TWI287037B

TWI287037B - Film-composition

Info

Publication number: TWI287037B
Application number: TW90110143A
Authority: TW
Inventors: Wen-Shu Jeng
Original assignee: Yung Chi Paint & Varnish Mfg C
Priority date: 2001-04-27
Filing date: 2001-04-27
Publication date: 2007-09-21

Abstract

The invention provides a coating composition on metal substrates, which coatings consist of film-forming resins, containing hydroxyl, carboxylic groups, or fluorine; amino-resins as the crosslinker, sulfonic acid as catalyst, amine as special additives etc. The ratio between film-forming resins and amino-resins could be from 7/3 to 9/1. And the weight percentage of sulfonic acid is from 7 to 30, based on the weight of film-forming resins. The equivalent ratio between amine and sulfonic acid s from 0.1/5 to 1/1. Furthermore, the functional structured materials can be from 0.5%-6.0% by total weight of coatings. The coatings can provide the fine feeling of smooth touch, fussy appearance, wrinkle surface, or special patterns. And the structured surface will inflect the sunlight and extend the service life, which are applied for interior and exterior for decoration and protection.

Description

1287037 ---案號90110143 年月日修正五、發明說明（1) •發明領域本發明係有關於一種鋼板塗料組成物，而更特定言之’係有關於一種可產生良好皺摺之鋼板塗料組成物，以及摻雜有粒子的鋼板塗料組成物。發明背景按’一般於鋼板上形成保護膜，係藉由將包含具有讥或 C00H基之樹脂的塗料塗佈於鋼板上，並以聚胺化合物作為硬化劑，以酸（例如磺酸、磷酸、金屬氧化物）作為催化劑’將鋼板置於烤箱内烘烤，使樹脂、聚胺與酸催化劑產生反應（反應式（a) —>反應式（b)，或反應式（a)〜> 反應式 (c)) ’進而於鋼板之表面形成平整之表面膜。反應式（a) ·· 一 V - 肀"Θ 3 一 c心含 # 一一 , Η ' 反應式（b): 一 A/C"i + Rxifi ^ 一 # 一 Λ/ CHiOR 十 ti ㊉ 1 ’ M f 反應式（c): "υ η // <±> -Y C 1 + k<Z 0〇hj # — λ/CHiO <Z R h 11287037 --- Case No. 90110143 Rev. 5, Invention Description (1) • Field of the Invention The present invention relates to a steel sheet coating composition, and more particularly to a steel sheet coating which produces good wrinkles A composition, and a steel sheet coating composition doped with particles. BACKGROUND OF THE INVENTION A protective film is generally formed on a steel sheet by applying a coating containing a resin having a ruthenium or C00H group to a steel sheet, and using a polyamine compound as a hardener, and an acid (for example, sulfonic acid, phosphoric acid, The metal oxide is used as a catalyst to bake the steel sheet in an oven to cause a reaction between the resin and the polyamine and the acid catalyst (reaction formula (a) -> reaction formula (b), or reaction formula (a) to > The reaction formula (c)) 'further forms a flat surface film on the surface of the steel sheet. Reaction formula (a) ·· 一 V - 肀"Θ 3 一c心含# 一一, Η ' Reaction formula (b): A A/C"i + Rxifi ^ 一# 一Λ / CHiOR 十蒂十 1 ' M f Reaction formula (c): "υ η // <±> -YC 1 + k<Z 0〇hj # — λ/CHiO <ZR h 1

1287037 1 號 90110143 五、發明說明（2) 月曰修正胺（特別疋二級胺）加入該塗料成份時係先與酸產生鍵結： — A/— 待胺受熱表面層與，使得塗酸先與樹層表面所平整的表絨毛狀之裝潢使用著重於彩速。然而愈南，且的控制。後逸出，塗佈層最佈層之每脂反應，形成的膜面膜，本觸感，而色鋼捲塗，溫度愈溫度愈南酸才能與樹脂反底層之胺受熱脫一層的反應時間而後逐層反應至係會產生非平滑發明所形成之皺具有較佳之質感料’而彩色鋼捲高’對塗料中胺 ’反應時間愈快之後烘烤加熱時，則需應。如此一來，塗佈層離係會產生一段時間差皆不相同。在表面層之 ^底層的情況下，塗佈且皺摺之紋路。相較於摺紋路以手觸摸係如同 ’故更適於室内或室外本發明之重點乃係塗料之重點為高溫、高揮發之控制的困難度則 ’難以達成反應均一性發明概述本發明的目的在於提供一種可高溫烘烤的、，，，其係適用於高溫、高速連續性塗裝線製種、。〃 /、系本發明的另一目的在於藉由調整胺與酸之 ^控制胺之脫離速度，以及酸與樹脂的反匕：，而適表層獲得良好皺摺紋路者。運而使塗料再者，本發明的另一目的在於藉由在塗料1287037 No. 1 90110143 V. INSTRUCTIONS (2) The ruthenium modified amine (especially the secondary amine) is firstly added to the acid when it is added to the coating composition: — A/—the surface layer of the amine to be heated, so that the acid is first The fluffy decoration that is flat with the surface of the tree layer focuses on the color speed. However, the more south, and the control. After the escape, the coating layer of the most layer of each lip reaction, the formation of the film mask, the touch of the touch, and the color steel coil coating, the temperature of the more the temperature of the south acid can be combined with the resin back to the bottom of the amine heat removal reaction time and then The layer-by-layer reaction to produce a wrinkle formed by a non-smooth invention has a better texture, and the color steel roll height is faster when the reaction time of the amine in the paint is faster. As a result, the coating layer will be different for a period of time. In the case of the bottom layer of the surface layer, the wrinkles are applied. Compared with the crease road, the hand touch is like 'so it is more suitable for indoor or outdoor. The focus of the invention is that the focus of the coating is the difficulty of high temperature and high volatilization control. 'It is difficult to achieve reaction uniformity. SUMMARY OF THE INVENTION It is to provide a high temperature baking, which is suitable for high temperature, high speed continuous coating line seed production. 〃 /, another object of the present invention is to obtain a good wrinkle pattern by adjusting the rate of separation of the amine from the acid and the acid and the reaction of the acid with the resin. Another coating of the present invention is by coating

δ if 贴 ·ΕΗ Wf k JGtFlO BIAIVVM outbiTiv t J 第7頁 1287037 Γ--年月曰狄工五、發明說明（3) ------- 材料’使添加的粒子受到陽光照射時會產生折射或反射，可進一步保護塗料膜，進而延長使用壽命。一 ★根據本發明，係提供一種鋼板塗料組成物，其包含： :薄f成形樹脂，其係選自由含有羥基或羧基之聚合物及 s有氟之聚合物所構成之組群中；一聚胺化合物，其係作為:硬化劑；一粒子材料其係以總配份1〇〇份為準，〇.5一6 重里份及一磺酸，其中該薄膜成形樹脂對該聚胺化合物之固=份重量比係7/3至9/1，以該薄膜成形樹脂之重量為準 ’石夤酸之重量百分比係為7至3 〇。本發明之鋼板塗料組成物可進一步包含一胺，而該胺對該磺酸之當量比係〇.丨/ 5至丨/ 1。再者，本發明之鋼板塗料組成物該粒子材料係選自由聚酸胺、腊及丙烯腈所構成之組群中，並具有3-1〇〇#爪之大小。 ^ 於本發明之鋼板塗料組成物中，該薄膜成形樹脂較佳係具有約2000-6000之數目平均分子量。δ if 贴·ΕΗ Wf k JGtFlO BIAIVVM outbiTiv t J Page 7 1287037 Γ--年月曰工工五、发明说明(3) ------- The material 'will cause the added particles to be exposed to sunlight Refraction or reflection further protects the coating film and extends its service life. According to the present invention, there is provided a steel sheet coating composition comprising: a thin f-forming resin selected from the group consisting of a polymer having a hydroxyl group or a carboxyl group and a polymer having fluorine; An amine compound as a curing agent; a particulate material which is based on 1 part by weight of the total component, 一5-6 parts by weight and monosulfonic acid, wherein the film forming resin is solidified to the polyamine compound The weight ratio of parts to parts is 7/3 to 9/1, and the weight percentage of the stone forming resin is 7 to 3 Torr. The steel sheet coating composition of the present invention may further comprise an amine, and the equivalent ratio of the amine to the sulfonic acid is 〇.丨 / 5 to 丨 / 1. Further, in the steel sheet coating composition of the present invention, the particulate material is selected from the group consisting of polyamine, wax and acrylonitrile, and has a size of 3-1 〇〇 #爪. In the steel sheet coating composition of the present invention, the film forming resin preferably has a number average molecular weight of about 2,000 to 6,000.

再者，於本發明之鋼板塗料組成物中，可用之薄膜成形樹脂較佳係選自由壓克力、多元聚酯、矽酮化多元聚酉旨以及聚偏二氟乙烯樹脂所構成之組群中。可用之聚胺化人物有甲基化聚胺與乙基化聚胺等等。 Q 再者，於本發明之鋼板塗料組成物中，該磺酸較佳係為含有苯磺酸根之磺酸，例如對甲苯磺酸（pTSA)舆二壬基石尹、酸等（DNNSA)。而該胺較佳係為三級胺，例如三乙胺 (T.E.A)、二異丙醇胺（DIPA)與曱基乙醇胺（DMEA)等。Further, in the steel sheet coating composition of the present invention, the film forming resin which can be used is preferably selected from the group consisting of acrylic, polyester, fluorenone, and polyvinylidene fluoride resin. in. Useful polyaminated species are methylated polyamines and ethylated polyamines and the like. Further, in the steel sheet coating composition of the present invention, the sulfonic acid is preferably a sulfonic acid containing a benzenesulfonate such as p-toluenesulfonic acid (pTSA) fluorenyl fluorenyl, an acid or the like (DNNSA). The amine is preferably a tertiary amine such as triethylamine (T.E.A.), diisopropanolamine (DIPA) and mercaptoethanolamine (DMEA).

12870371287037

第9頁 1287037 _案號90110143_年月日_ 五、發明說明（5) 實施例 1 2 3 4 5 聚酯樹脂 50 50 5 0 … — 壓克力樹脂 — — … 17.6 5 0 聚偏二氟乙烯樹脂 … — — 48 … 甲基化聚胺 6 6 6 — 6 乙基化聚胺 … — --- 1.4 … 對曱苯磺酸 1 — — … 1 嵌段對甲笨磺酸 … 0.5 0.5 … — 胺 1 … — … 1 多元聚酯 2 — 2.5 … — 聚醯胺粒子 … 2.5 … … 2.5 丙烯牦粒子 — — — 2.5 — 腊粒子 … — 2.5 … — 壓克力系流平劑 3.1 3.1 3.1 1.5 3.1 PU增黏劑 2.5 2.5 I 2.5 0.25 2.5 C.H溶劑 M.4 15.4 ! 12.9 8.75 13.9 平光劑(二氡化矽）1 1 — j — | — | — 顏料丨20 20 20 20 20 | 將本案實施例1至5所製得之組成物施加至鋼板表面，並加熱至160至3 0 0 °C之溫度，係分別獲得如本案第1至5圖所示之具有皺摺及/或粒子之鋼板塗層表面。再者，將本案第1至5圖所得之具有皺摺及/ 或粒子的鋼板塗層表面，以下列條件進行各種性質的測試，結果係如表（2 )所示。表⑺ 實施例 1 2 3 4 5 溫度 2I6〇C 232°C 24 1〇C 249〇C 24 1〇C 方格試驗 100/100 100/100 100/100 100/100 100/100 光澤 <5% <60% <60% <60% <5% MEK擦栻 >100 >100 >100 >100 >100 光澤保持率 290 290 290 290 290 鉛筆硬度 Η Η Η F Η 加工性 ΟΤ ΟΤ ΟΤ ΟΤ ΟΤPage 9 1287037 _ Case No. 90110143_年月日日_ V. Invention Description (5) Example 1 2 3 4 5 Polyester Resin 50 50 5 0 ... — Acrylic Resin — — 17.6 5 0 Polydifluoroethylene Vinyl resin... — 48 ... methylated polyamine 6 6 6 — 6 ethylated polyamine... — --- 1.4 ... p-toluenesulfonic acid 1 — — 1 1 block to methyl sulfonic acid... 0.5 0.5 ... —amine 1 ... — ... 1 Polyester 2 — 2.5 ... — Polyamide particles... 2.5 ... 2.5 Acrylonitrile particles — — 2.5 — Wax particles... — 2.5 ... — Acrylic leveling agent 3.1 3.1 3.1 1.5 3.1 PU tackifier 2.5 2.5 I 2.5 0.25 2.5 CH solvent M.4 15.4 ! 12.9 8.75 13.9 flat light agent (2 — 矽) 1 1 — j — | — | — 丨丨 20 20 20 20 20 | The composition prepared in 1 to 5 is applied to the surface of the steel sheet and heated to a temperature of 160 to 300 ° C to obtain a steel sheet having wrinkles and/or particles as shown in Figs. 1 to 5, respectively. Layer surface. Further, the surface of the steel sheet coating having wrinkles and/or particles obtained in Figs. 1 to 5 of the present invention was tested for various properties under the following conditions, and the results are shown in Table (2). Table (7) Example 1 2 3 4 5 Temperature 2I6〇C 232°C 24 1〇C 249〇C 24 1〇C Checking test 100/100 100/100 100/100 100/100 100/100 Gloss <5% <60% <60% <60% <5% MEK Wipe>100 >100 >100 >100 >100 Gloss Retention Rate 290 290 290 290 290 Pencil Hardness Η Η Η F Η Processing ΟΤ ΟΤ ΟΤ ΟΤ ΟΤ

第10頁 1287037 _案號 90110143_年月日_ 五、發明說明（6) 註：方格試驗：CNS 10757(單位：1 0 0 / 1 0 0 ) 光澤：CNS 1 0 75 7 (單位：°/〇) MEK 擦拭：NCCA II -18(單位：次）光澤保持率：CNS 1 0 75 7 (單位：％) 鉛筆硬度：ASTM D33 6 3-74 (單位：Η、F、2H、3H …）、加工性（Τ 變）：CNS 1 0 75 7 (單位：0Τ/0Τ、IT、2Τ …）本發明已特別參照其較佳形式加以描述。對熟習此項技藝者而言，在不偏離如下列申請專利範圍所定義之本發明的精神與範圍下的改變與修飾是明顯的。Page 10 1287037 _ Case No. 90110143_Year of the month _ V. Invention description (6) Note: Square test: CNS 10757 (unit: 1 0 0 / 1 0 0 ) Gloss: CNS 1 0 75 7 (Unit: ° /〇) MEK Wipe: NCCA II -18 (unit: time) Gloss retention: CNS 1 0 75 7 (unit: %) Pencil hardness: ASTM D33 6 3-74 (Unit: Η, F, 2H, 3H ...) , Processability (Τ): CNS 1 0 75 7 (Unit: 0Τ/0Τ, IT, 2Τ ...) The present invention has been described with particular reference to preferred forms thereof. It will be apparent to those skilled in the art that changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

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Claims

1287037

1 . A steel sheet coating composition comprising: a film forming resin selected from the group consisting of a polymer containing a hydroxyl group or a carboxyl group and a polymer containing fluorine; a polyamine compound which is used as a hardening a compatibilized acid, and a particulate material selected from the group consisting of polyamine, wax, and acrylonitrile, and having a size of 3 - 1 0 0 // m, which is 100 parts by total a weight ratio of 0.5-6 parts by weight, wherein the weight ratio of the film forming resin to the polyamine compound is 7 / 3 to 9 / 1, based on the weight of the film forming resin, and the weight percentage of the sulfonic acid is 7 to 30. 2. The steel sheet coating composition of claim 1, which further comprises a monoamine, and the equivalent ratio of the amine to the acid is 0.1/5 to 1/1. 3. The steel sheet coating composition of claim 1, wherein the film forming resin has a number average molecular weight of from about 2,000 to 6,000. 4. The steel sheet coating composition of claim 1, wherein the sulfonic acid comprises benzenesulfonate, and the amine is a tertiary amine. 5. The steel sheet coating composition according to claim 1, wherein the film forming resin is selected from the group consisting of acrylic, multi-polyester, fluorenated polyester, and polyvinylidene fluoride resin. .

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