which can be usually esterified with the alcohol component (a2) by the following polybasic acid component (al) It is produced by a reaction or a transesterification reaction. As the polybasic acid component (al), a compound which is usually used as a polybasic acid component in the production of a polyester resin can be used. As the polybasic acid component (al), for example, an alicyclic polybasic acid (al-oxime), an aliphatic polybasic acid (al-2), an aromatic polybasic acid (al-3), or the like can be used. An alicyclic polybasic acid (al-oxime) is generally a structure having one or more alicyclic groups in one molecule (for example, a 4 to 6 member ring), a compound having two or more carboxyl groups, an acid anhydride of the compound, and An esterified product of the compound. Examples of the alicyclic polybasic acid (al-fluorene) include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. 4-cyclohexene-1,2-dicarboxylic acid, 3-mercapto-1,2-cyclohexanedicarboxylic acid, 4-mercapto-1,2-cyclohexanedicarboxylic acid, 1,2, An alicyclic polyvalent carboxylic acid such as 4-cyclohexanetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic acid; an anhydride of the alicyclic polyvalent carboxylic acid; The lower alkyl ester of a carboxylic acid (herein, in the present specification, "lower alkane" means, for example, an alkyl group having a carbon number of about 1 to 5). The alicyclic polybasic acid (al-oxime) can be used singly or in combination of two or more. As the alicyclic polybasic acid (al-oxime), particularly, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, and 1,3-cyclohexanedicarboxylic acid can be suitably used. 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride. Among the above, from the viewpoint of hydrolysis resistance, it is particularly preferable to use 1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic anhydride as 10 201217468. In the reaction for obtaining the above-mentioned hydroxyl group-containing polyester resin (A1), the total content of the alicyclic polybasic acid (al-oxime) is a polybasic acid component from the viewpoint of hydrolysis resistance and stain resistance. The total amount is preferably from 50 to 100 mol%, particularly preferably from 70 to 100 mol%, more preferably from 80 to 100 mol%. The aliphatic polybasic acid (al-2) is generally an aliphatic compound containing two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, an esterified product of the aliphatic compound, and the like. Specifically, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, -J-succinic acid, dodecanedioic acid, and ten An aliphatic polyvalent carboxylic acid such as trisuccinic acid, octadecanoic acid or citric acid; an acid anhydride of the aliphatic polyvalent carboxylic acid; a lower alkyl esterified product of the aliphatic polyvalent carboxylic acid; and the like. The aliphatic polybasic acid (al-2) may be used singly or in combination of two or more. As the aliphatic polybasic acid (al-2), a dicarboxylic acid having an alkyl chain having 4 to 18 carbon atoms is preferably used. Examples of the dicarboxylic acid having an alkyl chain having 4 to 18 carbon atoms include adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, succinic acid, and dodecanedioic acid. And tridecanedioic acid, octadecandioic acid, and the like, among which adipic acid can be suitably used. The aromatic polybasic acid (al-3) is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, an esterified product of the aromatic compound, and the like. Specifically, for example, phthalic acid, isophthalic acid, p-nonanoic acid, naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4, An aromatic polyvalent carboxylic acid such as 5-benzenetetracarboxylic acid; an acid anhydride of the aromatic polyvalent carboxylic acid 201217468; a lower alkyl esterified product of the aromatic polyvalent carboxylic acid. The aromatic polybasic acid (al-3) may be used singly or in combination of two or more. Other than the polybasic acid (a1), examples of the acid component include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, pine oil fatty acid, soybean oil fatty acid, and linseed oil fatty acid. Fatty acids such as tung oil fatty acid, rapeseed oil fatty acid, dry sesame oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid; dodecanoic acid, tetradecanoic acid, hexadecanic acid, octadecanoic acid, octadecanoic acid, octadecaene a monocarboxylic acid such as acid, octadecatrienoic acid, benzoic acid, p-t-butylbenzoic acid, cyclohexane acid or 10-phenyl stearic acid; lactic acid, citric acid, 3-hydroxybutyric acid, A hydroxycarboxylic acid such as 3-hydroxy-4-ethoxybenzoic acid or the like. The acid component other than the polybasic acid (al) may be used singly or in combination of two or more. Among the acid components other than the polybasic acid (al), a fatty acid (a3) can be suitably used. The fatty acid (a3) is a monovalent carboxylic acid of a linear hydrocarbon, and examples thereof include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid 'rice oil fatty acid, fish oil fatty acid, pine oil fatty acid, soybean oil fatty acid, and linseed. Fatty acids such as oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid; dodecanoic acid, tetradecanoic acid, palmitic acid, octadecanoic acid, oleic acid, eighteen carbon Dienoic acid, octadecatrienoic acid, and the like. These fatty acids may be used alone or in combination of two or more. Among these, from the viewpoint of weather resistance, those having a low degree of subsufficiency can be suitably used. Specifically, the iodine value is 20 or less, particularly 1 Å or less. The iodine value is a numerical value indicating an unsaturation of a compound, and is expressed in grams of iodine absorbed by a sample of 1 〇〇g. The measurement can be carried out in accordance with the standard of JIS κ 5421 12 201217468. From the viewpoint of the above-mentioned degree of unsaturation, coconut oil fatty acid, dodecanoic acid, tetradecanoic acid, palmitic acid, octadecanoic acid, particularly coconut oil fatty acid can be suitably used as the fatty acid (a3). As the alcohol component (a2), a polyol having two or more hydroxyl groups in one molecule can be suitably used. The polyhydric alcohol may, for example, be an alicyclic diol (a2_i), an aliphatic diol (a2·2) or an aromatic diol (a2-3). The alicyclic diol (a2-l) is generally a compound having one or more alicyclic structures (e.g., 4 to 6 membered rings) and two hydroxyl groups in the oxime molecule. The alicyclic diol (a2-l) may, for example, be a dihydric alcohol such as 1, 4-cyclohexanedimethanol 'tricyclodecane dinonanol, hydrogenated bisphenol A or hydrogenated bisphenol F; The di-mercapto alcohol is added to the glycerin or the like obtained by the internal vinegar compound, and the like may be used alone or in combination of two or more. The aliphatic diol (a2-2) is generally an aliphatic compound having two radicals in one molecule. Examples of the aliphatic diol (a2-2) include, for example, ethyl-if, propanone, yeast, 1,3-propanediol, triethylene glycol, triethylene glycol, and dipropylene glycol. , 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butan, 3-mercapto-1,2-butanol '2-butyl -2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-hydrazine diol, 2,4-pentylene glycol , 2,3-dimethyl-1,3-propanediol, tetradecyl glycol, 3-methyl-i, 5-pentanediol, 2,2,4-dimethyl-1,3-pentane Diol, 1,6-hexane diol, ι,5_ hexane, one yeast, 1,4-hexanol, 2,5-hexamycin, 1,9-formaldehyde diol, 1 , 10-decanediol, 1,12-dodecanediol, neopentyl glycol, etc.; these may be used alone or in combination of two or more. 13 201217468 The aromatic diol (a2-3) is generally an aromatic compound having two hydroxyl groups in one molecule. Examples of the aromatic diol (a2-3) include an ester diol compound such as p-citric acid bis(hydroxyethyl) ester; an alkylene oxide adduct of bisphenol A; and the like; Two or more types are used in combination. Examples of the polyhydric alcohol other than the alicyclic diol (a2-l), the aliphatic diol (a2-2), and the aromatic diol (a2-3) include polyethylene glycol, polypropylene glycol, and poly a polyether diol compound such as butanediol; glycerin, tris(hydroxymethyl)ethane, tris(sulfonium)propane, diglycerin, triglycerin, 1,2,6-hexane triol, pentaerythritol, a trivalent or higher alcohol such as dipentaerythritol, tris(2-hydroxyethyl) isocyanate, sorbitol or mannitol; or a lactone compound such as ε-caprolactone A polylactone polyol compound obtained by addition is obtained. Among the above, from the viewpoint of high molecular weight and improvement of the reactivity with the fatty acid (a3) in the modification reaction using the fatty acid (a3), a trivalent or higher alcohol can be suitably used. Examples of the trivalent or higher polyhydric alcohols include tris(hydroxyindole)ethyl bromide, tris(A) propylamine, diglycerin, triglycerin, 1,2,6-hexane triol, and pentaerythritol. a trivalent or higher alcohol such as dipentaerythritol, sorbitol or mannitol; and a polylactone polyol compound obtained by adding a lactone compound such as ε-caprolactone to an alcohol having a trivalent or higher value Trimeric isocyanuric acid tris(2-hydroxyethyl)S, tris(2-hydroxypropyl) isocyanate, tris(2-hydroxybutyl) isocyanate Tris(hydroxyalkyl)cyanate and the like. Among these, it is particularly preferable to use tris(hydroxyindole)propane. When a trivalent or higher polyhydric alcohol is used, the total content of the trivalent or higher polyhydric alcohol in the alcohol component (a2) is based on the total amount of the alcohol component (a2), and is 10 to 70 mol% at 14 201217468, especially It is preferably in the range of 20 to 65 m〇i%, more particularly in the range of 3 〇 to 6 〇 m 〇 1%. Further, as the alcohol component (a2) other than the above polyol, a unit alcohol such as decyl alcohol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol or 2-phenoxyethanol may be used as needed; An alcohol compound obtained by reacting a monoepoxy compound such as a glycidyl ester of a highly branched fatty acid (trade name "Cardura El" HEXION Specialty Chemicals Co., Ltd.) with an acid. The production of the hydroxyl group-containing polyester resin (A1) is not particularly limited and can be carried out in accordance with a general method. For example, the esterification reaction can be carried out by reacting the acid component containing the polybasic acid component (al) as an essential component and the alcohol component (a2) in a nitrogen stream at 15 Torr to 250 ° C for 5 to 10 hours. It is produced by transesterification. In the above esterification reaction or transesterification reaction, the acid component and the alcohol component (a2) may be added at once or may be added in several portions. Further, after starting the synthesis of the carboxyl group-containing polyester resin, a part of the carboxyl groups in the carboxyl group-containing polyester resin may be esterified using the above alcohol component (a2). Further, after the synthesis of the hydroxyl group-containing polyester resin is started, the acid anhydride may be reacted to half-esterify the hydroxyl group-containing polyester resin. When the above esterification or transesterification reaction is carried out, a catalyst may also be used in order to promote the reaction. As the catalyst system, a known catalyst such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl vinegar or tetraisopropyl titanate can be used. Further, the hydroxyl group-containing polyester resin (A1) can be modified with a fatty acid, a monoepoxy compound, a polyisocyanate compound or the like in the preparation of the resin, after the acetation reaction, or after the transesterification reaction. 15 201217468 As the above fatty acid, for example, coconut oil fatty acid, cottonseed oil, lung acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, pine oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed Oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, and the like.

上述單環氧化合物例如可適宜地使用合成高度分支飽 和脂肪酸的環氧丙基酯（商品名「Cardui<a e 1 〇」HEXIONAs the above monoepoxy compound, for example, a glycidyl ester of a highly branched fatty acid can be suitably used (trade name "Cardui<a e 1 〇" HEXION

Specialty Chemicals公司製）。 作為上述聚異氣酸醋化合物係可舉例如：離胺酸二異 說酸酉旨、六亞甲二異氰酸g旨、三甲基己院二異氰酸§旨等脂 肪族二異氰酸酯化合物；氫化伸茬基二異氰酸酯、異佛酮 一異氰酸酯、甲基環己烷-2,4-二異氰酸酯、甲基環己烷_2,6_ 二異氰酸醋、4,4，-亞曱雙(環己基異氰酸醋）、u_(異氰酸合 曱基)環己烧等脂環族二異氰酸酯化合物；曱伸苯基二異氰 酸酿、伸I基二異氰酸g旨、二苯甲院二異氰酸g旨等芳香族 二異氰酸酯化合物；離胺酸三異氰酸酯等3價以上之聚異氰 酸酉旨等的有《異氰_其本身，或該等各有機聚異氣酸 醋與多元醇、低分子量聚s旨樹脂或水等的加成物加成物， 或上述各有機二異氰_旨彼此的環化聚合物(例如，三聚異 氰酸酯）、雙脲型加成物等。該等可單獨或組合2種以上來 使用。 含經基聚醋樹脂⑷）的數平均分子量，從所獲得之塗 膜的加工性、平滑性的觀點看來，具有在_〜編〇 ,特 別是7000〜25000,更特別是1〇〇〇〇〜2〇〇〇〇之範圍内之數平均Specialty Chemicals Co., Ltd.). The polyisophthalic acid vinegar compound may, for example, be an aliphatic diisocyanate compound such as an acid of a dibasic acid, a hexamethylene diisocyanate, or a trimethylhexyl diisocyanate. Hydrogenated decyl diisocyanate, isophorone monoisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane_2,6-diisocyanate, 4,4,-arylene An alicyclic diisocyanate compound such as (cyclohexyl isocyanate vinegar), u_(isocyanatosyl) cyclohexane or the like; phenylphenyl diisocyanate, thiol diisocyanate, and Benzene diisocyanate g is an aromatic diisocyanate compound; trivalent or higher polyisocyanate such as tristearic acid triamide or the like has "isocyanate" itself, or these organic polyisogas An adduct adduct of a sweet vinegar, a polyhydric alcohol, a low molecular weight poly s resin or water, or each of the above-mentioned organic diisocyanines (for example, a trimeric isocyanate) and a diurea type Adults and so on. These may be used alone or in combination of two or more. The number average molecular weight of the transuretic-containing polyacetal resin (4)) has a composition of _~~, especially 7000~25000, more especially 1〇〇〇 from the viewpoint of the processability and smoothness of the obtained coating film. Number average within the range of 〇~2〇〇〇〇

S 16 201217468 分子量是適宜的。 再者，在本說明書中，數平均分子量及重量平均分子 量將使用凝膠滲透層析法(GP C)所測得之數平均分子量及 重量平均分子量，以為標準聚苯乙烯的分子量為基準進行 換算所獲得的值。具體而言，凝膠滲透層析法可使用 「HLC812〇GPC」（商品名 ’Tosoh(股）製），並使用「TSK_gel G4000HXL」、「TSK_gel G3000hxl」、「TSK_gd g25〇〇h几」及 「TSK-gelG2000HXL」（商品名，皆T〇s〇h(股）製）作為管柱， 在移動相四氫呋喃、測定溫度4(TC、流迷丨mL/min及檢測器 RI的條件下進行測定。S 16 201217468 Molecular weight is suitable. In the present specification, the number average molecular weight and the weight average molecular weight are converted using the number average molecular weight and the weight average molecular weight measured by gel permeation chromatography (GP C), based on the molecular weight of the standard polystyrene. The value obtained. Specifically, gel permeation chromatography can use "HLC812 GPC" (trade name "Tosoh"), and use "TSK_gel G4000HXL", "TSK_gel G3000hxl", "TSK_gd g25〇〇h" and " TSK-gel G2000HXL (trade name, manufactured by T〇s〇h) was used as a column, and was measured under the conditions of mobile phase tetrahydrofuran, measurement temperature 4 (TC, flow enthalpy mL/min, and detector RI).

含羥基聚酯樹脂(A1)之羥值，從所獲得之塗膜的硬化 性的觀點看來，具有5〜l〇〇mgKOH/g，特別是丨〇〜9〇mgK〇H /g，更特別是40〜80mgKOH/g之範圍内的羥值是適宜的。 又，含經基聚酯樹脂（A1)之酸價，從加工性及耐水性 等的觀點看來’適宜的範圍宜在^mgKOH/g以下，更宜在 2〇mgKOH/g以下之範圍内。 含羥基聚酯樹脂(A1)之數平均分子量、羥值及酸價的 調整可藉由例如調整將前述多元酸成分(al)作為必需成分 之酸成分（多元酸成分(al)、及視需要在多元酸(al)以外的酸 成刀）中之竣基與前述醇成分（a2)中經基的當量比 (COOH/OH)之方法，或在前述酯化反應或酯交換反應中調 整反應溫度或時間的方法等來進行。 就將上述多元酸成分（al)作為必需成分之酸成分中之 緩基與前述醇成分(a2)中羥基的當量比(COOH/OH)而言， 17 201217468 一般係以在0.5〜0.98之範圍内為佳。 又，含羥基聚酯樹脂（A1)，從所獲得之塗膜的硬度、 加工性等的觀點看來，以具有在0〜50°C、更宜為在10〜40 °C之範圍内之玻璃轉移溫度為適切。在本說明書中，玻璃 轉移溫度(Tg)係藉由視差掃描卡計(DSC)所測定出的值（玻 璃轉移溫度）。 使用前述脂肪酸(a3)作為酸成分時，含羥基聚酯樹脂 (A1)從所獲得之塗膜耐候性的觀點看來，宜具有3〜30%、更 宜為5〜20%之範圍内的油長。此處，油長係指脂肪酸成分(a3) 相對於以構成成分之多元酸成分（al)及脂肪酸(a3)為必需 成分的酸成分及醇成分(a2)之總量的質量％。 作為聚酯樹脂成分(A)，亦可包含含羥基聚酯樹脂(A1) 以外的聚目旨樹脂(A2)。 聚酯樹脂（A2)係依一般方法，藉由以多元酸成分（al) 為必需成分之酸成分及醇成分(a2)的酯化反應或酯交換反 應所獲得之聚酯樹脂，就以多元酸成分(al)為必需成分之酸 成分及醇成分(a2)而言，可進行與上述含羥基聚酯樹脂(A1) 所例示之方法，以相同的方式來製造。 在本發明中，相對於聚酯樹脂成分(A)的固體成分總 量，從所獲得之塗膜的耐污染性等觀點看來，係在50〜100 質量％之範圍内。且以60〜100質量％，更以70〜100質量％之 範圍内為佳。 三聚氰胺樹脂成分(B) 在本發明之塗料組成物中，三聚氰胺樹脂成分(B)係含 18 201217468 有相對於三聚氰胺樹脂成分(B)之固體成分總量3〇〜loo質 量％之下述丁基醚化三聚氰胺樹脂(Bl)。 (B1) 丁基醚化三聚氰胺樹脂 丁基醚化三聚氰胺樹脂係將三聚氰胺與甲醛、聚曱醛 等酸成分之加成反應生成物（1量體及多量體中任一者皆可） 技曱化三聚氰胺樹脂中的經曱基之一部分或全部以正丁基 醇或異丁基醇進行醚化所獲得之三聚氰胺樹脂。此處，丁 基醚化三聚氰胺樹脂之中係包含下述任一者：將羥曱化三 聚氰胺樹脂中之羥曱基的一部分或全部以正丁基醇進行醚 化而得之三聚氰胺樹脂、以異丁基醇進行醚化而得之三聚 氰胺樹脂、及以正丁基醇及異丁基醇進行醚化而得之三聚 氰胺樹脂。從所獲得之塗膜的加工性及耐污染性等點看 來’該丁基醚化三聚氰胺樹脂的數平均分子量係以在 800〜8000 ’特別是在1〇〇〇〜5〇〇〇之範圍内為佳。丁基醚化三聚 氰胺樹脂(B1)係可以1種或2種以上之混合物的形式來使用。The hydroxyl value of the hydroxyl group-containing polyester resin (A1) has 5 to 1 〇〇mgKOH/g, particularly 丨〇~9〇mgK〇H /g, from the viewpoint of the hardenability of the obtained coating film, In particular, a hydroxyl value in the range of 40 to 80 mgKOH/g is suitable. In addition, the acid value of the transesterified polyester resin (A1) is preferably in the range of from 2 mg KOH/g or less, more preferably in the range of 2 〇 mg KOH/g or less, from the viewpoints of workability and water resistance. . The number average molecular weight, the hydroxyl value, and the acid value of the hydroxyl group-containing polyester resin (A1) can be adjusted, for example, by adjusting the acid component (poly acid component (al) having the polybasic acid component (al) as an essential component, and if necessary a method of adjusting the reaction ratio of the mercapto group in the acid-forming knives other than the polybasic acid (al) to the above-mentioned equivalent ratio (COOH/OH) in the alcohol component (a2) or in the aforementioned esterification reaction or transesterification reaction The method of temperature or time is performed. With respect to the equivalent ratio (COOH/OH) of the slow-acting group in the acid component of the above polybasic acid component (al) as an essential component to the hydroxyl group in the alcohol component (a2), 17 201217468 is generally in the range of 0.5 to 0.98. It is better inside. Further, the hydroxyl group-containing polyester resin (A1) has a hardness of from 0 to 50 ° C, more preferably from 10 to 40 ° C from the viewpoint of hardness, workability, and the like of the obtained coating film. The glass transition temperature is suitable. In the present specification, the glass transition temperature (Tg) is a value (glass transition temperature) measured by a parallax scanner card (DSC). When the fatty acid (a3) is used as the acid component, the hydroxyl group-containing polyester resin (A1) preferably has a range of from 3 to 30%, more preferably from 5 to 20%, from the viewpoint of weather resistance of the obtained coating film. Oil length. Here, the oil length refers to the mass % of the total amount of the fatty acid component (a3) relative to the acid component and the alcohol component (a2) which are essential components of the polybasic acid component (al) and the fatty acid (a3) which are constituent components. The polyester resin component (A) may further contain a polyimide resin (A2) other than the hydroxyl group-containing polyester resin (A1). The polyester resin (A2) is a polyester resin obtained by an esterification reaction or a transesterification reaction of an acid component having an essential acid component (al) as an essential component and an alcohol component (a2) according to a general method. The acid component (al) which is an essential component and the alcohol component (a2) can be produced in the same manner as the method exemplified above for the hydroxyl group-containing polyester resin (A1). In the present invention, the total solid content of the polyester resin component (A) is in the range of 50 to 100% by mass from the viewpoint of the stain resistance of the obtained coating film. Further, it is preferably in the range of 60 to 100% by mass, more preferably 70 to 100% by mass. Melamine resin component (B) In the coating composition of the present invention, the melamine resin component (B) contains 18 201217468 having the following butyl groups in a total amount of 3 〇 to loo% by mass relative to the solid content of the melamine resin component (B) Etherified melamine resin (Bl). (B1) butyl etherified melamine resin butyl etherified melamine resin is an addition reaction product of melamine and an acid component such as formaldehyde or polyacetal (one of a quantitative body and a multi-volume). A melamine resin obtained by etherifying a part or all of a mercapto group in a melamine resin by n-butyl alcohol or isobutyl alcohol. Here, among the butyl etherified melamine resins, any one of the following: a melamine resin obtained by etherifying a part or all of a hydroxy group of a hydroxylated melamine resin with n-butyl alcohol, A melamine resin obtained by etherification of butyl alcohol, and a melamine resin obtained by etherification with n-butyl alcohol and isobutyl alcohol. From the point of view of the processability and stain resistance of the obtained coating film, the number average molecular weight of the butyl etherified melamine resin is in the range of 800 to 8000', particularly in the range of 1 〇〇〇 to 5 〇〇〇. It is better inside. The butyl etherified melamine resin (B1) may be used singly or in combination of two or more kinds.

丁基醚化三聚氰胺樹脂(B1)之市售品係可列舉如：U-VAN20SE、U-VAN225(以上任一者皆三井化學（股）製，商品 名）、SUPER BECKAMINE J820-60、SUPER BECKAMINCommercial products of the butyl etherified melamine resin (B1) include, for example, U-VAN20SE and U-VAN225 (all of which are manufactured by Mitsui Chemicals Co., Ltd., trade name), SUPER BECKAMINE J820-60, SUPER BECKAMIN.

E L-117-60 ' SUPER BECKAMINE L-109-65 > SUPER BE CKAMINE 47-508-60、SUPER BECKAMINE L-l 18-60、S UPER BECKAMINE G821-60(以上任一者皆 DIC(股）製，商 品名）等。 三聚氰胺樹脂成分(B)係可含有上述丁基醚化三聚氰 胺樹脂(B1)以外的三聚氰胺樹脂（三聚氰胺樹脂(B2))。 19 201217468 具體而言，係可舉例如：將三聚氰胺與甲醛、聚曱酿 等醛成分之加成反應生成物（1量體及多量體中任一者皆可） 羥甲化三聚氰胺樹脂中之羥曱基的一部分或全部，藉由正 丁基醇及異丁基醇以外之1種或2種以上的醇進行峻化所獲 得之三聚氰胺樹脂；藉由正丁基醇及/或異丁基醇，以及正 丁基醇及異丁基醇以外之1種或2種以上的醇進行鱗化所獲 得之三聚氰胺樹脂。就用於進行醚化之正丁基醇及異丁基 醇以外的醇之例子而言，係可列舉如：曱基醇、乙基醇、 正丙基醇、異丙基醇、2-乙基丁醇、2-乙基己醇等的1價醇。 就三聚氰胺樹脂(B2)的具體例而言，可列舉如：藉甲基醇 進行醚化之三聚氰胺樹脂（甲基醚化三聚氰胺樹脂）；藉甲基 醇及丁基醇進行醚化之三聚氰胺樹脂（曱基/丁基混合醚化 三聚氰胺樹脂）等。 藉甲基醇進行醚化之三聚氰胺樹脂係可舉例如：E L-117-60 ' SUPER BECKAMINE L-109-65 > SUPER BE CKAMINE 47-508-60, SUPER BECKAMINE Ll 18-60, S UPER BECKAMINE G821-60 (all of the above are DIC (share) system, Product name). The melamine resin component (B) may contain a melamine resin (melamine resin (B2)) other than the above butyl etherified melamine resin (B1). 19 201217468 Specifically, for example, an addition reaction product of melamine, an aldehyde component such as formaldehyde or polybromide (any one of a quantitative amount and a multi-component) can be used. Hydroxyl in a hydroxymethylated melamine resin a melamine resin obtained by preliminating a part or all of a thiol group with one or more alcohols other than n-butyl alcohol and isobutyl alcohol; by n-butyl alcohol and/or isobutyl alcohol And a melamine resin obtained by scalding one or more alcohols other than n-butyl alcohol and isobutyl alcohol. Examples of the alcohol other than n-butyl alcohol and isobutyl alcohol used for etherification include, for example, mercapto alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, 2-B. A monovalent alcohol such as butylbutanol or 2-ethylhexanol. Specific examples of the melamine resin (B2) include, for example, a melamine resin (methyl etherified melamine resin) which is etherified with methyl alcohol; a melamine resin which is etherified with methyl alcohol and butyl alcohol ( Mercapto/butyl mixed etherified melamine resin) and the like. The melamine resin which is etherified by methyl alcohol can be exemplified by, for example:

Sumi-mal M-100、Sumi-mal M-40S、Sumi-mal M-55(任一者 皆為住友化學(股）製，商品名）、Cymel 300、Cymel 303、 Cymel 325、Cymel 327、Cymel 350、Cymel 370、Cymem〇、 Cymel 736、Cymel 738(以上任一者皆日本Cytece工業公司 (股）製，商品名）、Melan 522、Melan 523(以上任一者皆曰 立化成工業（股）製，商品名）、NIKARAKMS17、NIKARAK MS15 > NIKARAK MS001 > NIKARAK MX430 ' NIKARAK MX650(任一者皆（股）三和化學製，商品名）、瑞吉明740、 瑞吉明741、瑞吉明747(以上任一者皆孟山都公司製，商品 名）等的甲基醚化三聚氰胺樹脂。Sumi-mal M-100, Sumi-mal M-40S, Sumi-mal M-55 (all of which are manufactured by Sumitomo Chemical Co., Ltd., trade name), Cymel 300, Cymel 303, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymem〇, Cymel 736, Cymel 738 (all of which are made by Japan Cytece Industries Co., Ltd., trade name), Melan 522, Melan 523 (all of which are 曰立化成工业) System, product name), NIKARAKMS17, NIKARAK MS15 > NIKARAK MS001 > NIKARAK MX430 'NIKARAK MX650 (any one (share) Sanhe Chemical, trade name), Ruiji Ming 740, Ruiji Ming 741, Ruiji Ming 747 ( Any of the above is a methyl etherified melamine resin such as Monsanto Corporation, trade name.

S 20 201217468 藉由甲基醇及丁基醇進行醚化之三聚氰胺樹脂係可舉 例如：Cymel 232、Cymel 235、Cymel 202、Cymel 238、 Cymel 254、v266、Cymel 272、Cymel 1130、Cymel XV-514、 Cymel XV805(任一者皆曰本Cytece工業公司（股）製，商品 名）、Sumi-mal M66B(住友化學（股）製，商品名）、瑞吉明 753、瑞吉明755(以上任一者皆孟山都公司製，商品名）等的 甲基/丁基混合醚化三聚氰胺樹脂。 本發明中，相對於三聚氰胺樹脂成分之固體成分總 量’丁基醚化三聚氰胺樹脂(B1)之固體成分含量從所獲得 塗膜之加工性及耐污染性的保持性之觀點看來，係在 30〜100質量°/〇之範圍内。宜為5〇〜1〇〇質量％，更宜為7〇〜1〇〇 質量％之範圍内。 丁基鱗化二聚氰胺樹脂（B1)與甲基喊化三聚氰胺樹 脂、甲基/丁基混合醚化三聚氰胺樹脂等相較下極性低，且 與屬基體樹脂之聚酯樹脂(A)之相溶性良好。因此，自含有 丁基醚化三聚氰胺樹脂(B1)之耐污染塗料組成物所獲得之 塗膜係交聯的均勻性優異。 又’丁基醚化三聚氰胺樹脂(B1)與甲基醚化三聚氰胺 樹脂、甲基/丁基混合醚化三聚氰胺樹脂相比，塗膜中不易 產生向表層的局部化。因此，自含有丁基醚化三聚氰胺樹 脂(B1)之耐污染塗料組成物所獲得之塗膜，耐侯性亦優異。 又’為了促進聚酯樹脂成分(A)與三聚氰胺樹脂成分(B) 之硬化反應，可視需要使用硬化觸媒。作為用於促進硬化 反應之硬化觸媒，一般而言，可使用磺酸化合物或磺酸化 21 201217468 合物的中和物。 就石黃酸化合物而言，可列舉如：對_甲苯、十二基 苯〜Ί —壬基、二壬基蔡二績酸等。作為石黃酸化 合物之中和物的中和劑係可列舉如：i級胺、2級胺、3級胺、 氨、苛性鈉、苛性斜等驗性化合物。 本發明之对污染塗料組成4勿中，上述聚g旨樹脂成分(A) 及三聚氰胺樹脂成分(B)之比率，以聚酯樹脂成分(A)及三聚 氰胺樹脂成分(B)之總量為基準，聚酯樹脂成分(A)為5〇〜9〇 質量％，特別是60〜80質量。三聚氰胺樹脂成分(B)為1〇〜5〇 質量％，特別是20〜40質量。/。時，從所獲得塗膜之硬化性、 耐污染性、機械強纟、加工性、耐溶劑性、耐蝕性、耐候 性等的觀點看來係較佳。 (C)有機矽酸鹽及/或其縮合物成分 本發明之(C)成分係由 通式：（I^n-Si-COR2)^ [式中R1亦可由環氧基或疏基取代之碳數1〜18之院基或笨 基’汉2係碳數1~6之炫基，η為〇或1。] 所表示之有機矽酸鹽及/或其縮合物。 本發明之塗料組成物所使用之(C)成分係用於在塗布 後巧致率地在基材表面發揮親水化效果而摻混者，從該效 果的觀點看來，以上述有機矽酸鹽之縮合物為較佳。 上述通式中R1具體例係可列舉如：曱基、乙基、正丙 基、異丙基、正丁基、異丁基、戊基、己基、庚基、正辛 2、乙基己基、壬基、癸基、十一基、十二基、十四基、 22 201217468 十/ = A 氧丙基、甲基環氧丙基(2-甲基環氧丙 基）、谈基甲基、2-疏基乙基、2遵基丙基、3_疏基丙基、 4-酼基丁基、笨基、對_巯基笨基等。 ()成之有機石夕酸鹽的具體例係可列舉如：四甲氧石夕 烧、四“頻、四丙氧魏、四異丙氧料、四丁氧石夕 烧四異丁氧石夕貌等4官能基石夕烧；甲基三甲氧石夕烧、甲基 三乙氧矽烷、甲基三丙氧矽烷、曱基三異丙氧矽烷、甲基 三正丁氧賴、甲基三異丁氧魏、苯基三甲氧械、苯 基三乙氧矽烷、苯基三丙氧矽烷、苯基三異丙氧矽烷、苯 基二正丁氧石夕燒、苯基三異丁氧石夕烧、己基三甲氧石夕院、 己基二乙氧魏、月桂基三曱氧石夕烧、月桂基三乙氧石夕烧、 疏基曱基二甲氧⑪院、職乙基三甲氧魏、魏基甲基三 乙氧矽烷、巯基乙基三乙氧矽烷、巯基丙基三甲氧矽烷、 锍基丙基二乙氧矽烷等3官能基矽烷。上述有機矽酸鹽之縮 合物係可列舉如組合該等4官能基或3官能基矽烷之丨種或2 種以上的縮合物。 有機矽酸鹽之縮合物係可依一般方法製造，就市售品 而言係可舉例如：MKC矽酸鹽MS51、MS56、MS57、MS5 6S、MS56SB5、MS58B15、MS58B30、ES40、EMS31、B TS(以上任一者皆三菱化學（股）製，商品名）、甲基矽酸鹽5 1、乙基矽酸鹽40、乙基矽酸鹽40T、乙基矽酸鹽48(以上任 一者皆COLCOAT(股)製，商品名）、KR500、KR9218、X-4 1-1805、X-41-1810、X-41-1818、X-41-1053、X-4M056(以 上任一者皆信越化學工業（股)製，商品名）等。又，亦可藉 23 201217468 、專有機矽酸鹽的縮合物以單體或組合2種以上，部分 & “解縮合來獲得。有機料鹽之縮合物係分枝狀或直 „缩合物，縮合度以2〜10。為佳，以2〜2。為較佳。本發 ^料、且成物中’（C)成分之有機矽酸鹽或有機矽酸鹽的 縮合物係可單獨使用’亦可將2種以上組合使用。 由則述通式所表示之有機矽酸鹽及/或其縮合物中，作 為〇R2基係具有f氧基與碳原子數2〜峨氧基，f氧基/碳原 子數2〜6之烷氧基之數量比在95/5〜30/70之範圍内，這從塗 料作成後之可使用時間（適用期）之觀點看來是較適宜的。 本發明之塗料組成物中，（C)成分的固體成分含量以(a) 成分及(B)成分的固體成分總量為基準，宜為1〜20質量％， 較宜為1〜1〇質量％ ,更宜為3〜7質量0/〇。 (C)成分量因在上述範圍内’可發揮含有（c)成分摻混的 效果，從所獲得之塗膜之初期耐污染性及耐污染性的保持 性’以及塗膜的機械強度及耐久性的面看來亦適宜。 (D)含有氟原子的非水性分散液型樹脂成分 本發明之塗料組成物(D)成分係含有氟原子的非水性 分散液(Non Aqueous Dispersion、NAD)型樹脂。含有氟原 子的非水性分散液型樹脂亦可稱為含有氟原子的非水性分 散液。該(D)成分具體而言係可列舉如：在含有含氟原子的 分散穩定劑之有機溶劑液中有聚合物粒子分散之非水性分 散液型樹脂(D1)，及在含有分散穩定劑之有機溶劑液中有 以含有氟烷基之（甲基）丙烯酸酯為構成成分之聚合物粒子 分散的非水性分散液型樹脂(D2)等。 24 201217468 再者，在本說明書中，「（曱基）丙烯酸酯」係表示丙烯 酸酯或甲基丙烯酸酯。 就非水性分散液型樹脂(D1)之具體例而言，可例示如 可藉由下述方式來調製的非水性分散液型樹脂：在含有氟 原子的分散穩定劑(D1 a)與有機溶劑(D丨b )之混合液中，使聚 & I1 生不飽和單體共聚合而在該混合液中形成不溶的聚合物 粒子(Die)。非水性分散液型樹脂(D1)雖亦可說是在含有分 散媒、聚合物粒子（分散粒子)及分散穩定劑之非水性分散液 型樹脂中，分散穩定劑為含有氟原子之分散穩定劑的非水 性分散液型樹脂，但並非受限於此者。或，非水性分散液 型树知(D1)為在含有含氟原子之分散穩定劑的有機溶劑液 中有聚合物粒子分散之非水性分散液；在含有含氟原子的 分散穩定劑(Dla)之有機溶劑(Dlb)中，有不溶於該等之中的 聚合物粒子(Die)分散之非水性分散液。 分散穩定劑(Dla)係含有氟原子，用於使聚合物粒子 (Die)安定地分散於有機溶劑(Dlb)中的分散穩定劑。分散穩 定劑(Dla)係與有機溶劑(Dlb)互溶，而與聚合物粒子(Dlc) 不相溶者。 聚合物粒子(Die)係可適用例如將含有氟烧基之（曱基) 丙烯酸酯（F-丙烯酸酯）及/或含有氟化烯烴之聚合性不飽和 單體進行共聚合所獲得之聚合物。該聚合物亦可視需要使 每分子含有1個以上選自羥基、羧基、環氧基、矽醇基、烧 氧矽烷基等的官能基。 上述含有氟烧基之（甲基）丙烯酸酯（F-丙稀酸酯）係可 25 201217468 舉例如由 通式 CH2=C(R)-COO-(CH2)n-Rf [R係氫原子或甲基，η為1〜1 〇之整數， 似係碳數1〜21 個之直鏈狀或分枝狀的氟烷基] 所表示之化合物。在此「氟烷基」係碳原子數工 鏈狀或分枝狀烴基之氫的一部分或全部經取代成個之直 該F-丙烯酸酯係可舉例如：全氟甲基曱基丙烯酸酽一 甲基甲基曱基丙稀酸醋、全氟丁基乙基兩稀酸醋、全3 基乙基甲基丙稀酸醋、全氟異壬基乙基丙稀酸酿、全氣異 壬基乙基曱基丙稀酸醋、全氟辛基乙基丙稀酸醋、全氣; 基乙基曱基丙稀酸醋、2,2,3,3-四氟丙基丙稀酸醋、2,2,3,3_ 四氟丙基甲基丙烯酸醋、1H，1H，5H_八氣戊基丙稀酸略、 1H，1H，5H-八氟戊基曱基丙晞酸酯等。 又’氟化烯烴係可舉例如：四氟乙歸、六就乙稀、三氣 氣乙烯、氟乙烯ϋ乙稀、三氟乙烯等。用於獲得分散 穩定劑(ma)之聚合性不飽和單體，可使用由上财_丙_ 醋及上述氟化_所構紅群_㈣之1#或2種以上。 分散穩定劑_)係可藉由下財式調製：使由F_ “及鼠化稀煙所構成之群選出之丨種或2種以上聚合 ==丙稀動旨魏化_所構成之群選出之i種或2種以 上與其他的聚合性不飽和單體聚合。 其他的t合性不飽和單體尸 和單雜即可無特別限制。例如可=二基聚合性的不飽 單體。 j舉以下的聚合性不飽和 26 201217468 丙烯酸或曱基丙烯酸之酯類（i):丙烯酸曱酯、曱基丙 烯酸甲S旨、丙稀酸乙S旨、甲基丙稀酸乙醋、丙稀酸丙自旨、 曱基丙烯酸丙酯、丙烯酸異丙酯、曱基丙烯酸異丙酯、丙 烯酸丁酯、甲基丙烯酸丁酯、丙烯酸異莰酯、甲基丙烯酸 異莰酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸辛酯、曱 基丙烯酸辛酯、丙烯酸月桂酯、曱基丙烯酸月桂酯等丙烯 酸或曱基丙烯酸的Cu烷基酯；丙烯酸環己酯、甲基丙烯 酸環己酯等丙烯酸或曱基丙烯酸的C3__2〇環烷基酯；丙烯酸 烯丙酯、曱基丙烯酸烯丙酯等丙烯酸或甲基丙烯酸的C2〜8 烯基酯；丙烯酸烯丙氧基乙酯、曱基丙烯酸烯丙氧基乙酯 等丙烯酸或甲基丙烯酸之C3~2〇烯氧基烷基酯等。 含有環氧丙基之不飽和單體(Π):丙烯酸環氧丙酯、曱 基丙烯酸環氧丙酯等。 含羥基的不飽和單體(iii):丙烯酸羥乙酯、甲基丙烯酸 羥乙酯、丙烯酸羥丙酯、甲基丙烯酸羥丙酯等丙烯酸或曱 基丙烯酸之C2~8羥烷基酯；羥丁基乙烯基醚等羥烷基乙烯基 醚；烯丙醇、曱基浠丙醇等。 含烷氧矽烷基之不飽和單體（iv) : γ-丙烯醯氧基丙基三 曱氧矽烷、γ-曱基丙烯醯氧基丙基三曱氧矽烷、β-丙烯醯氧 基乙基三曱氧矽烷、γ-曱基丙烯醯氧基乙基三曱氧矽烷、γ-丙稀醯氧基丙基三乙氧矽烷、γ-甲基丙烯醯氧基丙基三乙 氧矽烷、乙烯基三甲氧矽烷、乙烯基三乙氧矽烷、乙烯基 三(2-甲氧基乙氧基)矽烷等。 不飽和羧酸(ν):丙烯酸、曱基丙烯酸、衣康酸、順丁 27 201217468 烯二酸、反丁烯二酸、巴豆酸等。 含異氰酸酯基之不飽和單體(vi):丙烯酸異氰酸酯基乙 基酯、m-異丙基-α,οι-二甲基苄基異氰酸酯等。 具有2個以上之聚合性不飽和鍵結之不飽和單體 (vii):乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙 二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三（羥曱）丙烷 三丙烯酸酯、三（羥曱）丙烷三甲基丙烯酸酯等。 乙烯基芳香族化合物（viii):苯乙烯、α-曱基苯乙烯、 乙烯基曱苯、對-氣苯乙烯乙烯吼啶等。 (i)〜(viii)以外之其他的聚合性不飽和單體（iv):丙烯 晴、甲基丙烯晴、甲基異丙基酮、乙酸乙烯酯、貝歐巴單 體（殼牌化學公司製，商品名）、丙酸乙烯酯、三甲基乙酸乙 烯酯、丙酸乙烯酯、乙基乙烯基醚、正丙基乙烯基醚、異 丙基乙烯基醚、丁基乙烯基醚、辛基乙烯基醚、環己基乙 烯基醚、苯基乙烯基醚、苄基乙烯基醚、乙烯、丙烯、丁 烯、Ν,Ν-二曱基胺基乙基丙烯酸酯、Ν,Ν-二曱基胺基乙基 曱基丙烯酸酯、丙烯醯胺、乙烯吡啶等。 在用於調製分散穩定劑（Dla)之聚合反應中，在將F-丙 烯酸酯及/或氟化烯烴與其他聚合性不飽和單體共聚合所 形成之系統中之兩者(F-丙烯酸酯及/或氟化烯烴，以及其他 聚合性不飽和單體之2成分）的比率係可任意地選擇。從耐 污染性的觀點看來，以該兩成分的固體成分總量為基準，F-丙烯酸酯及/或氟化烯烴作為固體成分宜為100〜1質量％，特 宜為30〜5質量％ :其他聚合性不飽和單體作為固體成分宜 28 201217468 為0〜99質量％，特宜為70〜95質量。/。之範圍内。 從F-丙烯酸酯及氟化烯烴所選出之丨種或2種以上的聚 合反應’或該等與其他聚合性不飽和單體的共聚合反應係 宜在自由基聚合起始劑的存在下進行。自由基聚合起始劑 係可舉例如：2,2-偶氮異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈) 等偶氮化合物、過氧化苯曱醯、月桂基過氧化物、第三丁 基過氧化物等的過氧化物。該等起始劑的使用量相對於1?_ 丙烯酸酯及/或氟化烯烴與是需要所使用之其他聚合性不 飽和單體之固體成分總量’作為固體成分，宜為〇.2〜1〇質 量％，特宜為0.5〜5質量％之範圍内。 在用於調製分散穩定劑(Dla)之聚合反應中，藉由使用 (ii)含有環氧丙基之不飽和單體、（iii)含經基的不飽和單 體、（iv)含有烷氧矽烷基之不飽和單體、（v)不飽和羧酸、（Vi) 含異氰酸酯基之不飽和單體等來作為其他聚合性不飽和單 體，可獲得具有環氧丙基、羥基、院氧矽烧基、羧基、異 氰酸酯基等官能基之分散穩定劑。特別是，具有經基之分 散穩定劑與使具有經基之聚合物教子(D1 c)和三聚氣胺樹 脂成分(B)及前述有機矽酸鹽及/或其縮合物成分(c)反應， 可形成三維交聯之硬化塗膜。 作為分散穩定劑(Dla)係可適宜地使用在1分子中平均 具有0.1個以上的聚合性不飽和韃結者。若使分散穩定劑 (Dla)中具有聚合性不飽和鍵結，由於可使其與聚合物粒子 (Die)間形成共價鍵，提高非水性分散液型樹脂之貯藏安定 性、機械的安定性 '耐污染性等之故而為佳。 29 201217468 於分散穩定劑（Dla)中導入聚合性不飽和鍵結之方法 係可舉如，對令其存在於分散穩定劑中的官能基，使含有 會與該官能基進行反應之其他官能基的聚合性不飽和單體 進行反應的方法。例如，可在含有羧基之分散穩定劑(Dla) 中使含有環氧丙基之聚合性不飽和單體（例如丙烯酸環氧 丙酯、甲基丙烯酸環氧丙酯、烯丙基環氧丙基醚等）進行反 應’藉以將聚合性不飽和鍵結導入該分散穩定劑。又，相 反地’亦可藉由在含有環氧丙基之分散穩定劑(Dla)中使聚 合性單體(例如丙烯酸、甲基丙烯酸、順丁烯二酸、反丁烯 —酸、衣康酸等）進行反應’來將聚合性不飽和鍵結導入該 分散穩定劑。就該種官能基的組合而言，除上述之外，可 列舉如：酸酐基與羥基、酸酐基與硫醇基、異氰酸酯基與 羥基等。 作為分散穩定劑(Dla) ’係可適宜地使用含有氟原子之 樹脂（氟樹脂，例如：F-丙稀酸酯及/或氟化烯烴與其他聚合 性不飽和單體共聚合所獲得之樹脂）或於該氟樹脂中導入 有聚合性不飽和鍵結而成之分散穩定劑。就該種氟樹脂而 言，可列舉如Lumiflon LF800(旭硝子（股))等市售的氟樹脂。 分散穩定劑(Dla)之分子量雖無特別限制，但以數平均 分子量計，係以1〇〇〇〜60000、特別是2〇〇〇〜3〇〇〇〇之範圍内 為佳。 作為有機溶劑(Dlb)係可使用：將用於調製上述分散穩 定劑(Dla)及聚合物粒子(Dlc)之含有氟烷基之（甲基）丙烯 酸醋及/或I化雜、以及其他聚合料飽和單體等的聚合 30 201217468 性不飽和單體溶解，但實質上不會將自該聚合性不飽和單 體所獲得之聚合物粒子(Die)溶解者。 因此，可依所使用之分散穩定劑（Dla)及聚合物粒子 (Die)之組成或分子量等的特性值任意地選擇，可舉例如： 己烷、庚烷、辛烷等的脂肪族烴；苯、二曱苯、曱苯、環 己烷等芳香族烴；醋酸甲酯、醋酸乙酯、醋酸異丁酯、醯 基醋酸、醋酸乙二醇單甲基醚、醋酸-2-乙基己酯、醋酸二 乙二醇單甲基醚等酯化合物；赛珞蘇、丁基賽珞蘇、異丙 基醚、乙二醇單曱基醚、二乙二醇單丁基醚等醚化合物； 乙基醇、異丙基醇、正丁基醇、i-丁基醇、辛基醇、己基醇 等醇；曱基異丁基酮、二異丁基酮、甲基乙基酮、異佛酮、 苯乙酮、乙基異戊基酮、甲基異戊基酮、乙基丁基酮等酮 化合物等之有機溶劑。一般而言，係使用以脂肪族烴有機 溶劑為主體，對其進一步組合適宜的芳香族烴、醇、醚化 合物、酯化合物或酮化合物等有機溶劑而成者。就該種較 佳之有機溶劑而言，係可舉例如將原油分餾所獲得之礦油 精（例如，規定於JIS K 2201 4號者。）。 非水性分散液型樹脂(D1)，係可藉由例如在含有氟原 子的分散穩定劑(D1 a)與有機溶劑(D1 b)之混合液中，使聚合 性不飽和單體進行共聚合而形成不溶於該混合液之聚合物 粒子(Die)來調製。 用於獲得聚合物粒子（D1 c)之聚合性不飽和單體只要 是自由基聚合性的不飽和單體即可而無特別限制。具體而 言，在上述含有氟原子的分散穩定劑(Dla)中例示作為「其 31 201217468 他聚合性不飽和單體」之㈣酸或甲基丙稀酸的醋⑴含 有％氧丙基之不飽和單體(ii)、含羥基的不飽和單體（出）、 含有烧氧石夕院基之不飽和單體㈣、不飽和緩酸(V)、含異氛 酸醋基之不飽和單體(vi)、具有2個以上聚合性不飽和鍵結 之不飽和單體(vii)、乙稀衫㈣化合物(viii)、⑴〜㈤丨) 以外的其他聚合性不飽和單體(iv)等。進—步，作為用於調 製聚合物粒子(Die:)之聚合性不飽和單體，亦可使用前述F_ 丙稀酸醋。 用於獲得聚合物粒子（D1 c)之上述聚合性不飽和單體 的聚合反應宜在自由基聚合起始劑存在下進行。作為自由 基聚合性起始劑係可舉例如：2 2_偶氮異丁腈、2,2，_偶氮雙 (2,4-二甲基戊腈）等偶氮化合物、過氧化苯甲醯、月桂基過 乳化物、第二丁基過氧化物等過氧化物，該等起始劑的使用 量以聚合性不飽和單體的總量為基準，為〇2〜1〇質量％，特 別是以在0.5〜5質量％之範圍内為佳。 聚合物粒子（Die)藉由使用前述含有環氧丙基之不飽 和單體（ii)、含羥基的不飽和單體(iH)、含有烷氧矽烷基之 不飽和單體(iv)、不飽和羧酸(v)、含異氰酸酯基之不飽和單 體(vi)等來作為聚合性不飽和單體，可獲得具有該等官能基 之聚合物粒子(D1 c)。 特別是，具有羥基的聚合物粒子係與使具有羥基之分 散穩定劑(Dla)’和前述三聚氰胺樹脂成分(B)及有機矽酸鹽 及/或其縮合物成分(C)進行反應，而可形成三維交聯的硬化 塗膜。 32 201217468 聚合物粒子(Die)的數平均分子量，從耐污染性的觀點 看來，宜為10000以上，特別是以在20000以上之範圍内為佳。 作為聚合物粒子(Die)，從提高对污染性的觀點看來， 可適宜地使用經粒子内交聯之聚合物粒子。 用於形成經粒子内交聯之聚合物粒子的方法係可舉例 如：將具有會相互反應之官能基的聚合性不飽和單體之組 合作為聚合性不飽和單體的構成成分使用的方法；將具有2 個以上聚合性不飽和鍵結之不飽和單體(vii)作為聚合性不 飽和單體之構成成分使用的方法。 上述之中’從聚合反應的安定性之觀點看來，可適宜 地使用將具有互相反應之官能基的聚合性不飽和單體之組 合使用作為聚合性不飽和單體的構成成分的方法。 具體而言，例如使用含羧基之聚合性不飽和單體（例如 丙烯酸、甲基丙烯酸、順丁烯二酸、反丁烯二酸、衣康酸 等）與含有環氧丙基之聚合性不飽和單體（例如丙烯酸環氧 丙醋、甲基丙烯酸環氧㈣、稀丙基環氧丙細等)作為聚 合性不飽和單體的構成成分，可藉由各個聚合性不飽和單 體所具有之叛基與環氧丙基進行加成反應，來調整經粒子 内交聯之聚合物粒子。 作為該種S能基的組合，在羧基與環氧丙基之外，可 列舉如.酸if基㈣基、酸縣與硫醇基、異氰酸醋基與 羥基等組合。 在非水性分散液型樹脂(Dl)巾，分散献劑(Dla)與聚 合物粒子(Die)之比率雖可任意地選擇，但從非水性分散液 33 201217468 型樹脂㈣之貯藏安定性與耐污染性的觀點看來，以該兩 成分的總里為基準，分散穩定劑(D丨a)係以3〜70質量％，特 別是5〜60質量％之範圍内為佳；聚合物粒子(D丨c)係以97〜3〇 質量％，特別是95〜40質量。/。之範圍内為佳。 又，分散穩定劑(Dla)與聚合物粒子(Dlc)之合計濃度， 以分散穩定劑（Dla)、有機溶劑（Dlb)及聚合物粒子（Dic)之 總ϊ為基準，係以30〜70質量，特別是4〇〜6〇質量％之範圍 内為佳。 在含有分散穩定劑（D1 a)之有機溶劑(D丨b)中，用於獲得 聚合物粒子(Die)之聚合性不飽和單體的聚合反應，—般而 吕，可在60〜160 C左右溫度下進行約〗〜15小時。如此所獲 得之非水性分散液型樹脂(D1)，特別是在聚合物粒子(di = 的點，係分散安定性極為優異。 非水性为散液型樹脂（D1)之平均粒徑，從耐污染性的 觀點看來，以在20〜500nm，特別是在50〜4〇〇nm，更特別是 在100〜300nm之範圍内為佳。 在本說明書中，平均粒徑係指使用次微米粒度分布測 疋裝置「COULTER N4型」（Beckman Coulter公司製），將樣 本以一曱本稀釋’在20 C的條件下所測定之彳直。 非水性分散液型樹脂(D2)係在含有分散穩定劑之有機 溶劑液中有以含氟烷基之（甲基）丙烯酸酯為構成成分之聚 合物粒子分散之非水性分散液型樹脂。就非水性分散液型 樹脂(D2)之具體例而言，係可列舉如：可藉由在分散穩定 劑(D2a)與有機溶劑(D2b)之混合液中，使含有i院基之（甲S 20 201217468 The melamine resin which is etherified by methyl alcohol and butyl alcohol may, for example, be Cymel 232, Cymel 235, Cymel 202, Cymel 238, Cymel 254, v266, Cymel 272, Cymel 1130, Cymel XV-514. , Cymel XV805 (any one is based on Cytece Industrial Co., Ltd., trade name), Sumi-mal M66B (Sumitomo Chemical Co., Ltd., trade name), Ruiji Ming 753, Ruiji Ming 755 (any of the above) Methyl/butyl mixed etherified melamine resin, etc., manufactured by Monsanto Co., Ltd., trade name). In the present invention, the solid content of the butyl etherified melamine resin (B1) relative to the total solid content of the melamine resin component is determined from the viewpoint of the processability of the obtained coating film and the retention of stain resistance. 30 to 100 mass ° / 〇 within the range. It is preferably 5〇~1〇〇% by mass, more preferably 7〇~1〇〇% by mass. The butyl fluorinated melamine resin (B1) is lower in polarity than the methyl melamine resin, the methyl/butyl mixed etherified melamine resin, and the polyester resin (A) which is a matrix resin. Good compatibility. Therefore, the coating film obtained from the pollution-resistant coating composition containing the butyl etherified melamine resin (B1) is excellent in uniformity of crosslinking. Further, the butyl etherified melamine resin (B1) is less likely to be localized to the surface layer than the methyl etherified melamine resin or the methyl/butyl mixed etherified melamine resin. Therefore, the coating film obtained from the pollution-resistant coating composition containing the butyl etherified melamine resin (B1) is also excellent in weather resistance. Further, in order to promote the hardening reaction between the polyester resin component (A) and the melamine resin component (B), a curing catalyst may be used as needed. As the hardening catalyst for promoting the hardening reaction, generally, a neutralizing substance of a sulfonic acid compound or a sulfonated 21 201217468 compound can be used. Examples of the rhein compound include p-toluene, dodecylbenzene-nonyl-fluorenyl group, dimercapto-Caidi acid, and the like. The neutralizing agent of the neutralized product of the rhein compound may, for example, be an i-grade amine, a secondary amine, a tertiary amine, ammonia, caustic soda or caustic oblique compound. In the composition of the contaminated coating material of the present invention, the ratio of the resin component (A) and the melamine resin component (B) is based on the total amount of the polyester resin component (A) and the melamine resin component (B). The polyester resin component (A) is 5 〇 to 9 〇 mass%, particularly 60 to 80 mass. The melamine resin component (B) is 1 〇 to 5 〇 mass%, particularly 20 to 40 mass. /. In view of the curable property, the stain resistance, the mechanical strength, the workability, the solvent resistance, the corrosion resistance, the weather resistance, and the like of the obtained coating film, it is preferred. (C) Organic citrate and/or its condensate component The component (C) of the present invention is represented by the formula: (I^n-Si-COR2)^ [wherein R1 may also be substituted by an epoxy group or a sulfhydryl group. The base of the carbon number 1 to 18 or the base of the stupid 'Han 2 series carbon number 1 to 6, η is 〇 or 1. The organic citrate and/or its condensate. The component (C) used in the coating composition of the present invention is blended for exerting a hydrophilizing effect on the surface of the substrate after application, and from the viewpoint of the effect, the above organic citrate The condensate is preferred. Specific examples of R1 in the above formula include, for example, anthracenyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, n-octyl 2, ethylhexyl, Sulfhydryl, fluorenyl, undecyl, dodecyl, tetradecyl, 22 201217468 ten / = A oxypropyl, methyl epoxypropyl (2-methylepoxypropyl), ethylmethyl, 2-carbylethyl, 2 benzylpropyl, 3-benzylpropyl, 4-nonylbutyl, stupyl, p-mentyl and the like. Specific examples of the organic oxalate salt can be exemplified by: tetramethoxine, four "frequency, tetrapropoxy oxime, tetraisopropyl oxychloride, tetrabutoxyx sulphide tetraisobutoxide Si-Xi et al. 4-functional base Xixia; methyl methoxymethene, methyl triethoxy decane, methyl tripropoxy decane, decyl triisopropoxy decane, methyl tri-n-butoxy lysine, methyl tri Isobutoxy Wei, Phenyl Trimethoate, Phenyltriethoxyoxane, Phenyltripropoxydecane, Phenyltriisopropoxydecane, Phenyl Di-n-Butane Oxide, Phenyl Triisobutoxide Xishou, hexyl trimethoxide yew, hexyl diethoxy Wei, lauryl trioxon sulphur, lauryl triethoxylate, sulphur-based dimethoxy-11, occupational ethyl trimethoxy a trifunctional decane such as a thiol methyl triethoxy decane, a mercaptoethyl triethoxy decane, a mercaptopropyl trimethoxy decane or a mercaptopropyl diethoxy decane. The condensate of the above organic decanoate may be exemplified by a combination The above-mentioned tetrafunctional or trifunctional decane or two or more kinds of condensates. The condensate of the organic phthalate can be produced by a general method and is commercially available. For example, MKC citrate MS51, MS56, MS57, MS5 6S, MS56SB5, MS58B15, MS58B30, ES40, EMS31, B TS (all of which are manufactured by Mitsubishi Chemical Corporation, trade name), A Sulfate 5 1 , ethyl citrate 40 , ethyl citrate 40T , ethyl citrate 48 (all of which are manufactured by COLCOAT), KR500, KR9218, X-4 1-1805, X-41-1810, X-41-1818, X-41-1053, X-4M056 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd., trade name), etc. 201217468, a condensate of a specific organic citrate is obtained by a monomer or a combination of two or more, a part & "decondensation. The condensate of the organic salt is a branched or straight condensate, and the degree of condensation is from 2 to 10. Preferably, it is from 2 to 2. It is preferred that the present invention has a '(C) component. The condensate of the organic citrate or the organic decanoate may be used singly or in combination of two or more kinds thereof. The organic citrate represented by the above formula and/or its condensate may be used as the fluorene R2 group. The ratio of the number of alkoxy groups having a f-oxy group and a carbon number of 2 to decyloxy group and having an oxy group having 2 to 6 carbon atoms is in the range of 95/5 to 30/70, which is formed from a coating material. The coating composition of the present invention has a solid content of the component (C) based on the total solid content of the component (a) and the component (B). It is preferably 1 to 20% by mass, more preferably 1 to 1% by mass, more preferably 3 to 7% by mass. (C) The amount of the component is within the above range, and it can be blended with the component (c). The effect is also suitable from the viewpoint of the initial stain resistance and stain resistance retention of the obtained coating film and the mechanical strength and durability of the coating film. (D) Containing fluorine atoms Aqueous dispersion type resin component The coating composition (D) component of the present invention is a non-aqueous dispersion liquid (Non Aqueous Dispersion, NAD) type resin containing fluorine atoms. The non-aqueous dispersion liquid type resin containing fluorine atoms may also be referred to as containing The non-aqueous dispersion liquid of the fluorine atom. The component (D) is specifically a non-aqueous dispersion type resin (D1) in which the polymer particles are dispersed in an organic solvent liquid containing a fluorine atom-containing dispersion stabilizer. And an organic solvent solution containing a dispersion stabilizer, which is a non-aqueous dispersion type resin (D2) in which polymer particles containing a fluoroalkyl group (meth) acrylate is dispersed, and the like. 24 201217468 Furthermore, In the present specification, "(fluorenyl) acrylate" means acrylate or methacrylate. As a specific example of the non-aqueous dispersion-type resin (D1), a non-aqueous dispersion type resin which can be prepared by dispersing a stabilizer containing a fluorine atom (D1 a) and an organic solvent can be exemplified. In the mixed solution of (D丨b), the poly- & I1 unsaturated monomer is copolymerized to form insoluble polymer particles (Die) in the mixed solution. The non-aqueous dispersion type resin (D1) can be said to be a non-aqueous dispersion type resin containing a dispersion medium, polymer particles (dispersed particles) and a dispersion stabilizer, and the dispersion stabilizer is a dispersion stabilizer containing a fluorine atom. A non-aqueous dispersion type resin, but is not limited thereto. Or, the non-aqueous dispersion type tree (D1) is a non-aqueous dispersion in which a polymer particle is dispersed in an organic solvent liquid containing a fluorine atom-containing dispersion stabilizer; and a dispersion stabilizer containing a fluorine atom (Dla) Among the organic solvents (Dlb), there are non-aqueous dispersions in which polymer particles (Die) which are insoluble in these are dispersed. The dispersion stabilizer (Dla) is a dispersion stabilizer containing a fluorine atom and stably dispersing the polymer particles (Die) in an organic solvent (Dlb). The dispersion stabilizer (Dla) is miscible with the organic solvent (Dlb) and is incompatible with the polymer particles (Dlc). The polymer particles (Die) are applicable, for example, to a polymer obtained by copolymerizing a fluoroalkyl group-containing (fluorenyl) acrylate (F-acrylate) and/or a fluorinated olefin-containing polymerizable unsaturated monomer. . The polymer may further contain one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a decyl group, a decyloxy group, and the like per molecule. The above-mentioned fluoroalkyl group-containing (meth) acrylate (F-acrylic acid ester) can be 25 201217468 as exemplified by the formula CH2=C(R)-COO-(CH2)n-Rf [R-based hydrogen atom or The methyl group, η is an integer of 1 to 1 〇, and is a compound represented by a linear or branched fluoroalkyl group having 1 to 21 carbon atoms. Here, a part or all of hydrogen of a "fluoroalkyl group"-based carbon atom chain or a branched hydrocarbon group may be substituted. The F-acrylate type may, for example, be perfluoromethyl decyl acrylate. Methylmethyl mercapto acrylate, perfluorobutyl ethyl diacetate, all 3 ethyl ethyl methacrylate, perfluoroisodecyl ethyl acrylate, whole sulphur Ethyl thioglycolic acid vinegar, perfluorooctyl ethyl acrylate vinegar, whole gas; ethyl thioglycolic acid vinegar, 2,2,3,3-tetrafluoropropyl acrylate vinegar 2,2,3,3_tetrafluoropropyl methacrylate, 1H, 1H, 5H_ octapentyl acrylic acid slightly, 1H, 1H, 5H-octafluoropentyl decyl propyl phthalate. Further, the fluorinated olefin may, for example, be tetrafluoroethylene, hexaethylene, triethylene gas, vinyl fluoride or trifluoroethylene. As the polymerizable unsaturated monomer for obtaining the dispersion stabilizer (ma), one or two or more of the above-mentioned fluorinated _ _ vinegar and the above fluorinated constitutive red group _ (four) can be used. The dispersion stabilizer _) can be prepared by the following formula: a group consisting of F_" and a group of rodent smokes or a mixture of two or more types of polymerization == propylene" The other type or two or more types are polymerized with other polymerizable unsaturated monomers. The other t-unsaturated monomer corpses and mono-hetero is not particularly limited. For example, it may be a dibasic polymerizable unsaturated monomer. j The following polymerizable unsaturated 26 201217468 Acrylic acid or methacrylic acid ester (i): decyl acrylate, methacrylic acid, S, acrylic acid, ethyl methacrylate, propylene Acid, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isodecyl acrylate, isodecyl methacrylate, hexyl acrylate, A Acrylic acid such as hexyl acrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate or the like, or a Cu alkyl ester of acrylic acid or mercaptoacrylic acid; acrylic acid such as cyclohexyl acrylate or cyclohexyl methacrylate; C3__2〇cycloalkyl methacrylate; acrylate C2~8 alkenyl ester of acrylic acid or methacrylic acid such as ester or allyl methacrylate; C3~2 of acrylic acid or methacrylic acid such as allyl oxyethyl acrylate or allyl methoxy acrylate; Alkenyloxyalkyl ester, etc. Epoxypropyl group-containing unsaturated monomer (Π): glycidyl acrylate, glycidyl methacrylate, etc. Hydroxyl-containing unsaturated monomer (iii): hydroxy acrylate a C2-8 hydroxyalkyl ester of acrylic acid or mercaptoacrylic acid such as ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate; a hydroxyalkyl vinyl ether such as hydroxybutyl vinyl ether; Allyl alcohol, mercaptopropanol, etc. Alkoxyalkyl group-containing unsaturated monomer (iv): γ-acryloxypropyl trioxoxane, γ-mercapto propylene methoxypropyl triterpene Oxane, β-propylene methoxyethyl trioxoxane, γ-mercapto propylene methoxyethyl trioxoxane, γ-acryloxypropyl triethoxy decane, γ-methyl propylene醯-methoxypropyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, etc. And carboxylic acid (ν): acrylic acid, mercaptoacrylic acid, itaconic acid, cis-butyl 27 201217468 enedionic acid, fumaric acid, crotonic acid, etc. Isocyanate group-containing unsaturated monomer (vi): acrylic acid isocyanate group Ethyl ester, m-isopropyl-α, οι-dimethylbenzyl isocyanate, etc. Unsaturated monomer having two or more polymerizable unsaturated bonds (vii): ethylene glycol diacrylate, B Glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tris(hydroxyindole) propane triacrylate, tris(hydroxyindole) propane trimethacrylate, etc. Aromatic aromatic compound (viii): styrene, α-mercaptostyrene, vinyl anthracene, p-styrene styrene acridine, etc. (i) other polymerizable unsaturated monomers other than ~(viii) (iv): acrylonitrile, methacrylic acid, methyl isopropyl ketone, vinyl acetate, beobar monomer (manufactured by Shell Chemical Co., Ltd., trade name), vinyl propionate, trimethyl vinyl acetate, Vinyl propionate, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl Ether, octyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethylene, propylene, butene, anthracene, fluorenyl-didecylaminoethyl acrylate, hydrazine, hydrazine - Dimercaptoethyl decyl acrylate, acrylamide, vinyl pyridine, and the like. In a polymerization reaction for preparing a dispersion stabilizer (Dla), a system formed by copolymerizing an F-acrylate and/or a fluorinated olefin with another polymerizable unsaturated monomer (F-acrylate) The ratio of the fluorinated olefin and the two components of the other polymerizable unsaturated monomer can be arbitrarily selected. From the viewpoint of the stain resistance, the F-acrylate and/or the fluorinated olefin is preferably 100 to 1% by mass, particularly preferably 30 to 5% by mass based on the total of the solid components of the two components. The other polymerizable unsaturated monomer is preferably a solid component of 28 201217468 of 0 to 99% by mass, particularly preferably 70 to 95% by mass. /. Within the scope. The above-mentioned two or more kinds of polymerization reactions selected from F-acrylates and fluorinated olefins or the copolymerization reaction with other polymerizable unsaturated monomers are preferably carried out in the presence of a radical polymerization initiator . The radical polymerization initiator may, for example, be an azo compound such as 2,2-azoisobutyronitrile or 2,2'-azobis(2,4-dimethylvaleronitrile) or benzoquinone peroxide. A peroxide such as lauryl peroxide or tert-butyl peroxide. The amount of the initiator to be used is preferably 〇. 2~ relative to the total amount of the solid content of the acrylate and/or fluorinated olefin and other polymerizable unsaturated monomers used. 1% by mass, particularly preferably in the range of 0.5 to 5% by mass. In the polymerization for preparing the dispersion stabilizer (Dla), by using (ii) an epoxy group-containing unsaturated monomer, (iii) a trans group-containing unsaturated monomer, and (iv) an alkoxy group. As the other polymerizable unsaturated monomer, a nonylidyl monomer of a decyl group, (v) an unsaturated carboxylic acid, (Vi) an unsaturated monomer containing an isocyanate group, etc. can be obtained with a glycidyl group, a hydroxyl group, and a hospital oxygen. A dispersion stabilizer of a functional group such as a mercapto group, a carboxyl group or an isocyanate group. In particular, a dispersion stabilizer having a radical is reacted with a polymer group (D1 c) having a warp group and a trimeric gas amine resin component (B) and the above organic silicate and/or a condensate component thereof (c) , can form a three-dimensional crosslinked hard coating film. As the dispersion stabilizer (Dla), those having an average of 0.1 or more polymerizable unsaturated oxime in one molecule can be suitably used. When the dispersion stabilizer (Dla) has a polymerizable unsaturated bond, it can form a covalent bond with the polymer particles (Die), thereby improving the storage stability and mechanical stability of the non-aqueous dispersion type resin. 'It is better for pollution resistance and the like. 29 201217468 A method of introducing a polymerizable unsaturated bond into a dispersion stabilizer (Dla) is, for example, a functional group which is present in a dispersion stabilizer, and contains other functional groups which will react with the functional group. A method in which a polymerizable unsaturated monomer is reacted. For example, a polymerizable unsaturated monomer containing a propylene group (for example, glycidyl acrylate, glycidyl methacrylate, allyl propyl propyl group) can be used in a dispersion stabilizer containing a carboxyl group (Dla). The reaction is carried out by ether or the like 'by which a polymerizable unsaturated bond is introduced into the dispersion stabilizer. Further, conversely, a polymerizable monomer (for example, acrylic acid, methacrylic acid, maleic acid, antibutene-acid, and itacon) can also be used in a dispersion stabilizer (Dla) containing a glycidyl group. The acid or the like is subjected to a reaction to introduce a polymerizable unsaturated bond into the dispersion stabilizer. In addition to the above, examples of the combination of such functional groups include an acid anhydride group and a hydroxyl group, an acid anhydride group and a thiol group, an isocyanate group and a hydroxyl group. As the dispersion stabilizer (Dla), a resin containing a fluorine atom (a resin obtained by copolymerizing a fluororesin such as F-acrylic acid ester and/or a fluorinated olefin with another polymerizable unsaturated monomer) can be suitably used. Or a dispersion stabilizer in which a polymerizable unsaturated bond is bonded to the fluororesin. As such a fluororesin, a commercially available fluororesin such as Lumiflon LF800 (Asahi Glass Co., Ltd.) may be mentioned. The molecular weight of the dispersion stabilizer (Dla) is not particularly limited, but is preferably in the range of from 1 Å to 60,000, particularly from 2 Å to 3 Torr, based on the number average molecular weight. As the organic solvent (Dlb), a fluoroalkyl group-containing (meth)acrylic acid vinegar and/or I-form, and other polymerizations for preparing the above-mentioned dispersion stabilizer (Dla) and polymer particles (Dlc) can be used. Polymerization of a saturated monomer or the like 30 201217468 The unsaturated monomer is dissolved, but substantially no polymer particles (Die) obtained from the polymerizable unsaturated monomer are dissolved. Therefore, it can be arbitrarily selected depending on the characteristic values such as the composition or molecular weight of the dispersion stabilizer (Dla) and the polymer particles (Die) to be used, and examples thereof include aliphatic hydrocarbons such as hexane, heptane, and octane; Aromatic hydrocarbons such as benzene, diphenylbenzene, toluene, cyclohexane; methyl acetate, ethyl acetate, isobutyl acetate, mercaptoacetic acid, ethylene glycol monomethyl ether, acetic acid-2-ethylhexyl An ester compound such as ester, diethylene glycol monomethyl ether or the like; an ether compound such as cyanidin, butyl cyanidin, isopropyl ether, ethylene glycol monodecyl ether or diethylene glycol monobutyl ether; Ethyl alcohol, isopropyl alcohol, n-butyl alcohol, i-butyl alcohol, octyl alcohol, hexyl alcohol, etc.; mercapto isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, different buddha An organic solvent such as a ketone compound such as a ketone, acetophenone, ethyl isoamyl ketone, methyl isoamyl ketone or ethyl butyl ketone. In general, an organic solvent such as an aromatic hydrocarbon, an alcohol, an ether compound, an ester compound or a ketone compound is further used in the form of an aliphatic hydrocarbon organic solvent. For the preferred organic solvent, for example, mineral spirits obtained by fractionating crude oil (for example, those prescribed in JIS K 2201 No. 4) can be mentioned. The non-aqueous dispersion type resin (D1) can be copolymerized by, for example, a mixture of a dispersion stabilizer (D1 a) containing a fluorine atom and an organic solvent (D1 b). The polymer particles (Die) which are insoluble in the mixed solution are formed to prepare. The polymerizable unsaturated monomer for obtaining the polymer particles (D1 c) is not particularly limited as long as it is a radical polymerizable unsaturated monomer. Specifically, in the above-mentioned fluorine atom-containing dispersion stabilizer (Dla), vinegar (1) which is a "tetracarboxylic acid or methyl acrylate" which is "31 201217468 other polymerizable unsaturated monomer" is exemplified to contain % oxypropyl group. Saturated monomer (ii), hydroxyl group-containing unsaturated monomer (out), unsaturated group containing anthraquinone base (tetra), unsaturated acid (V), unsaturated acid containing succinic acid (vi), unsaturated monomer (vii) having two or more polymerizable unsaturated bonds, polymer (viii), (1) to (f), and other polymerizable unsaturated monomers (iv) Wait. Further, as the polymerizable unsaturated monomer for adjusting the polymer particles (Die:), the aforementioned F_acrylic acid vinegar may also be used. The polymerization of the above polymerizable unsaturated monomer for obtaining the polymer particles (D1 c) is preferably carried out in the presence of a radical polymerization initiator. Examples of the radical polymerizable initiator include azo compounds such as 2 2 -azoisobutyronitrile and 2,2,-azobis(2,4-dimethylvaleronitrile), and benzoic acid peroxide. a peroxide such as hydrazine, lauryl peroxide or a second butyl peroxide, and the amount of the initiator used is 〇2 to 1% by mass based on the total amount of the polymerizable unsaturated monomer. In particular, it is preferably in the range of 0.5 to 5% by mass. The polymer particles (Die) are used by using the above-mentioned epoxy group-containing unsaturated monomer (ii), hydroxyl group-containing unsaturated monomer (iH), alkoxyalkyl group-containing unsaturated monomer (iv), As the polymerizable unsaturated monomer, a saturated carboxylic acid (v), an isocyanate group-containing unsaturated monomer (vi) or the like can be obtained, and polymer particles (D1 c) having the functional groups can be obtained. In particular, the polymer particles having a hydroxyl group are reacted with a dispersion stabilizer (Dla) having a hydroxyl group and the melamine resin component (B) and an organic silicate and/or a condensate component thereof (C). A three-dimensionally crosslinked hard coat film is formed. 32 201217468 The number average molecular weight of the polymer particles (Die) is preferably 10,000 or more from the viewpoint of stain resistance, and particularly preferably in the range of 20,000 or more. As the polymer particles (Die), polymer particles cross-linked by particles can be suitably used from the viewpoint of improving the contamination property. The method for forming the polymer particles cross-linked in the particles is, for example, a method in which a combination of polymerizable unsaturated monomers having functional groups that react with each other is used as a constituent component of the polymerizable unsaturated monomer; A method in which an unsaturated monomer (vii) having two or more polymerizable unsaturated bonds is used as a constituent component of a polymerizable unsaturated monomer. In the above, from the viewpoint of the stability of the polymerization reaction, a method of using a combination of a polymerizable unsaturated monomer having a functional group reactive with each other as a constituent component of the polymerizable unsaturated monomer can be suitably used. Specifically, for example, a carboxyl group-containing polymerizable unsaturated monomer (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.) and a polymerizable group containing an epoxy group are not used. A saturated monomer (for example, acrylic propylene acrylate, methacrylic epoxy (tetra), propylene propylene acrylate, etc.) as a constituent component of the polymerizable unsaturated monomer can be obtained by each polymerizable unsaturated monomer. The thiol group is subjected to an addition reaction with a glycidyl group to adjust the cross-linked polymer particles. Examples of the combination of such an S-energy group include a carboxyl group and a glycidyl group, and an acid group such as an acid group, an acid group, a thiol group, an isocyanate group, and a hydroxyl group. In the non-aqueous dispersion type resin (Dl) towel, the ratio of the dispersing agent (Dla) to the polymer particles (Die) can be arbitrarily selected, but from the non-aqueous dispersion liquid 33 201217468 type resin (four) storage stability and resistance From the viewpoint of contamination, the dispersion stabilizer (D丨a) is preferably in the range of 3 to 70% by mass, particularly 5 to 60% by mass based on the total of the two components; the polymer particles ( D丨c) is 97% by mass by mass, especially 95 to 40% by mass. /. The range is better. Further, the total concentration of the dispersion stabilizer (Dla) and the polymer particles (Dlc) is 30 to 70 based on the total enthalpy of the dispersion stabilizer (Dla), the organic solvent (Dlb), and the polymer particles (Dic). The quality is particularly preferably in the range of 4 〇 to 6 〇 mass%. In the organic solvent (D丨b) containing the dispersion stabilizer (D1 a), the polymerization reaction of the polymerizable unsaturated monomer for obtaining the polymer particles (Die) can be carried out at 60 to 160 C. Perform about ～15 hours at the left and right temperature. The non-aqueous dispersion-type resin (D1) thus obtained is particularly excellent in dispersion stability at the point of the polymer particles (di = . The average particle diameter of the non-aqueous dispersion resin (D1) is resistant. The contamination point of view is preferably in the range of 20 to 500 nm, particularly 50 to 4 Å, more particularly 100 to 300 nm. In the present specification, the average particle size means the use of sub-micron particle size. The distribution measuring device "COULTER N4 type" (manufactured by Beckman Coulter Co., Ltd.) was used to dilute the sample to a straightness measured at 20 C. The non-aqueous dispersion type resin (D2) contained dispersion stability. In the organic solvent solution of the agent, there is a non-aqueous dispersion type resin in which polymer particles having a fluorine-containing alkyl (meth) acrylate as a constituent component are dispersed. Specific examples of the non-aqueous dispersion type resin (D2) For example, it can be exemplified by a mixture of a dispersion stabilizer (D2a) and an organic solvent (D2b).

34 201217468 基）丙稀酸酯與其他聚合性不飽和單體共聚合而在該混合 液中形成不溶的聚合物粒子（D2c)來調整之非水性分散液 型樹脂。非水性分散液型樹脂（D2)係在含有分散穩定劑 (D2a)之有機溶劑(D2b)中’有不溶於該分散穩定劑及有機溶 劑之聚合物粒子(D2c)分散之非水性分散液型樹脂，該聚合 物粒子(D2c)係由含有氟烷基之（甲基）丙烯酸酯與其他聚合 性不飽和單體之共聚合物所構成之非水性分散液型樹脂。 分散穩定劑（D2a)係用於使聚合物粒子（D2c)安定地分 散於有機溶劑(D2b)中的物質，宜為與有機溶劑(D2b)相互 溶解，而不與聚合物粒子(D2c)相溶者。 具體而言，可舉例如：丙稀酸樹脂、乙稀基樹脂、聚 酯樹脂、酸醇樹脂、胺基甲酸酯樹脂、含氟樹脂等。在該 等樹脂中可視需要使每1分子含有1個以上選自經基、羧 基、環氧基、矽醇基、矽氧烷基等之官能基。 進一步，作為分散穩定劑(D2a)係可使用每1分子具有 平均0.1個以上的聚合性不飽和鍵結者。就導入聚合性不飽 和鍵結之方法而言，係可舉例如，在含有竣基之分散穩定 劑中使含有環氧丙基之聚合性不飽和單體（例如環氧丙基 丙烯酸酯、環氧丙基曱基丙烯酸酯、烯丙基環氧丙基醚等) 進行反應的方法，又，相反地，在含有環氧兩基之分散穩 定劑中，使含羧基之聚合性不飽和單體(例如丙烯酸、甲基 丙烯酸、順丁烯二酸、反丁烯二酸、衣康酸等）進行反應之 方法等。就上述之官能基組合而言，在上述之外，可列舉 如酸酐基與羥基、酸酐基與硫醇基、異氰酸酯基與經基的 35 201217468 組合等。 若預先於分散穩定劑（D2a)申導入聚合性不飽和鍵 結，則由於可使其在與♦合形成物粒子(D2c)之間形成共價 鍵，因可提高非水性分散液型樹脂之貯藏安定性、機械的 安定性、耐污染性等而為佳。 .分散穩定劑(D2a)分子量雖無特別限制，但以數平均分子 量計為1000〜60000，特別是2000〜30000之範圍内者為佳。 有機溶劑（D2b)係可使用會溶解用於調製上述分散穩 定劑(D2a)及聚合物粒子(D2c)之含i说基的（甲基）丙稀酸 酯及其他聚合性不飽和單體等聚合性不飽和單體，但實質 上不會溶解自該聚合性殘和單體賴得之聚合物粒子 (D2c)者。 因此，可依所使用之分散穩定劑(D2a)及聚合物粒子 之組成及分子量等特性值任意地進行，作為有機 溶劑(D2b)，可同樣地使用例如作為前述有機㈣所 η示者般而°，且使用以脂肪族煙有機溶劑為主體， 並進-步組合適宜芳香族烴、醇、㈣合物、s旨化合物或 ㈣合物等有機溶劑者。作為該種較佳之有機溶劑，可列 舉士將原/由刀顧所獲得之礦油精(例如，規定於瓜κ 22〇1 4 號者。）。 非水性分散液型樹脂㈣係可藉由，例如，在分散穩 定劑(D2a)與有機溶劑(議)之混合液中，使含有氟烧基之 (甲基)㈣咖與魏聚合性讀和單體絲合而於該混 合液中形成不溶的聚合物粒子(D2e)來進行調整。 36 201217468 就用於獲得聚合物粒子(D2c)之含有氟烷基的（曱基）丙 烯酸酯（F-丙烯酸酯）而言，可舉例如由 通式 CH2=C(R)-COO-(CH2)n-Rf [R係氫原子或曱基’ η係1〜1〇之整數，Rf係碳數1〜21 個之直鏈狀或分枝狀的氟烷基] 所表示之化合物。在此，「氟烷基」係將碳原子數卜21 個之直鏈狀或分枝狀烴基之氫的一部分或全部取代為氟原 子之基。具體而言，可同樣地使用在前述分散穩定劑(Dla) 所例示者。 就其他聚合性不飽和單體而言，只要是上述心丙烯酸酯 以外之自由基聚合性的不飽和單體便可無特別限制地使用。 具體而言，係可同樣地使用在前述分散穩定劑(Dla)中 例不為「其他聚合性不飽和單體」之丙烯酸或甲基丙烯酸 的酯（i)、含有環氧丙基之不飽和單體(ii)、含羥基的不飽和 單體(iii)、含有烧氧石夕院基之不飽和單體(iv)、不飽和缓酸 (V)、含異氰酸酯基之不飽和單體(vi)、具有2個以上聚合性 不飽和鍵結之不飽和單體（vii)、乙烯基芳香族化合物 (V111)、⑴〜(viii)以外之其他聚合性不飽和單體(iv)等。 在聚合物粒子(D2c)中，F-丙烯酸酯與其他聚合性不飽 和單體之比率雖可任意地選擇，但從耐污染性之觀點看來， 以該兩成分之總量為基準，F_丙烯酸酯係以卯〜丨質量％，特 別以30〜5質量％之範_為佳；其他聚合性不飽和單體係 以10〜99質量％，特別以7〇〜95質量％之範圍内為佳。 F·丙烯酸酯與其他聚合性不飽和單體之共聚合反應係 37 201217468 宜在自由基聚合㈣劑之存在下進行。作為自由基聚合起 始劑’係可舉例如2,2_偶氮異丁腈、以·偶氮雙(2,4_二甲基 戊腈）等偶氮化合物、過氧化苯⑽、月桂基過氧化物、第 三丁基過氧化物等過氧化物；該等起始劑之使用量相對於 F-丙烯酸酿與其他聚合性不飽和單體之總量係以在〇2〜1〇 重量％，特別是在0.5〜5重量％之範圍内為佳。 聚合物粒子(D2c)係藉由使用前述含有環氧丙基之不 飽和單體(ii)、含Μ的讀和單體㈣、含⑽氧石夕烧基 之不飽和單體(iv)、不飽和紐(v)、含異氰_纟之不飽和 單體(vi)等作為聚合性不飽和單體，可藉以獲得具有該等官 能基之聚合物粒子。 特別是，具有羥基之聚合物粒子係可與令其具有羥基 之分散穩定劑（D2a) —起和前述三聚氰胺樹脂成分(B)及有 機矽酸鹽及/或其縮合物成分(C)進行反應而形成三維交聯 之硬化塗膜。 聚合物粒子(D2c)之數平均分子量，從耐污染性的觀點 看來，係以在10000以上，特別是在20000以上之範圍内為佳。 作為聚合物粒子(D2c) ’從提高耐污染性的觀點看來， 係可適宜地使用經粒子内交聯之聚合物粒子。 要形成經粒子内交聯之聚合物粒子係可舉例如：將具 有會互相反應之g此基之聚合性不飽和單體的組合作為聚 合性不飽和單體之構成成分來使用的方法；將前述具有2個 以上聚合性不飽和鍵結之不飽和單體(vii)作為聚合性不飽 和單體之構成成分來使用的方法等。 b) 38 201217468 上述之中，從聚合反應之安定性的觀點看來，可適宜 地使用將具有會互相反應之官能基之聚合性不飽和單體的 組合作為聚合性不飽和單體之構成成分使用的方法。 具體而言，例如’將含緩基之聚合性不飽和單體(例如 丙烯酸、曱基丙烯酸、順丁烯二酸、反丁烯二酸、衣康酸 等）與含有環氧丙基之聚合性不飽和單體(例如丙烯酸環氧 丙酯、曱基丙烯酸環氧丙酯、烯丙基環氧丙基醚等）作為聚 合性不飽和單體之構成成分使用，藉由使各個聚合性不飽 和單體所具有之羧基與環氧丙基進行加成反應，可調整經 粒子内交聯之聚合物粒子。 就该種g能基之組合而言’在叛基環氧丙基之外，係 可列舉如：酸酐基與羥基、酸酐基與硫醇基、異氰酸酯基 與羥基等之組合。 在非水性分散液型樹脂(D2)中，分散穩定劑(D2a)與聚 合物粒子(D2c)之比率雖可任意地選擇，但從非水性分散液 型樹脂(D2)之貯藏安定性與耐污染性的觀點看來，以該兩 成分之總量為準’分散穩定劑(D2a)係以3〜70質量％，特別 是5〜60質量％之範圍内為佳；聚合物粒子(p2c)係以97〜30 質量％，特別是95〜40質量％之範圍内為佳。 又’分散穩定劑(D2a)與聚合物粒子(D2c)之合計濃度， 以分散穩定劑(D2a)、有機溶劑(〇2b)及聚合物粒子(D2c)之 總量為基準’係以30-70質量％，特別是以4〇〜60質量％之範 圍内為佳。 在含有分散穩定劑(D2a)之有機溶劑(D2b)中，用於獲得 39 201217468 聚合物粒子(D2e)《F丙稀_與其他聚合性不飽和單體的 聚合反應—般可在6G〜_°c左右的溫度下進行約κ20小 時。如此賴得之非水性分散㈣樹脂⑽)在分散安定性 方面極為優異。 非JU生刀放液型樹脂(D2)的平均粒徑，從对污染性的 觀點看來，係以20〜500nm，特別是50〜彻nm，更特別是 100〜3OOrnn之範圍内為佳。 作為3有氟原子的非水性分散液型樹脂成分⑼，可代 替或是與在含有含氟原子之分散穩定劑的有機溶劑液中有 聚合物粒子分散之非水性分散液型樹脂㈣—起使用在含 有分散穩定劑之有機溶劑液中有以含㈣基之（甲基）丙稀 酸酿作為構成成分之聚合物粒子分散之非水性分散液型樹 脂(D2)。 在本發明之塗料組成物中，⑼成分的量以(A)成分及 (B)成刀之總里為基準，作為固體成分係$〜骑量％，而以 0 30¾里/〇為佳’以15〜25質量％之範圍内為更佳。 由於(D)成分1係在上述範圍内，⑼成分的效果可被 ^揮而k塗膜之初期耐污染性、耐污染性之保持性及塗 膜的機械強度、耐久性面看來亦為佳。 本發明之塗料組成物中，除前述之(A)、（B)、（C)及(D) 之外在不阻害本發明之效果的範圍内，亦可使用表 見酉文I·生之界面•性劑及含删酸之化合物等加水分解促進 1著色顏料氧化石夕微粒子等體質顏料；有機樹脂粉末、 無機質骨材、顏料分散劑、紫外線吸收劑、紫外線安定劑、34 201217468 A non-aqueous dispersion type resin in which acrylic acid ester is copolymerized with another polymerizable unsaturated monomer to form insoluble polymer particles (D2c) in the mixed solution. The non-aqueous dispersion type resin (D2) is a non-aqueous dispersion type in which the polymer particles (D2c) which are insoluble in the dispersion stabilizer and the organic solvent are dispersed in the organic solvent (D2b) containing the dispersion stabilizer (D2a). The resin, the polymer particles (D2c) is a non-aqueous dispersion type resin composed of a copolymer of a fluoroalkyl group-containing (meth) acrylate and another polymerizable unsaturated monomer. The dispersion stabilizer (D2a) is a substance for stably dispersing the polymer particles (D2c) in the organic solvent (D2b), and is preferably dissolved in the organic solvent (D2b) without being polymerized with the polymer particles (D2c). Soluble. Specific examples thereof include an acrylic resin, an ethylene-based resin, a polyester resin, an acid alcohol resin, a urethane resin, and a fluorine-containing resin. In the above-mentioned resin, one or more functional groups selected from a group consisting of a trans group, a carboxyl group, an epoxy group, a decyl group, a decyloxy group, and the like may be contained per molecule. Further, as the dispersion stabilizer (D2a), an average of 0.1 or more polymerizable unsaturated bonds per molecule can be used. In the method of introducing a polymerizable unsaturated bond, for example, a polymerizable unsaturated monomer containing a glycidyl group (for example, a glycidyl acrylate, a ring) in a dispersion stabilizer containing a mercapto group a method of reacting oxypropyl methacrylate, allyl epoxypropyl ether, etc., and conversely, a carboxyl group-containing polymerizable unsaturated monomer in a dispersion stabilizer containing an epoxy group A method of reacting (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.). In the above-mentioned functional group combination, in addition to the above, a combination of an acid anhydride group and a hydroxyl group, an acid anhydride group and a thiol group, an isocyanate group and a trans group 35 201217468 may be mentioned. When a polymerizable unsaturated bond is introduced in advance to the dispersion stabilizer (D2a), a covalent bond can be formed between the particles and the formed particles (D2c), so that the non-aqueous dispersion type resin can be improved. It is preferable to store stability, mechanical stability, and pollution resistance. The molecular weight of the dispersion stabilizer (D2a) is not particularly limited, but it is preferably from 1,000 to 60,000, particularly in the range of from 2,000 to 30,000, in terms of number average molecular weight. The organic solvent (D2b) may be a (meth) acrylate or other polymerizable unsaturated monomer which dissolves the above-mentioned dispersion stabilizer (D2a) and polymer particles (D2c). The polymerizable unsaturated monomer does not substantially dissolve the polymer particles (D2c) obtained from the polymerizable residue and the monomer. Therefore, it can be arbitrarily carried out depending on the dispersion stabilizer (D2a) and the composition and molecular weight of the polymer particles, and the organic solvent (D2b) can be similarly used, for example, as the organic (four) °, and an organic solvent such as an aromatic hydrocarbon, an alcohol, a (tetra) compound, a s-based compound or a (tetra) compound is further combined and used. As such a preferred organic solvent, it is possible to list the mineral spirits obtained by the original/manufactured by Knife (for example, those prescribed in the melon κ 22〇14). The non-aqueous dispersion type resin (4) can be obtained by, for example, mixing a mixture of a dispersion stabilizer (D2a) and an organic solvent (co) with a fluoroalkyl group (meth) The monomer is conjugated to form insoluble polymer particles (D2e) in the mixed solution for adjustment. 36 201217468 For the fluoroalkyl group-containing (fluorenyl) acrylate (F-acrylate) for obtaining polymer particles (D2c), for example, the formula CH2=C(R)-COO-(CH2) n-Rf [R-based hydrogen atom or fluorenyl ' η is an integer of 1 to 1 ,, and Rf is a compound represented by a linear or branched fluoroalkyl group having 1 to 21 carbon atoms]. Here, the "fluoroalkyl group" is a group in which a part or all of hydrogen having 21 linear or branched hydrocarbon groups having a carbon number is substituted with a fluorine atom. Specifically, those exemplified in the aforementioned dispersion stabilizer (Dla) can be used similarly. The other polymerizable unsaturated monomer is not particularly limited as long as it is a radical polymerizable unsaturated monomer other than the above-mentioned cardiac acrylate. Specifically, an ester of acrylic acid or methacrylic acid (i) which is not referred to as "other polymerizable unsaturated monomer" in the above-mentioned dispersion stabilizer (Dla), and an unsaturated group containing an epoxy group can be used in the same manner. Monomer (ii), hydroxyl group-containing unsaturated monomer (iii), non-saturated monomer (iv) containing anthraquinone, unsaturated acid (V), isocyanate group-containing unsaturated monomer ( Vi) an unsaturated monomer (vii) having two or more polymerizable unsaturated bonds, a vinyl aromatic compound (V111), and other polymerizable unsaturated monomer (iv) other than (1) to (viii). In the polymer particles (D2c), the ratio of the F-acrylate to the other polymerizable unsaturated monomer can be arbitrarily selected, but from the viewpoint of stain resistance, based on the total amount of the two components, F The acrylate is preferably 卯 丨 丨 by mass, particularly preferably 30 to 5% by mass; the other polymerizable unsaturated single system is in the range of 10 to 99% by mass, particularly 7 to 95% by mass. It is better. The copolymerization reaction system of F·acrylate and other polymerizable unsaturated monomer is preferably carried out in the presence of a radical polymerization (four) agent. Examples of the radical polymerization initiator include a azo compound such as 2,2-azoibutyronitrile or azobis(2,4-dimethylvaleronitrile), benzoyl peroxide (10), and lauryl. a peroxide such as a peroxide or a third butyl peroxide; the amount of the initiator used is relative to the total amount of F-acrylic acid and other polymerizable unsaturated monomers at a weight of 〇2 to 1 〇 % is particularly preferably in the range of 0.5 to 5% by weight. The polymer particles (D2c) are obtained by using the above-mentioned epoxy group-containing unsaturated monomer (ii), ruthenium-containing read and monomer (4), (10) oxysulphate-containing unsaturated monomer (iv), As the unsaturated unsaturated monomer (v), the isocyanate-containing unsaturated monomer (vi) or the like, a polymerizable unsaturated monomer can be obtained to obtain polymer particles having the functional groups. In particular, the polymer particles having a hydroxyl group can react with the dispersion stabilizer (D2a) having a hydroxyl group and the melamine resin component (B) and the organic citrate and/or its condensate component (C). A three-dimensional crosslinked hardened coating film is formed. The number average molecular weight of the polymer particles (D2c) is preferably in the range of 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of stain resistance. As the polymer particles (D2c)', from the viewpoint of improving the stain resistance, polymer particles cross-linked in the particles can be suitably used. The method of forming a polymer particle cross-linked by intraparticles, for example, a method of using a combination of polymerizable unsaturated monomers having such a group which reacts with each other as a constituent component of a polymerizable unsaturated monomer; The method of using the unsaturated monomer (vii) having two or more polymerizable unsaturated bonds as a constituent component of a polymerizable unsaturated monomer. b) 38 201217468 In the above, from the viewpoint of the stability of the polymerization reaction, a combination of polymerizable unsaturated monomers having functional groups reactive with each other can be suitably used as a constituent component of the polymerizable unsaturated monomer. usage instructions. Specifically, for example, 'polymerization of a polymerizable unsaturated monomer containing a buffer (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.) and a glycidyl group-containing polymerization An unsaturated monomer (for example, glycidyl acrylate, glycidyl methacrylate, allyl epoxypropyl ether, etc.) is used as a constituent component of the polymerizable unsaturated monomer, and the respective polymerizability is not The carboxyl group of the saturated monomer is subjected to an addition reaction with the epoxy propyl group, and the polymer particles cross-linked by the particles can be adjusted. In the case of such a combination of g groups, the combination of an acid group and a hydroxyl group, an acid anhydride group and a thiol group, an isocyanate group and a hydroxyl group may be mentioned. In the non-aqueous dispersion type resin (D2), the ratio of the dispersion stabilizer (D2a) to the polymer particles (D2c) can be arbitrarily selected, but the storage stability and resistance from the non-aqueous dispersion type resin (D2) From the viewpoint of pollution, it is preferred that the dispersion stabilizer (D2a) is in the range of 3 to 70% by mass, particularly 5 to 60% by mass, based on the total amount of the two components; polymer particles (p2c) It is preferably in the range of 97 to 30% by mass, particularly 95 to 40% by mass. Further, the total concentration of the dispersion stabilizer (D2a) and the polymer particles (D2c) is based on the total amount of the dispersion stabilizer (D2a), the organic solvent (〇2b), and the polymer particles (D2c). 70% by mass, particularly preferably in the range of 4 to 60% by mass. In the organic solvent (D2b) containing the dispersion stabilizer (D2a), used to obtain 39 201217468 polymer particles (D2e) "F propylene_polymerization with other polymerizable unsaturated monomers - generally in 6G~_ About κ 20 hours was carried out at a temperature of about ° c. The non-aqueous dispersion (4) resin (10) thus obtained is extremely excellent in dispersion stability. The average particle diameter of the non-JU raw knife discharge type resin (D2) is preferably in the range of 20 to 500 nm, particularly 50 to 100 nm, and more particularly 100 to 300 rnn from the viewpoint of contamination. The non-aqueous dispersion type resin component (9) having three fluorine atoms may be used instead of or in combination with a non-aqueous dispersion type resin (four) having polymer particles dispersed in an organic solvent liquid containing a fluorine atom-containing dispersion stabilizer. In the organic solvent liquid containing the dispersion stabilizer, there is a non-aqueous dispersion liquid type resin (D2) in which polymer particles having a (tetra)-based (meth)acrylic acid-containing constituent component are dispersed. In the coating composition of the present invention, the amount of the component (9) is based on the total amount of the components (A) and (B), and the solid component is % to the amount of riding, and 0 303⁄4 liters/inch is preferred. It is more preferably in the range of 15 to 25 mass%. Since the component (D) 1 is in the above range, the effect of the component (9) can be improved, and the initial stain resistance and the stain resistance retention of the k coating film, and the mechanical strength and durability of the coating film are also good. In the coating composition of the present invention, in addition to the above (A), (B), (C) and (D), in the range which does not impair the effects of the present invention, it can also be used as a table. Interfacial agent and acid-containing compound, etc., hydrolyzed to promote 1 color pigment such as oxidized stone granules; organic resin powder, inorganic bone material, pigment dispersant, ultraviolet absorber, ultraviolet stabilizer,

S 40 201217468 消泡劑及表面調整劑等塗料添加劑；及溶劑等迄今使用於 塗料之公知的材料。 上述溶劑係以對各(C )成分及(D)成分之溶解性良好之 溶劑為佳。藉由使用該種溶剤，可在使各(C)成分及(D)成分 在不產生粗大化的情況下分散，而可形成耐污染性特別優 異的塗膜。 上述表現醆性之界面活性劑及含硼酸的化合物係具有 促進上述有機矽酸鹽及/或其縮合物成分(C)之加水分解的 作用者。表現酸性之界面活性劑及含硼酸的化合物等加水 分解促進劑若併用雖會造成本發明之塗料組成物的適用期 縮短，但從提高耐污染性的觀點看來是可以使用的。 表現酸性之界面活性劑係可舉例如：聚氧乙烯磷酸 酯、烷基磷酸酯鹽等酸酯鹽；例如月桂基磺酸鈉、十二基 苯猶鈉等找基歧基苯俩鹽；w基料酸納等之 烧基萘《鹽、縣二苯㈣俩鹽料酸鹽；例如燒基 或烧基苯硫Μ、（聚）氧乙馳絲基㈣酸鹽等硫酸醋 鹽；例城基俩丁二酸鹽等__$ 作為含喊的化合物係可舉例如：職三曱自旨、酸三乙 酯、硼酸三丁酯等硼酸二栌i此 一烷基自曰；硼酸等。該等加水分解 促進劑之摻混量，相對於俞、+·/Λ、， 質 則述(八)成分及(Β)成分之總量，為 30質量％以下，特別是以〇5〜2〇 “菫為 量％為佳。 „ #L 質里/° ’更特別是以1〜1〇 作為上述體質顏料 石、雲母粉、鋇氧等。 ’係可列舉如： 體質顏料之摻混 氧化矽微粒子、滑 量，相對於前述(A) 41 201217468 成分及(B)成分之總量，為0.1〜20質量％，特別是以0.5〜15 質量％，更特別是以1〜10質量％為佳。 又，在本發明之塗料組成物中，在用來將所獲得之塗 膜消光、或用於使其成為半光等成品外觀之光澤調整的目 的上，亦可使用消光劑（E)。消光劑（E)係用於降低所獲得之 塗膜的光澤者，可為有機系消光劑及無機系消光劑中任一 者，又，該等係可單獨或組合2種以上使用。 本發明之耐污染塗料組成物係可形成在消光、半光等 光澤經降低之成品外觀的塗膜中，耐污染性、耐蝕性之保 持性特別優異的塗膜。 作為有機系消光劑係可舉例如完全不會因塗膜形成時 的焙燒而熔融的有機樹脂微粒子。該有機樹脂微粒子通常 平均粒徑在3〜80μιη，較宜為5〜60μιη之範圍内，從塗膜外 觀、塗裝作業性等的觀點看來係較為適宜。作為有機系消 光劑係可舉例如：聚偏二氟乙烯及聚四氟乙烯等氟樹脂、 聚醯胺、丙稀酸樹脂、聚胺基曱酸S旨、紛樹脂、石夕氧樹脂、 聚丙烯、耐綸11及耐綸12等聚醯胺等。 作為無機系消光劑係可列舉如：氧化矽、雲母、氧化 鋁、滑石、黏土、碳酸鈣、硫酸鋇等。 上述消光劑（Ε)係可單獨或組合2種以上來使用。消光 劑(Ε)之摻混量，相對於前述(Α)成分及(Β)成分之總量係以 0.1〜30質量％，特別是以0.5〜20質量％為佳。 本發明之耐污染塗料組成物係可藉由將上述(Α)〜(D) 成分及視需要之上述其他的成分均勻地混合來製造。較佳 42 201217468 的成分混合來料。捕糊’再將該顏料糊與剩餘 本發明之塗料組成物可作成—液型塗料亦 點看來，係以作成二液型塗料為佳。Μ杨臧f生之規 就塗裝本發明之耐污染塗料組成物的方法而言，可列 mr法：㈣視需麵加有機溶劑將塗料組成物調整 t所期望之黏度後，使用利用空氣噴射、靜電空氣喷射、輥 塗抹機、流動塗膜、熱浸形式的㈣機、刷毛、塗布桿^ 施器等，以使乾燥後塗膜的膜厚一般成為05〜300μπ1、較宜 方式進行塗布，並在通常8嗔之溫度下加 熱5秒〜1小時左右使其硬化。再者，就塗裝方法而言’在上 述方法之中，係以嘴射塗裝及輕塗抹機塗裝為適宜。 塗膜形成方法 本㈣之塗_成方法的魏切：在金屬板上之單面 开利用特徵為不含含絡_成分的無鉻底漆塗料來 形成底漆塗膜；在底漆塗膜之至少其 上述本發明之财污染塗料組成物所構成之I塗塗=成利用 換句話說，本發明之塗膜形成方法的特徵在 述步驟： 2屬板上之單面或兩面上，藉由無鉻底漆塗料所構 成之底漆料來形成紐塗朗步驟；及 43 201217468 在前述所形成之底漆塗膜之至少一者上，利用上述本 發明之耐污染塗料組成物來形成表塗塗膜的步驟。 又，本發明亦提供包含上述塗膜形成方法之各步驟的 塗裝金屬板製造方法，及利用上述塗膜形成方法或塗裝金 屬板製造方法所獲得之塗裝金屬板。 本發明之塗膜形成方法可使用於預塗塗裝亦可使用於 成品塗裝。適宜的使用例係可列舉如對前述之室外基材（例 如建造物、展示物、柵攔、器具、機械等）之塗裝。 舊本發明之塗膜形成方法中屬被塗物之金屬板而言， 係可列舉如：冷延鋼板、熔融鍍鋅鋼板、電鍍鋅鋼板、合 金鍍鋅鋼板(鐵-鋅、鋁-鋅、鎳-鋅等合金鍍鋅鋼板）、鋁板、 不鏽鋼板、銅板、鍍銅鋼板、鍍錫鋼板等。 在塗裝於金屬類時，屬被塗裝材之金屬表面若未受油 等污染物質所污染，雖亦可直接塗裝底漆，但為了改善與 塗膜間之附著性、耐蝕性，期望實施公知的金屬表面處理。 就該等公知的表面處理方法而言，係可列舉如磷酸鹽系表 面處理、鉻酸鹽系表面處理、锆系表面處理等。 本發明中，作為在金屬板上形成底漆塗膜之底漆，從 環境保護的觀點出發，使用以不含有含鉻防鏽成分為特徵 之無鉻底漆塗料。上述底漆若為無鉻底漆塗料即可，可適 宜地使用在著色彩色鋼板塗裝領域、産業用機械塗裝領 域、金屬零件塗裝領域等中所使用之公知的底漆。 無鉻底漆塗料係可依被塗裝材的種類、金屬表面處理 的種類來適宜地選擇，特別是以環氧系、聚酯系底漆塗料 44 201217468 及其等之改質底漆塗料為佳；而在特別要求加讀的情況 下係以a s曰系底漆塗料為佳。就形成底漆塗膜之具體的 手段而言，係可例示如塗裝底漆塗料，並於其後視需要進 行加熱使其硬化的手段。此時，底漆塗料係可藉由概塗裝、 噴射塗裝等公知的塗裝方法，以使底漆塗膜厚度呈 1〜30μηι、較宜為呈2〜2〇μηι的方式進行塗裝通常，以環境 氣體溫度之溫度加熱使其硬化。進行預塗塗裝 時’係以在料料最《度^⑽〜2贼之條件下加熱15 秒~120秒使其硬化為佳。 底漆塗膜之層構造係無特別限定者，例如，可為一層， 亦可在第1底漆塗膜上形成第2底漆塗膜（中塗塗膜）而形成 兩層底漆塗膜為兩層時，亦可使兩層的底漆塗膜具備不 同機能，如使第丄底漆塗膜具備防钮機能，而使第2底漆塗 膜（中塗塗膜）具備加工性、财剝馨性能等。 接著，在本發明之塗膜形成方法中，於上述金屬板上 之單面或兩面上所形成之底漆塗膜的至少一者上，形成利 用本發明之耐污染塗料組成物的表塗塗膜。即，表塗塗膜 係重疊形成於所形成之底漆塗臈的至少單面上。此處，「底 漆塗膜之至J/ -者上」係指，在金屬板上之片面上形成底 漆塗膜時在該單面上所形成之底漆塗膜上；在金屬板上之 兩面上A成底漆塗膜時，係指在該面上所形成之底漆塗膜 之中在金屬板上之單面上所形成之底漆塗膜之上，或在該 兩面上所形成之底漆塗膜之上。 就形成表塗塗膜之具體的手段而言，係可例示如：塗 45 201217468 裝本發明之耐污染塗料組成物，其後視需要進行加熱使其 硬化之手段。就塗裝方法而言，簾式塗裝、魅抹機塗裝、、 浸潰塗裝、噴射塗裝等。膜厚—般係在乾燥後之塗膜厚呈 5〜50μιη，宜為8〜25μηι之範圍内進行塗裝。 干 將本發明之塗料組絲進行預塗塗裂時，纟塗裝方法 雖無限制，但從預塗鋼板塗裝之經濟性觀點看來，係 式塗裝、輥塗抹機塗裝為佳。在適用輥塗抹機塗農時，從 實用性的觀點看來’係以利用雙觀之底送料方式（即H 然反向(論ralreve㈣塗裝、自然(natural)塗裝)為佳。I 使塗面之均勻性達到最佳之觀點看來，亦可進行利用攸 頂送料或底送料方式。 *之 本發明之塗料組成物所構成之表塗塗暝的硬化條件 般為素材到達最高溫度120〜26(TC，15秒〜30分鐘产士 及右。在轎 由線圈塗布等進行塗裝之預塗塗裝領域中，通常是在素才才 達最高溫度160〜260°C，焙燒時間15〜90秒之範圍内進行 【實施例】 以下利用製造例、實施例來較具體地說明本發明。本 發明並非受限於下述實施例者。再者’以下「份」及「S 40 201217468 Coating additives such as defoamers and surface conditioners; and solvents and the like which have hitherto been used in coatings. The solvent is preferably a solvent having good solubility in each of the components (C) and (D). By using such a solvent, the components (C) and (D) can be dispersed without causing coarsening, and a coating film having particularly excellent stain resistance can be formed. The surfactant and the boric acid-containing compound which exhibits the above-mentioned properties have a function of promoting the hydrolysis of the organic citrate and/or its condensate component (C). When the water-removing accelerator, such as an acidic surfactant and a boric acid-containing compound, is used together, the pot life of the coating composition of the present invention is shortened, but it can be used from the viewpoint of improving stain resistance. Examples of the surfactant which exhibits acidity include ester salts such as polyoxyethylene phosphate and alkyl phosphate; and, for example, sodium lauryl sulfonate and dodecyl phenyl sulphate; a naphthyl salt of a salt or a naphthyl salt such as a salt or a diphenyl sulfonate; for example, a sulphuric acid vinegar salt such as a ruthenium or a benzoyl sulfonium hydride; The bismuth succinate or the like __$ may be, for example, a succinct compound such as a triterpenoid, a triethyl citrate or a tributyl borate, such as an alkyl group; The blending amount of the water-splitting accelerators is 30% by mass or less, particularly 〇5 to 2, based on the total amount of the (VIII) component and the (Β) component with respect to Yu, +·/Λ, and the mass. 〇 “菫% is better. „#L 质/°' is more specifically 1~1〇 as the above-mentioned body pigment stone, mica powder, 钡 oxygen, etc. The system can be exemplified by the following: (1) The composition of the (A) 41 201217468 component and the component (B) is 0.1 to 20% by mass, particularly 0.5 to 15 by mass. %, more preferably 1 to 10% by mass. Further, in the coating composition of the present invention, a matting agent (E) may be used for the purpose of matting the obtained coating film or for adjusting the gloss of the finished product such as semi-gloss. The matting agent (E) is used for reducing the gloss of the obtained coating film, and may be any of an organic matting agent and an inorganic matting agent, and these may be used alone or in combination of two or more. The coating composition of the present invention can form a coating film which is particularly excellent in stain resistance and corrosion resistance in a coating film having a reduced appearance such as matt or semi-gloss. The organic matting agent is, for example, an organic resin fine particle which is not melted at all by baking at the time of formation of a coating film. The organic resin fine particles usually have an average particle diameter of from 3 to 80 μm, preferably from 5 to 60 μm, and are suitable from the viewpoints of coating appearance and coating workability. Examples of the organic matting agent include a fluororesin such as polyvinylidene fluoride and polytetrafluoroethylene, a polyamine, an acrylic resin, a polyamino phthalic acid, a resin, a sulphuric acid resin, and a polysiloxane. Polyacrylamide such as propylene, nylon 11 and nylon 12. Examples of the inorganic matting agent include cerium oxide, mica, alumina, talc, clay, calcium carbonate, barium sulfate, and the like. The above-mentioned matting agents may be used singly or in combination of two or more. The blending amount of the matting agent (Ε) is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 20% by mass based on the total of the above (Α) component and the (Β) component. The antifouling coating composition of the present invention can be produced by uniformly mixing the above (Α) to (D) components and optionally other components as described above. Preferably, the ingredients of 2012 201268 are mixed. The paste-preserving paste and the remaining paint composition of the present invention can be made into a liquid-based paint, and it is preferable to form a two-liquid type paint. In the method of coating the composition of the pollution-resistant coating of the present invention, the mr method can be listed: (4) using the organic solvent to adjust the viscosity of the coating composition to the desired viscosity, and then using the air. Spraying, electrostatic air jetting, roll coating machine, flow coating film, (4) machine in hot dip form, bristles, coating bar, etc., so that the film thickness of the coating film after drying is generally 05 to 300 μπ1, and coating is preferably carried out. And it is hardened by heating at a temperature of usually 8 Torr for about 5 seconds to about 1 hour. Further, in terms of the coating method, it is preferable to apply the nozzle coating and the light applicator in the above methods. Coating film forming method The coating method of the present invention (4): The single-sided opening on the metal plate is characterized by the absence of a chrome-free primer coating containing a ketone-containing component to form a primer coating film; in the primer coating film At least one of the above-described coating materials of the present invention is coated with a coating method. In other words, the coating film forming method of the present invention is characterized by the steps described in the following steps: 2 on one side or both sides of the board Forming a Newcoating step from a primer material composed of a chrome-free primer coating; and 43 201217468 forming a watch using the above-described pollution-resistant coating composition of the present invention on at least one of the primer coating films formed as described above The step of applying a film. Further, the present invention provides a method for producing a coated metal sheet comprising the steps of the method for forming a coating film, and a coated metal sheet obtained by the method for forming a coating film or the method for producing a metal sheet. The coating film forming method of the present invention can be used for precoating or for finished coating. Suitable use examples include the coating of the aforementioned outdoor substrates (e.g., structures, displays, barriers, utensils, machinery, etc.). In the method for forming a coating film of the present invention, the metal sheet to be coated may be, for example, a cold-rolled steel sheet, a hot-dip galvanized steel sheet, an electrogalvanized steel sheet, or an alloy galvanized steel sheet (iron-zinc, aluminum-zinc, Nickel-zinc alloy galvanized steel sheet), aluminum plate, stainless steel plate, copper plate, copper plated steel plate, tin plated steel plate, and the like. When it is applied to a metal, the metal surface of the coated material may be directly coated with a primer if it is not contaminated with a pollutant such as oil. However, in order to improve the adhesion to the coating film and corrosion resistance, it is desirable. A known metal surface treatment is carried out. Examples of such known surface treatment methods include a phosphate-based surface treatment, a chromate-based surface treatment, and a zirconium-based surface treatment. In the present invention, as a primer for forming a primer coating film on a metal plate, a chromium-free primer coating material which does not contain a chromium-containing rust-preventing component is used from the viewpoint of environmental protection. When the primer is a chrome-free primer coating material, a known primer used in the field of colored color steel sheet coating, industrial mechanical coating, and metal parts coating can be suitably used. The chrome-free primer coating can be appropriately selected depending on the type of the coated material and the type of the metal surface treatment, in particular, the epoxy-based, polyester-based primer coating 44 201217468 and the like. It is better to use as-based primer paint in case of special reading. As a specific means for forming the primer coating film, for example, a primer coating paint can be exemplified, and a means for heating and hardening as needed thereafter can be exemplified. In this case, the primer coating can be applied by a known coating method such as general coating or spray coating so that the thickness of the primer coating film is 1 to 30 μm, preferably 2 to 2 μm. Usually, it is hardened by heating at a temperature of the ambient gas temperature. When pre-coating is applied, it is preferred to heat it for 15 seconds to 120 seconds under the condition of the most "10" to 2 thieves. The layer structure of the primer coating film is not particularly limited. For example, it may be one layer, or a second primer coating film (middle coating film) may be formed on the first primer coating film to form a two-layer primer coating film. In the case of two layers, the two layers of the primer coating film can also have different functions, such as the second primer coating film (the intermediate coating film) having the processing function and the financial stripping. Sweet performance and so on. Next, in the method for forming a coating film of the present invention, at least one of the primer coating films formed on one or both sides of the metal sheet is formed by surface coating using the composition of the pollution-resistant coating of the present invention. membrane. That is, the top coat film is formed on at least one side of the formed primer coat. Here, the "primer coating film to J/-on" means a primer coating film formed on the one surface when a primer coating film is formed on a sheet surface of a metal plate; on a metal plate When A is a primer coating film on both sides, it means that the primer coating film formed on the surface is formed on the primer coating film formed on one side of the metal plate, or on both sides Formed on the primer coating film. As a specific means for forming the top coat film, for example, the coating composition of the present invention can be exemplified by the coating of the coating composition of the present invention, which is followed by heating and hardening. In terms of the coating method, the curtain coating, the glaze coating, the dipping coating, the spray coating, and the like. The film thickness is generally coated in a range of 5 to 50 μm, preferably 8 to 25 μm, after drying. Drying When the coating composition yarn of the present invention is pre-coated and coated, the enamel coating method is not limited, but from the viewpoint of economicality of pre-coated steel sheet coating, it is preferred to apply a system coating or a roll coater. When applying the roller applicator to the farm, from the point of view of practicality, it is preferable to use the double bottom feeding method (that is, H is reversed (on ralreve (four) coating, natural coating). In view of the fact that the uniformity of the coated surface is optimal, it is also possible to use the dome feeding or the bottom feeding method. * The coating composition of the coating composition of the present invention has a hardening condition of the surface coating, and the material reaches the maximum temperature of 120. ~26 (TC, 15 seconds ~ 30 minutes, the birth and the right. In the pre-coating field where the car is coated by coil coating, etc., usually in the prime temperature up to 160~260 ° C, roasting time 15 [Embodiment] The present invention will be specifically described below using the production examples and examples. The present invention is not limited to the following embodiments.

/〇 J 任一者皆是利用質量基準者。 含羥基聚酯樹脂(A1)之製造 製造例1 在具備溫度計、攪拌機、加熱裝置及精餾塔之繞瓶内 裝入下述原料： 1，2-環己院二羧酸酐 150.9份(0.98莫耳） 201217468 新戊二醇 38_9份(0.37莫耳） 丁基乙基丙烷二醇 9.6份(0.06莫耳） 三(羥甲）丙烷 77.8份(0_57莫耳） 椰子油脂肪酸 44.1份(0.21莫耳） 二丁基錫氧化物(觸媒） 〇.〇3份 接著，一邊攪拌内容物一邊升溫至160°C，花3小時從 160°C緩慢升溫至23(TC，在230°C下繼續反應30分鐘後，將 精餾塔以水分離器取代，為了促進副生之冷凝水的去除， 相對於總添加量，加入5%的二甲苯在230°C下進一步進行 反應，在酸價呈4mgKOH/g時停止加熱，加入SWAZOL 1500(烴系溶劑）稀釋，獲得固體成分65%之含羥基聚酯樹脂 (A1-1)溶液。 所獲得之樹脂係具有數平均分子量15000、羥值 75mgKOH/g、油長14.7%，及磁價5>。 製造例2〜3 以下述表1所示之調配，與製造例1同樣地進行，獲得 固體成分65%之各含羥基聚酯樹脂（A1 -2)〜(A1 -3)的溶液。 表1之各成分的組成比為莫耳比。 將各樹脂之數平均分子量、經值、油長及鐵價一併表 示於表1。 【表1】 製造例No. 1 2 3 含羥基聚酯樹脂(A1-X) 1 2 3 1,2-環己烷二羧酸酐 0.98 0.4 1，4-環己烷二羧酸 0.672 對苯二曱酸 0.3 47 201217468/〇 J Anyone who uses quality benchmarks. Production and manufacturing example 1 of a hydroxyl group-containing polyester resin (A1) The following raw materials were placed in a vial equipped with a thermometer, a stirrer, a heating device, and a rectification column: 1,2-cyclohexyl dicarboxylic anhydride 150.9 parts (0.98 mol) Ear) 201217468 Neopentyl glycol 38_9 parts (0.37 mol) butyl ethyl propane diol 9.6 parts (0.06 mol) Tris(hydroxymethyl)propane 77.8 parts (0_57 mol) Coconut oil fatty acid 44.1 parts (0.21 mol) Dibutyltin oxide (catalyst) 〇.〇3 parts Next, while stirring the contents, the temperature is raised to 160 ° C, and the temperature is slowly raised from 160 ° C to 23 (TC, 3 hours, and the reaction is continued at 230 ° C for 30 minutes). Thereafter, the rectification column was replaced with a water separator. In order to promote the removal of the condensed water of the by-producer, 5% of xylene was further added to the reaction at 230 ° C with respect to the total addition amount, and the acid value was 4 mgKOH/g. When the heating was stopped, it was diluted with SWAZOL 1500 (hydrocarbon solvent) to obtain a solution of a hydroxyl group-containing polyester resin (A1-1) having a solid content of 65%. The obtained resin had a number average molecular weight of 15,000, a hydroxyl value of 75 mgKOH/g, and an oil. 14.7%, and magnetic price 5> Manufacturing Examples 2 to 3 are prepared as shown in Table 1 below, and In the same manner as in the first example, a solution of each of the hydroxyl group-containing polyester resins (A1 - 2) to (A1 - 3) having a solid content of 65% was obtained. The composition ratio of each component in Table 1 was a molar ratio. The number average molecular weight, the menstrual value, the oil length and the iron price are shown in Table 1. [Table 1] Production Example No. 1 2 3 Hydroxy-containing polyester resin (A1-X) 1 2 3 1,2-cyclohexane Dicarboxylic anhydride 0.98 0.4 1,4-cyclohexanedicarboxylic acid 0.672 terephthalic acid 0.3 47 201217468

含有氟原子的非水性分散液型樹脂成分(D)之製造 分散穩定劑（Dla)之製造 製造例4 在具備攪拌裝置、溫度計、冷卻管、氧氣導入口之四 口燒瓶中，裝進Lumiflon LF800(旭硝子（股）製氟樹脂（氟乙 烯/乙烯基醚交互共聚合物），羥值38mgK〇H/g，酸價 2mgKOH/g，數平均分子量8100，樹脂質量固體成分 60%)1834份，曱基丙烯酸環氧丙酯：15.4份，第三丁基磷 苯二酚（聚合抑制劑）0.55份，二曱基乙醇胺（反應觸媒）1.1份 後，攪拌内容物並在氧氣環境下升溫至120°C，進行反應 (Lumiflon LF800的羧基與曱基丙烯酸環氧丙酯的環氧丙基 之反應）。固體成分酸價呈0.4mgKOH/g以下時停止加熱使 反應終止’獲得分散穩定劑(Dla-Ι)(羥值38mgKOH/g，數平 均分子量8100，樹脂質量固體成分60%)。 製造例5 在具備授拌裝置、溫度計、冷卻管、氧氣導入口之的四 口燒瓶中’裝入礦油精45.4份，在氮氣環境下升溫至i2〇°C， 花3小時將由2-全氟辛基乙基甲基丙烯酸酯15份、丙烯酸異 201217468 莰酯30份、2-乙基己基丙烯酸酯ι〇份、2-乙基己基曱基丙烯 酸酯37份、2-甲基丙烯酸羥乙酯5份、丙烯酸3份及2,2，-偶氮 雙異丁睛（聚合起始劑）7份所構成之混合物滴下。接者，在1 20°C下一邊將氣氣通氣熟成30分鐘後’進一步，花1小時將 礦油精8.3份及2,2，-偶氮雙異丁腈0.5份之混合物滴下。其 後，再進一步熟成2小時後，在氧氣環境下投入第三基碟 苯二酚(聚合抑制劑）〇.〇1份、甲基丙烯酸環氧丙酯2.17份及 二甲基乙醇胺(反應觸媒)〇.〇9份進行反應。至固體成分醆價 呈16.0mgKOH/g以下時停止加熱，終結反應，獲得分散穩 定劑(Dla-2)(經值22mgKOH/g，數平均分子量_〇，樹脂質 量固體成分60%)。 分散穩定劑(〇2a)之製迤 製造例6 在具備授拌裝置、溫度計、冷卻管、氮/氧氣導入口之四 口燒瓶中，裝入礦油精45.4份，在氮氣環境下升溫至12〇亡 花3小時將由丙烯酸異获醋30份、2_乙基己基丙烯酸醋1〇 份、2-乙基己基曱基丙烯酸醋52份、2_甲基丙烯酸經乙雖5 份、丙烯酸3伤及2,2 -偶氮雙異丁腈（聚合起始劑)7份所構成 之混合物滴下。接著，在120°C下一邊將氮氣通氣一邊使其 熟成30分鐘後，進一步，花1小時將礦油精8·3份及2,2，_偶氮 雙異丁腈0.5份之混合物滴下。其後，進—步熟成2小時後， 在氧氣環境下投入第三丁基磷苯二酚（聚合抑制劑）〇. 〇 i 份、甲基丙稀酸私氧丙自曰2.17份及二甲基乙醇胺（反應觸 媒）0.09份進行反應。當固體成分酸價呈l6.〇mgKOH/g以下 49 201217468 時停止加熱’終結反應，獲得分散穩定劑（D2a-1)(羥值 22mgKOH/g、數平均分子量6〇〇〇、樹脂質量固體成分60%)。 非水性分散液型樹脂(D丨）之製造 製造例7 在具備攪拌裴置、溫度計、冷卻管、氮氣導入口之四口 燒瓶中’裝入分散穩定劑(Dla-l)41.7份、礦油精56份、庚炫 46份’在氮氣環境下升溫至i〇〇°c，花3小時將由分散穩定劑 (Dla-l)125份、甲基丙烯酸曱酯4〇份、甲基丙烯酸酯29份、 2-丙烯酸羥乙酯25份、甲基丙烯酸環氧丙酯5份、曱基丙烯 酸1份及2,2^偶氮雙異丁腈1份所構成之混合物滴下。接著， 在100°C下一邊將氮氣通氣，一邊使其熟成30分鐘後，進一 步，花1小時將礦油精30份及2,2'-偶氮雙異丁腈〇·5份之混合 物滴下。其後，藉由使其進一步熟成1小時，獲得非水性分 散液塑樹脂(D1-1)(質量固體成分濃度5〇%)。將所獲得之非 水性分散液型樹脂(D1-1)的特徵值合併表示於表2。 製造例8〜17 以卜迷衣2所示之 ’ 1 J地進行， 非水性分散液型樹脂(D1-2)〜(D1-10)及(〇2 丁’费 )。將所擔; 各非水性分散液型樹脂（D1 -2)〜(D1 -10)及（叱 4 合併表示於表2。 ）之特植 【表2】Production Example 4 of Production of Dispersion Stabilizer (Dla) of Non-Aqueous Dispersion-Type Resin Component (D) Containing Fluorine Atom In a four-necked flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen introduction port, Lumiflon LF800 was placed. (Asahi Glass Co., Ltd. made fluororesin (fluoroethylene/vinyl ether cross-copolymer), hydroxyl value 38mgK〇H/g, acid value 2mgKOH/g, number average molecular weight 8100, resin mass solid content 60%) 1834 parts, Glycidyl methacrylate: 15.4 parts, 0.55 parts of t-butylphosphoric phenol (polymerization inhibitor), 1.1 parts of decylethanolamine (reaction catalyst), and then the contents were stirred and heated to an oxygen atmosphere. The reaction was carried out at 120 ° C (reaction of the carboxyl group of Lumiflon LF800 with the epoxypropyl group of glycidyl methacrylate). When the acid value of the solid content was 0.4 mgKOH/g or less, the heating was stopped to terminate the reaction. A dispersion stabilizer (Dla-ruthenium) (having a hydroxyl value of 38 mgKOH/g, a number average molecular weight of 8,100, and a resin mass solid content of 60%) was obtained. Production Example 5 45.4 parts of mineral spirits were placed in a four-necked flask equipped with a mixing device, a thermometer, a cooling tube, and an oxygen introduction port, and the temperature was raised to i2 〇 ° C in a nitrogen atmosphere, and the total temperature was 2 hours. 15 parts of fluorooctylethyl methacrylate, 30 parts of acrylate iso 201217468 decyl ester, 2-ethylhexyl acrylate ι, 37 parts of 2-ethylhexyl decyl acrylate, 2-hydroxy methacrylate A mixture of 5 parts of an ester, 3 parts of acrylic acid, and 7 parts of 2,2,-azobisisobutylene (polymerization initiator) was dropped. Then, the mixture was ventilated at 30 ° C for 30 minutes, and further, a mixture of 8.3 parts of mineral spirits and 0.5 parts of 2,2,-azobisisobutyronitrile was dropped for 1 hour. Thereafter, after further aging for 2 hours, a third base dish of benzenediol (polymerization inhibitor) 〇.〇1, 2.17 parts of glycidyl methacrylate and dimethylethanolamine (reaction touch) were placed in an oxygen atmosphere. Media) 〇. 〇 9 parts for the reaction. When the solid content valence was 16.0 mgKOH/g or less, the heating was stopped, and the reaction was terminated to obtain a dispersion stabilizer (Dla-2) (having a value of 22 mgKOH/g, a number average molecular weight 〇, a resin content solid content of 60%). Preparation Example 6 of dispersion stabilizer (〇2a) In a four-necked flask equipped with a mixing device, a thermometer, a cooling tube, and a nitrogen/oxygen inlet, 45.4 parts of mineral oil was charged, and the temperature was raised to 12 in a nitrogen atmosphere. 3 hours of sucrose will be 30 parts of acrylic vinegar, 1 part of 2-ethylhexyl acrylate, 52 parts of 2-ethylhexyl methacrylate, 2 parts of 2-methacrylic acid, 5 parts of acrylic acid, 3 And a mixture of 2 parts of 2,2-azobisisobutyronitrile (polymerization initiator) was dropped. Subsequently, the mixture was sterilized by aeration of nitrogen gas at 120 ° C for 30 minutes, and further, a mixture of 8.3 parts of mineral spirits and 0.5 part of 2,2,-azobisisobutyronitrile was dropped over 1 hour. Thereafter, after 2 hours of ripening, the third butyl hydroquinone (polymerization inhibitor) was added in an oxygen atmosphere. 〇i part, methyl propylene dihydrogen propylene self-purifying 2.17 parts and dimethyl The reaction was carried out by using 0.09 parts of basal ethanolamine (reaction catalyst). When the acid value of the solid component is below 16.6 KOHKOH/g 49 201217468, the heating is terminated, and the dispersion stabilizer (D2a-1) is obtained (hydroxyl value 22 mgKOH/g, number average molecular weight 6 〇〇〇, resin mass solid content). 60%). Production and Production Example 7 of Non-Aqueous Dispersion Type Resin (D丨) In a four-necked flask equipped with a stirring apparatus, a thermometer, a cooling tube, and a nitrogen inlet, 41.7 parts of a dispersion stabilizer (Dla-1) was placed, and mineral oil was added. Fine 56 parts, Gengxuan 46 parts 'heated to i〇〇°c under nitrogen atmosphere, and spent 3 hours will consist of 125 parts of dispersion stabilizer (Dla-1), 4 parts of decyl methacrylate, methacrylate 29 A mixture of 25 parts of 2-hydroxyethyl acrylate, 5 parts of glycidyl methacrylate, 1 part of methacrylic acid and 1 part of 2,2 azobisisobutyronitrile was dropped. Next, while ventilating the nitrogen gas at 100 ° C for 30 minutes, the mixture of 30 parts of mineral spirits and 5 parts of 2,2'-azobisisobutyronitrile was added for 1 hour. . Thereafter, by further aging for 1 hour, a non-aqueous dispersion liquid resin (D1-1) (mass solid content concentration: 5% by mass) was obtained. The characteristic values of the obtained non-aqueous dispersion type resin (D1-1) are shown in Table 2. Production Examples 8 to 17 were carried out in the manner of '1 J shown in the blister 2, and non-aqueous dispersion type resins (D1-2) to (D1-10) and (〇2 Ding' fee). The specific non-aqueous dispersion type resin (D1 - 2) ~ (D1 - 10) and (叱 4 are shown in Table 2.) [Table 2]

50 201217468 穩定劑 Dla-2 100 (固體成分) D2a-1 100 曱基丙烯酸甲酯 40 40 53 27 69 11 30 30 45 24 56 甲基丙烯酸a旨 29 29 6 52 58 24 24 30 17.4 14 2-丙烯酸羥乙酯 25 25 35 15 25 25 25 25 25 15 28 皁體 曱基丙烯酸環氧丙酯 5 5 5 5 5 5 5 5 3 5.6 甲基丙烯酸 1 1 一 1 1 1 1 1 0.6 1.4 全氟甲基甲基丙烯酸I旨 15 15 起始劑 2之-偶気雙異丁腈 1 1 1 1 1 1 1 1 0.6 1.4 質量固體成分濃度(％) 50 50 5〇 50 50 50 50 50 50 50 50 數平均分子量 無法測定 ιυ萬 無法測定 平均粒徑〇111〇 180 180 100 260 180 180 190 2U0 180 90 280 特徵值 玻璃轉移溫度 (°C)(粒子成分） 18 18 18 18 42 -2 11 11 19 18 18 經值(mgKOH/g) (粒子成分） 120 120 166 73 120 120 120 120 120 120 120 耐污染塗料組成物之製造及性能試驗 實施例1〜22及比較例1~6 以表示於後述表3及表4之組成來進行塗料化，獲得各 耐污染塗料組成物No.l〜28。耐污染塗料組成物No.23〜28 係比較例用之塗料組成物。 在經施予化成處理之厚度0·35mm的熔融55%銘-鋅鑛 鋼板(Galvalume鋼板)的表面及背面’個別將KP COLOR 8620 底漆(關西塗料(股)製、預塗鋼板用聚酯系底漆)以乾燥膜厚呈 5μιη之方式塗裝，加熱以使素材到達最高溫度為220°C並進行 焙燒40秒，獲得底漆塗裝鋼板。在該底漆塗裝鋼板表面上 將進行如上所述所獲得之各耐污染塗料組成物利用桿塗 布，以乾燥膜厚呈約15μιη之方式塗裝，加熱使素材到達最 高溫度呈23 0°C並焙燒5 〇秒而獲得各塗裝鋼板。對所獲得之 各塗裝鋼板進行了下述性能試驗。 將試驗結果合併表示於表3及表4。又，表3及表4中各 成分的量為固體成分質量。再者，在耐污染塗料組成物之 51 201217468 塗料化時，進行白色顏料二氧化鈦之分散。又，將環己酮 /SWAZOL 1500(丸善石油（股）製、芳香族石油系高沸點溶 劑）=60/40(質量比）之混合溶劑使用於塗料組成物的黏度調 整等目的。在進行塗裝時，將塗料組成物黏度以福特杯#4 調整為約100秒(25°C)。 【表3】50 201217468 Stabilizer Dla-2 100 (solid content) D2a-1 100 Methyl methacrylate 40 40 53 27 69 11 30 30 45 24 56 Methacrylic acid a 29 29 6 52 58 24 24 30 17.4 14 2-Acrylic Hydroxyethyl 25 25 35 15 25 25 25 25 25 15 28 Soap body glycidyl methacrylate 5 5 5 5 5 5 5 5 3 5.6 Methacrylic acid 1 1 -1 1 1 1 1 0.6 1.4 Perfluoromethyl Methacrylic acid I 15 15 Starting agent 2 - Even oxime double isobutyronitrile 1 1 1 1 1 1 1 1 0.6 1.4 Mass solid content concentration (%) 50 50 5〇50 50 50 50 50 50 50 50 Number average Molecular weight cannot be determined ιυ万 Can not measure average particle size 〇111〇180 180 100 260 180 180 190 2U0 180 90 280 Characteristic value Glass transition temperature (°C) (particle composition) 18 18 18 18 42 -2 11 11 19 18 18 Value (mgKOH/g) (Particle composition) 120 120 166 73 120 120 120 120 120 120 120 Manufacturing and performance test of the stain-resistant coating composition Examples 1 to 22 and Comparative Examples 1 to 6 are shown in Table 3 and Tables to be described later. 4 composition to carry out coating, to obtain each pollution-resistant coating composition No. l~28 . The stain-resistant coating composition No. 23 to 28 is a coating composition for a comparative example. KP COLOR 8620 primer (made by Kansai Paint Co., Ltd., polyester for precoated steel sheet) on the surface and back surface of molten 55% Ming-zinc ore steel sheet (Galvalume steel sheet) with a thickness of 0·35 mm applied by chemical conversion treatment The primer was applied in such a manner that the dry film thickness was 5 μm, and heating was carried out so that the material reached a maximum temperature of 220 ° C and baked for 40 seconds to obtain a primer-coated steel sheet. Each of the pollution-resistant coating compositions obtained as described above was coated on the surface of the primer-coated steel sheet by a rod, and the dried film thickness was applied at a thickness of about 15 μm, and heated to bring the material to a maximum temperature of 23 ° C. Each of the coated steel sheets was obtained by firing for 5 sec. The following performance tests were performed on each of the obtained coated steel sheets. The test results are combined and shown in Tables 3 and 4. Further, the amounts of the respective components in Tables 3 and 4 are the masses of the solid components. Further, when the coating of the pollution-resistant coating composition 51 201217468 is applied, the dispersion of the white pigment titanium dioxide is carried out. Further, a mixed solvent of cyclohexanone/SWAZOL 1500 (available from Maruzen Oil Co., Ltd., aromatic petroleum-based high-boiling solvent) = 60/40 (mass ratio) is used for the purpose of adjusting the viscosity of the coating composition. When coating, the viscosity of the coating composition was adjusted to about 100 seconds (25 ° C) with Ford Cup #4. 【table 3】

實施例 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 而ί污染塗料組成物No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 A成分 含羥基聚酯樹脂（A1-1) 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 含羥基聚酯樹脂（A1-2) 含羥基聚酯樹脂（A1-3) 含羥基聚酯樹脂（註1) B成分 U-VAN20SE-60 (註2) 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 C成分 MS56S (06) 5 5 5 5 5 5 5 5 5 5 5 1 20 MS58B30 (註7) 5 X41-1805 (註8) 5 D成分 D1-1 20 20 20 20 20 D1-2 20 D1-3 20 DM 20 D1-5 20 D2-1 20 D1-6 20 D1-7 20 D1-8 20 D1-9 20 D1-10 20 E成分 塞各ί尹德161W (till) 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 二氧化鈦 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 性能 結果 60。光澤 33 34 31 35 30 37 38 30 40 31 36 32 30 38 31 财污染性 S S S S S A A A S A A A A A S 财雨痕污染性 A A A A S A A S S A A A A A A 加工性 A A A A A A A A A A A A A A A 綜合評價 S S S S S A A S S A A A A A S 【表4】Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 and ί contaminated coating composition No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 A-component hydroxyl-containing polyester resin (A1- 1) 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 Hydroxy-containing polyester resin (A1-2) Hydroxy-containing polyester resin (A1-3) Hydroxy-containing polyester resin (Note 1) B-component U- VAN20SE-60 (Note 2) 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 C component MS56S (06) 5 5 5 5 5 5 5 5 5 5 5 1 20 MS58B30 (Note 7) 5 X41-1805 (Note 8) 5 D component D1-1 20 20 20 20 20 D1-2 20 D1-3 20 DM 20 D1-5 20 D2-1 20 D1-6 20 D1-7 20 D1-8 20 D1-9 20 D1 -10 20 E-component Seymour yin 161W (till) 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Titanium dioxide 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 Performance result 60. Luster 33 34 31 35 30 37 38 30 40 31 36 32 30 38 31 Contamination S S S S S A A A S A A A A A A A A A A A A S A A S S A A A A A A A Processability A A A A A A A A A A A A A A A A Comprehensive Evaluation S S S S S A A S S A A A A A S [Table 4]

S 纪施例 比較例 16 17 18 19 20 21 22 1 2 3 4 5 6 耐污染塗料組成物No. 16 17 18 19 20 21 22 23 24 25 26 27 28 A成分含羥基聚酯樹脂 (Al-1) 75 75 75 75 80 80 80 80 80 80 52 201217468S Formulation Comparative Example 16 17 18 19 20 21 22 1 2 3 4 5 6 Contaminant-Resistant Coating Composition No. 16 17 18 19 20 21 22 23 24 25 26 27 28 A-component hydroxyl-containing polyester resin (Al-1 ) 75 75 75 75 80 80 80 80 80 80 52 201217468

含羥基聚酯樹脂 (A1-2) 80 含羥基聚酯樹脂 (A1-3) 80 含經基聚酯樹脂 (註1) 75 U-VAN20SE40 m) 25 25 6 6 25 25 20 20 20 20 20 20 B成分 SUPER BECKAMINE (Ii3) J820-60 20 Cymel 303 (註4) 14 14 SUMIDURBL3175 («5) 5 MS56S ㈣ 5 5 5 5 5 5 5 25 5 5 5 5 C成分 MS58B30 (言主7) X41-1805 ㈣） D成分 Dl-1 5 30 20 20 20 20 20 20 20 40 DYNEONTF9205 (言主9) 20 Lumiflon LF800 (註 10) 10 E成分 塞洛伊德161W (»11) 3 3 3 3 3 20 3 3 3 3 3 3 其他 成分 Nacure 5225 (註 12) 1 1 FOAMATETK-1 (註 13) 0.2 二氧化鈦 80 80 80 80 80 80 80 80 80 80 80 80 80 60。光澤 41 29 33 34 32 76 13 31 40 42 26 29 38 性能 耐污染性 A S S S A A A A C A B B B 試驗 結果 财雨痕污染性 A S A A A A S B c B C C B 加工性 A A A A A A A C A A B A B 綜合評價 A S S S A A A C C B C C B 再者，表3及表4之(註1)~(註13)係如下所述。 (註1)含羥基聚酯樹脂：阿拉其德7018，商品名、荒川 化學工業（股）製，數平均分子量18000，羥值 6〜12mgKOH/g，酸價5mgKOH/g>，玻璃轉移溫度50°C (利用 DSC測定），酸成分為對酞酸、異酞酸及癸二酸的3成分含羥 基無油聚醋樹脂。 (註2)U-VAN20SE-60:三井化學（股）製，丁基醚化三聚 氰胺樹脂，重量平均分子量約4000。 (註3)SUPER BECKAMINE J820-60 :商品名「SUPER BECKAMINE J-820-60」，DIC(股)製，正丁基醚化三聚氰胺 樹脂溶液。 (註4)Cymel 303 :日本Cytece工業公司（股）製，低分子 53 201217468 量曱基化三聚氰胺樹脂。六八面體-(甲氧甲基）三聚氰胺之 含量為60重量％以上。 (註5)SUMIDUR BL3175: Sumitomo Bayer Urethane(股） 製，三（經甲）丙烧加成型六亞曱二異氰酸酯的曱基乙基酮肟 嵌段化合物。 (註6)MS56S :三菱化學（股）製，商品名「MKC矽酸鹽 MS56S」’屬四甲氧矽烷縮合物之甲基酯化矽酸鹽。 (註7)MS58B3〇:三菱化學（股）製，商品名「MKC矽酸 鹽MS58B30」，屬四矽氧烷縮合物之曱基/丁基混合酯化矽 酸鹽，曱基/丁基數的比率為70/30。 (註8)X-41-1805 :信越化學工業（股）公司製，商品名， 含疏烧基的三石夕氧烧縮合物，疏烧基之碳數為18以下，烧 氧基之碳數為6以下。 (註9)DYNEONTF9205 : HoechstJapan(股）公司製，商 品名，聚四氟乙稀的粉末，粒徑約5 μηι。 (註10)Lumiflon LF8〇0 :旭硝子（股）製，商品名，氟樹 脂（氟乙烯/乙烯基醚交互共聚合物），羥值38mgKOH/g，酸 價2mgKOH/g，數平均分子量81〇〇,樹脂質量固體成分6〇%。 (註11)塞洛伊德161W : GRACE GMBH公司製，商品 名，經有機處理之氧化矽微粉末，吸油量17〇111丨/1〇〇§。 (S主 12)Nacure5225 :美國 King Industries製，十二基苯 磺酸之2級胺中和物的異丙醇溶液。十二基苯磺酸/胺之中 和度約1·1(莫耳比）。有效成分約33重量％，其中，十二基 苯磺酸/胺（質量比）為約8/25。表2中的數値為十二基苯磺酸 54 201217468 之固體成分質量份。 (註l3)FOAMATETK-l :武田藥品工業（股）製之屬有機 錫溶液的硬化觸媒、嵌段化聚異氰酸酯化合物的解離觸媒。 表3及表4中的性能試驗係依照以下的方法及評價基準 來進行。 6〇°光澤：按照規定於JISK-5400 7.6(1990)之60度鏡面 光澤度’測定60度鏡面反射率。 室外曝曬試驗：將室外曝曬試驗試驗片（l〇〇x300mm) 以使塗膜面對北側的方式，安裝於簷緣經模型化的設置 台’在尼崎市神崎町關西塗料公司（股）屋頂上進行曝曬試 驗’將耐污染性及耐雨痕污染性（雨痕狀的污痕）以下述基準 進行評價。耐污染性係將曝曬前後的色差（ΔΕ)依據jIS Z8370 ’使用SUGA試驗機公司（股）製的多光源分光測色計 MSC-5N來進行測定。耐雨痕污染性係以目視進行判定。 耐污染性：從室外曝曬試驗前後之依據以下的基準 進行評價： S : ΔΕ小於2 ; A : ΔΕ為2以上且小於3 ; B : ΔΕ為3以上且小於5 ; C : ΔΕ為5以上。 而才雨痕污染性：將室外暴露試驗後的雨痕跡依據以下 的基準進行評價： S ·看不見雨痕跡； A :依稀可看出雨痕跡，但可用水浸透之紗布輕易地擦掉； 55 201217468 B :雨痕跡相當明顯，無法用水浸透之紗布完全地擦掉； C:雨痕跡濃厚殘留，幾乎無法無法用水浸透之紗布擦掉 加工性：在20°C之室内，使塗面在外側，將試驗板180 度折彎時，表示在折彎部分不再產生裂痕的T數。就T數而 言，係將在折彎部分内側沒有夾任何東西時進行180度折彎 的情況設為0T，夾住1枚與試驗板相同厚度的板折彎時設為 1T，2牧時設為2T，3牧時3T，4牧時4T、5牧5T、6牧時設 為6T。結果係依下述進行判定。 A : 4T彎曲加工中，幾乎看不出裂痕 B :在4T彎曲加工中雖可看出明顯裂痕，但在6T彎曲加工 中幾乎看不出裂痕 C :在6T彎曲加工中，可看出明顯裂痕 綜合評價： 耐污染塗料組成物中，被塗物之加工性、所獲得之塗 膜的耐污染性及耐雨痕污染性皆高是很重要的。因此，使 用以下的基準來進行綜合評價。 S :加工性、耐污染性及耐雨痕污染性之評價皆為S或A， 且至少1者為S ; A :加工性、耐污染性及耐雨痕污染性之評價皆為A;Hydroxy-containing polyester resin (A1-2) 80 Hydroxy-containing polyester resin (A1-3) 80 Permeable polyester resin (Note 1) 75 U-VAN20SE40 m) 25 25 6 6 25 25 20 20 20 20 20 20 B component SUPER BECKAMINE (Ii3) J820-60 20 Cymel 303 (Note 4) 14 14 SUMIDURBL3175 («5) 5 MS56S (4) 5 5 5 5 5 5 5 25 5 5 5 5 C component MS58B30 (word main 7) X41-1805 (4)) D component Dl-1 5 30 20 20 20 20 20 20 20 40 DYNEONTF9205 (speaker 9) 20 Lumiflon LF800 (Note 10) 10 E composition Seyloy 161W (»11) 3 3 3 3 3 20 3 3 3 3 3 3 Other ingredients Nacure 5225 (Note 12) 1 1 FOAMATETK-1 (Note 13) 0.2 Titanium dioxide 80 80 80 80 80 80 80 80 80 80 80 80 80 60. Gloss 41 29 33 34 32 76 13 31 40 42 26 29 38 Performance and pollution resistance ASSSAAAACABBB Test results Financial rain stains ASAAAASB c BCCB Processability AAAAAAACAABAB Comprehensive evaluation ASSSAAACCBCCB Again, Tables 3 and 4 (Note 1)~( Note 13) is as follows. (Note 1) Hydroxyl-containing polyester resin: Arachid 7018, trade name, manufactured by Arakawa Chemical Industry Co., Ltd., number average molecular weight 18000, hydroxyl value 6 to 12 mgKOH/g, acid value 5 mgKOH/g>, glass transition temperature 50 °C (measured by DSC), the acid component is a three-component hydroxyl-containing oil-free polyester resin for citric acid, isophthalic acid and sebacic acid. (Note 2) U-VAN20SE-60: manufactured by Mitsui Chemicals Co., Ltd., butyl etherified melamine resin, weight average molecular weight of about 4,000. (Note 3) SUPER BECKAMINE J820-60: trade name "SUPER BECKAMINE J-820-60", manufactured by DIC Co., Ltd., n-butyl etherified melamine resin solution. (Note 4) Cymel 303: Japan Cytece Industrial Co., Ltd., low molecular 53 201217468 thiolated melamine resin. The content of hexahedral-(methoxymethyl)melamine is 60% by weight or more. (Note 5) SUMIDUR BL3175: Sumitomo Bayer Urethane (manufactured by Sumitomo Bayer Urethane Co., Ltd.), a tris(A)-A-cylinder-added sulfhydryl ethyl ketone oxime block compound of hexamethylene diisocyanate. (Note 6) MS56S: manufactured by Mitsubishi Chemical Corporation, under the trade name "MKC citrate MS56S" is a methyl esterified decanoate of a tetramethoxy decane condensate. (Note 7) MS58B3〇: Mitsubishi Chemical Co., Ltd., trade name “MKC citrate MS58B30”, thiol/butyl mixed esterified decanoate of tetraoxane condensate, thiol/butyl number The ratio is 70/30. (Note 8) X-41-1805: manufactured by Shin-Etsu Chemical Co., Ltd., trade name, Sanshixi Oxygen Burn Condensate containing a sparingly-burning base, the carbon number of the subcooling base is 18 or less, and the carbon number of the alkoxy group It is 6 or less. (Note 9) DYNEONTF9205: manufactured by Hoechst Japan Co., Ltd., trade name, powder of polytetrafluoroethylene, particle size of about 5 μηι. (Note 10) Lumiflon LF8〇0: Asahi Glass Co., Ltd., trade name, fluororesin (fluoroethylene/vinyl ether cross-polymer), hydroxyl value 38 mgKOH/g, acid value 2 mgKOH/g, number average molecular weight 81〇 〇, the resin quality solid content is 6〇%. (Note 11) Seyloy 161W: manufactured by GRACE GMBH, trade name, organically treated cerium oxide micropowder, oil absorption of 17〇111丨/1〇〇§. (S. main 12) Nacure 5225: an isopropanol solution of a grade II amine neutralized product of dodecylbenzenesulfonic acid, manufactured by King Industries, USA. The degree of neutralization of dodecylbenzenesulfonic acid/amine is about 1.1 (mole ratio). The active ingredient was about 33% by weight, wherein the dodecylbenzenesulfonic acid/amine (mass ratio) was about 8/25. The number in Table 2 is the solid component mass fraction of dodecylbenzenesulfonic acid 54 201217468. (Note l3) FOAMATETK-l: A catalyzed catalyst of an organic tin solution and a dissociation catalyst of a blocked polyisocyanate compound manufactured by Takeda Pharmaceutical Co., Ltd. The performance tests in Tables 3 and 4 were carried out in accordance with the following methods and evaluation criteria. 6 〇 ° gloss: 60 degree specular reflectance was measured as specified in JISK-5400 7.6 (1990) 60 degree specular gloss. Outdoor exposure test: The outdoor exposure test piece (l〇〇x300mm) is placed on the roof of the Kansai Paint Co., Ltd. on the roof of the Kanazaki-machi, Kanazaki-cho, in a way that the coating film faces the north side. The exposure test was carried out. The contamination resistance and the rain stain resistance (rain mark-like stains) were evaluated on the basis of the following criteria. The stain resistance was measured by using a multi-source spectrophotometer MSC-5N manufactured by SUGA Test Instruments Co., Ltd. according to jIS Z8370' in accordance with JIS Z8370'. Rain stain resistance is determined by visual inspection. Pollution resistance: Evaluation was made from the following criteria before and after the outdoor exposure test: S: ΔΕ is less than 2; A: ΔΕ is 2 or more and less than 3; B: ΔΕ is 3 or more and less than 5; C: ΔΕ is 5 or more. Only rain stains: The rain marks after the outdoor exposure test are evaluated according to the following criteria: S · No rain marks are visible; A: Rain marks are faintly visible, but can be easily wiped off with water-soaked gauze; 201217468 B : The rain marks are quite obvious, and the gauze that cannot be soaked with water is completely wiped off; C: The rain marks are thick and residual, and it is almost impossible to wipe off the processability with water-soaked gauze: in the room at 20 ° C, the coated surface is on the outside, When the test plate is bent at 180 degrees, it indicates the number of Ts in which no cracks are generated in the bent portion. In the case of the T number, the case where the 180 degree bend is performed when there is nothing on the inside of the bent portion is set to 0T, and when one plate of the same thickness as the test plate is bent, it is set to 1T, 2 It is set to 2T, 3 to 3T, 3 to 4, 5 to 5, and 6 to 6T. The results were judged as follows. A : In the 4T bending process, almost no cracks are visible. B: Although cracks can be seen in the 4T bending process, cracks are hardly observed in the 6T bending process. C6 can be seen in the 6T bending process. Comprehensive evaluation: It is important that the composition of the stain-resistant coating is high in the processability of the coating, the stain resistance of the obtained coating film, and the stain resistance. Therefore, the following criteria are used for comprehensive evaluation. S: The evaluation of processability, pollution resistance and rain stain resistance is S or A, and at least one is S; A: the evaluation of processability, pollution resistance and rain stain resistance is A;

B :加工性、耐污染性及耐雨痕污染性之評價皆為S、A或B， 且至少一個為B C:加工性、耐污染性及耐雨痕污染性之評價中至少一者為C。 【圖式簡單說明3 (無） 56 201217468 【主要元件符號說明】 (無） 57B: The evaluation of processability, stain resistance, and rain stain resistance is S, A, or B, and at least one of B C: at least one of the evaluations of workability, stain resistance, and rain stain resistance is C. [Simple description of the diagram 3 (none) 56 201217468 [Description of main component symbols] (none) 57

Claims (1)

201217468 七、申請專利範圍： 1· 一種耐污染塗料組成物，其含有： (A)聚酯樹脂成分，其含有5〇至1〇〇質量％之數平均分子 量為5000至30000、羥值為^i〇〇mgK〇H/g之含羥基聚 酯樹脂(A1)作為固體成分，且該含羥基聚酯樹脂(Al)係 藉由 (al)多元酸成分，及 〇2)醇成分 之反應所獲得之聚酯樹脂成分； (B) 二聚氰胺樹脂成分’其含有至質量％之丁基醚 化三聚氰胺樹脂(B1)作為固體成分； (C) 由下述通式所表示之有機矽酸鹽及/或其縮合物成分： 通式：（R^-SKOR2；)^ · [式中’ R1係亦可由環氧基或酼基取代之碳數丨至18的烷 - 基或苯基，r2為碳數1至6的烷基，11為〇或1];及 (D) 含有氟原子的非水性分散液型樹脂； 且s玄财污染塗料組成物之特徵在於： 以（A)成分及(B)成分之固體成分總量為基準，作為固體 成分， (C) 成分之含量為1至2〇質量％ ; (D) 成分之含量為5至3〇質量％。 2·如申請專利範圍第1項之耐污染塗料組成物，其中含有 氟原子的非水性分散液型樹脂(D)為可藉由在含有氟原 子之分散穩定劑(Dla)與有機溶劑(Dlb)之混合液中，使 S 58 201217468 聚合性不飽和單體共聚合並在該混合液中形成不溶的 聚合物粒子(Die)來調製之非水性分散液型樹脂。 3. 如申請專利範圍第2項之耐污染塗料組成物，其中含有 氟原子的分散穩定劑(D1 a)係藉由將包含具有氟烷基之 (曱基）丙烯酸酯、及/或含氟烯烴之聚合性不飽和單體進 行共聚合所獲得之聚合物。 4. 如申請專利範圍第1項之耐污染塗料組成物，其中在獲 得含羥基聚酯樹脂(A1)的反應中，多元酸成分(al)中的 脂環族多元酸(al-Ι)之合計含量以多元酸成分（al)之總 量為基準，係在50至100mol°/。之範圍内。 5. 如申請專利範圍第1至3項中任一項之耐污染塗料組成 物，其中以聚酯樹脂成分(A)及三聚氰胺樹脂成分(B)之 固體成分總量作為基準，含有作為固體成分之50至90質 量％的聚酯樹脂成分(A)，及作為固體成分之10至50質量 %的三聚氰胺樹脂成分(B)。 6. 如申請專利範圍第1至4項中任一項之耐污染塗料組成 物，係進一步含有消光劑(E)。 7. —種塗膜形成方法，其特徵在於包含以下步驟： 於金屬板上之單面或兩面上，形成由無鉻底漆塗料 所形成之底漆塗膜的步驟；及 在底漆塗膜之至少一者上，形成由如申請專利範圍 第1項之耐污染塗料組成物所形成之表塗塗膜的步驟。 8. —種塗裝金屬板的製造方法，其特徵在於包含以下步 驟： 59 201217468 在金屬板上之單面或兩面上，形成由無鉻底漆塗料 所形成之底漆塗膜的步驟；及 在底漆塗膜之至少一者上，形成由如申請專利範圍 第1項之耐污染塗料組成物所形成之表塗塗膜的步驟。 9. 一種塗裝金屬板，係藉由如申請專利範圍第7或8項之方 法所獲得。 60 201217468 四、指定代表圖·· (一) 本案指定代表圖為：第（ ）圖。（無) (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201217468 VII. Patent application scope: 1. A pollution-resistant coating composition comprising: (A) a polyester resin component containing 5 to 1% by mass of a number average molecular weight of 5,000 to 30,000 and a hydroxyl value of ^ i〇〇mgK〇H/g of the hydroxyl group-containing polyester resin (A1) as a solid component, and the hydroxyl group-containing polyester resin (Al) is a reaction product of (al) polybasic acid component and 〇2) alcohol component The obtained polyester resin component; (B) a melamine resin component which contains a mass% of a butyl etherified melamine resin (B1) as a solid component; (C) an organic tannic acid represented by the following formula Salt and/or its condensate component: General formula: (R^-SKOR2;)^ [In the formula, R1 is an alkane- or phenyl group having a carbon number of 丨 to 18 which may be substituted by an epoxy group or a fluorenyl group, R2 is an alkyl group having 1 to 6 carbon atoms, 11 is ruthenium or 1]; and (D) a non-aqueous dispersion type resin containing a fluorine atom; and the composition of the smectic pollution coating is characterized by: (A) component And the total solid content of the component (B) is based on the solid content, and the content of the component (C) is 1 to 2% by mass; (D) the content of the component It is 5 to 3 % by mass. 2. The non-aqueous dispersion type resin (D) containing a fluorine atom as claimed in claim 1 is a dispersion stabilizer (Dla) and an organic solvent (Dlb) containing a fluorine atom. In the mixed liquid, a non-aqueous dispersion type resin prepared by copolymerizing S 58 201217468 polymerizable unsaturated monomer and forming insoluble polymer particles (Die) in the mixed liquid. 3. The stain-resistant coating composition of claim 2, wherein the fluorine atom-containing dispersion stabilizer (D1 a) is to contain a (fluorenyl) acrylate having a fluoroalkyl group, and/or a fluorine-containing A polymer obtained by copolymerizing a polymerizable unsaturated monomer of an olefin. 4. The antifouling coating composition according to claim 1, wherein in the reaction for obtaining the hydroxyl group-containing polyester resin (A1), the alicyclic polybasic acid (al-Ι) in the polybasic acid component (al) The total content is from 50 to 100 mol% based on the total amount of the polybasic acid component (al). Within the scope. 5. The pollution-resistant coating composition according to any one of claims 1 to 3, wherein the total amount of solid components of the polyester resin component (A) and the melamine resin component (B) is used as a solid component 50 to 90% by mass of the polyester resin component (A), and 10 to 50% by mass of the melamine resin component (B) as a solid component. 6. The stain-resistant coating composition according to any one of claims 1 to 4, further comprising a matting agent (E). 7. A method of forming a coating film, comprising the steps of: forming a primer coating film formed of a chrome-free primer coating on one or both sides of a metal plate; and coating the primer film In at least one of them, a step of forming a surface coating film formed of the pollution-resistant coating composition of claim 1 of the patent application is formed. 8. A method of manufacturing a coated metal sheet, comprising the steps of: 59 201217468 forming a primer coating film formed of a chrome-free primer coating on one or both sides of a metal sheet; On at least one of the primer coating films, a step of forming a surface coating film formed of the pollution-resistant coating composition of claim 1 of the patent application is formed. 9. A coated metal sheet obtained by the method of claim 7 or 8. 60 201217468 IV. Designation of Representative Representatives (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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