WO2001024944A1 - Method for applying thermosetting fluororesin powder coating - Google Patents
Method for applying thermosetting fluororesin powder coating Download PDFInfo
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- WO2001024944A1 WO2001024944A1 PCT/JP1999/005461 JP9905461W WO0124944A1 WO 2001024944 A1 WO2001024944 A1 WO 2001024944A1 JP 9905461 W JP9905461 W JP 9905461W WO 0124944 A1 WO0124944 A1 WO 0124944A1
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- coating
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- temperature
- powder coating
- thermosetting
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/06—Applying particulate materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0218—Pretreatment, e.g. heating the substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
Definitions
- the present invention relates to a coating method which is characterized by a preparatory treatment of an object to be coated when a thermosetting fluororesin powder coating is electrostatically applied.
- thermoplastic resins using thermoplastic resin (for example, published in Japanese Patent Application Laid-Open No. 9-32023) and thermosetting resin using thermosetting resin.
- the resin component is a general-purpose resin such as polyester, acrylic resin, epoxy resin, etc.
- thermosetting fluororesin is used as a resin component (Japanese Patent Publication No. Hei 6-1104792, etc.).
- Known methods of coating powder coatings include the fluid immersion method and the electrostatic coating method.
- the fluid immersion method is a method in which a heated base material is immersed in powder coating to perform coating, and is widely used for thick film coating of thermoplastic powder coating.
- the electrostatic coating method is a method of spraying a powder coating charged with static electricity onto a base material, and is widely used in thermosetting powder coatings.
- thermosetting fluororesin powder coatings are different from general-purpose resin powder coatings. Because of the electric conductivity, electric repulsion easily occurs between the powder coating particles, and the coating efficiency is reduced. There is no known specific solution to the problem of such a thermosetting fluororesin powder coating material.
- Japanese Patent Publication No. 6_1047972 discloses an electrostatic coating method for a thermosetting fluororesin powder coating, but the coating efficiency and the coating method are not disclosed. There is no suggestion from the viewpoint of improvement.
- the present invention provides an electrostatic coating method that improves both the coating efficiency and the smoothness of a thermosetting fluororesin powder coating, such as coating efficiency, and the like.
- the purpose is. Disclosure of the invention
- thermosetting fluororesin powder coating when a thermosetting fluororesin powder coating is electrostatically coated, the object to be coated is higher than the glass transition temperature of the powder coating and the curing start temperature. More than 1 o: A method of applying a thermosetting fluororesin powder coating characterized by heating in advance to a high temperature range or lower.
- the painted surface of the object to be coated is a surface on which a chemical treatment has been applied to a metal, or a plastic coating on a metal. It is preferred that the surface be coated with a coating or a coating with a water-based paint. Is preferred. Best form for carrying out the invention
- the coating method of the present invention is based on the fact that the object to be coated is cured at a temperature higher than the glass transition temperature of the thermosetting fluororesin powder coating and starts to cure. 1 ot above temperature: Except for pre-heating to a temperature range not higher than the high temperature, equipment used in the conventionally known electrostatic coating method, Conditions can be adopted.
- the glass transition temperature refers to the glass transition temperature of a thermosetting fluororesin used as a resin component of a powder coating, and is referred to as thermosetting. It is a property inherent to the mold fluororesin.
- Thermosetting fluororesin The thermosetting fluororesin used in powder coatings usually has a temperature of 30 to 7 Ot at a temperature higher than room temperature.
- the curing start temperature means that when the powder coating is not heated, the curing reaction starts due to the action of the hardener incorporated in the powder coating.
- the temperature at which the curing reaction starts which is determined by the combination of the thermosetting fluororesin and the curing agent, and is higher than the glass transition temperature It is.
- the range is usually from 120 to 150.
- the lower limit of the heating temperature of the object to be coated is preferably 5: higher than the glass transition temperature, and more preferably 10 higher.
- the upper limit of the heating temperature of the object to be coated is 10 degrees higher than the temperature at which hardening starts. If the temperature is higher than this temperature, the hardening reaction proceeds rapidly, and the hardening starts before the attached powder paint flows, and the surface of the obtained coating film is smooth. It will disappear.
- the upper limit of the heating temperature is preferably a temperature 5 higher than the curing start temperature, and more preferably the curing start temperature.
- thermosetting fluororesin powder coatings have weaker adhesion to coated objects, especially to metal substrates, than general-purpose resin powder coatings. Therefore, in order to further enhance the effect of the present invention, it is preferable to apply a specific treatment to the painted surface of the object to be coated.
- a specific treatment to the painted surface of the object to be coated.
- a chemical treatment, a plastic coating treatment, or a coating treatment with paint is preferred. No.
- coating treatment with water-based paint is preferred because it improves the adhesion to metal bases and is superior in protecting the environment.
- the dani-forming treatment includes, for example, immersion in zinc phosphate, iron phosphate, chromate, chromic acid, chromic linoleic acid, and spraying. It is preferred.
- the plastic coating processing includes polyamid, polyrefin, polyester, polyviel chloride, and the like. Coating by POLYVINYLIDEN FULL OID etc. is performed.
- the coating treatment with a paint is a water-based paint made of a thermosetting acrylic resin, a polyester resin, a urethane resin, an epoxy resin, or the like. , Etc., with a thickness of 1 to 50.
- thermosetting fluororesin powder coating used in the present invention is basically composed of a thermosetting fluororesin powder and a curing agent, and if necessary, a pigment and various additives. It is a usual thermosetting fluorine resin powder coating.
- thermosetting fluororesin as a resin component is particularly restricted if it is a polymer having a fluoromonomer unit and a crosslinkable reactive group as essential components. There is no limit.
- fluorine-containing monomer examples include tetrafluoroethylene, black mouth trifluoroethylene, and trifluorene. Len, vinylidene fluoride, hexafluoropropylen, pen fluorfluoropropylen, perfluorovinyl One or two such as ether, monofluoroethylene, etc. More than one species. If necessary, a non-fluorinated monomer may be copolymerized.
- the bridging reactive groups include, for example, a hydroxyl group, a carboxyl group, an amino group, an amide group, an epoxy group, and an isocyanate.
- halogen atoms such as bromine and iodine are exposed.
- thermosetting fluororesin as a powder resin component
- general-purpose thermosetting resin of non-fluorocarbon type for example, epoxy resin It may contain a mixture of xyl resin, acrylic resin, and polyester resin.
- thermosetting powder coatings those which have been conventionally used in thermosetting powder coatings can be used.
- a blocked isolating agent can be used. Examples include compounds, acid anhydrides, polyamine compounds, glycidyl compounds, isocyanurate compounds, polybasic acids, and the like.
- Cosmetic agents include condensed azo compounds, isoindolinone, quinacridone, dike pillow mouth pillow, antraquinone, and zeolide.
- Organic pigments such as xanthane; titanium oxide, iron oxide, carbon black, chromium oxide, lead chromate, white lead, molybden oren
- Organic oxide paints such as diene; metal powders such as aluminum powder and stainless steel powder are removed.
- additives commonly used in powder coatings such as fillers, UV absorbers, leveling agents, and flow regulation Agents, antioxidants, thermal degradation inhibitors, gloss adjusters, charge control agents, etc., may be appropriately combined.
- thermosetting fluororesin powder coating which can be particularly suitably used by the method of the present invention, for example, Japanese Patent Publication No. 6-107492, Kaihei 5 — 3 3 1 3 8 8 No. 2 Powder coatings using thermosetting fluororesin with a relatively low glass transition temperature, such as those described in the specification of No. 8 2 7 2 6, etc., are required.
- the method and conditions such as the application of an electrostatic charge may be normal.
- electrostatic coating there are two methods of applying static electricity during electrostatic coating: triboelectric charging and corona charging.However, is it easy for fluorocarbon resin to be negatively charged? The corona charging method is more suitable. Applied voltage is 20 to 80 kV, and more preferably 40 to 60 kV. If the voltage is too high, the surface of the coating film tends to be roughened, and if the voltage is too low, the coating efficiency decreases.
- thermosetting fluororesin powder coating (Preparation of thermosetting fluororesin powder coating)
- this fluororesin powder 44 parts by weight of this fluororesin powder, 30 parts by weight of a filler (titanium dioxide) and a curing agent (Hads' adduct: 1503) 26 parts by weight were uniformly mixed for about 1 minute with a drive blender (Henschel Mixer manufactured by Mitsui Chemicals, Ltd.), and then extruded at a temperature of 80-100. Kneading machine (Bus Conveyor PR-46 made by Bus) The mixture was further melt-kneaded, cooled, pulverized finely with a hammer impact pulverizer, and further coarsely pulverized using a 150 mesh wire mesh to remove the heat-cured heat used in the examples. Molded fluororesin powder coating was prepared.
- the glass transition temperature of the thermosetting fluororesin was measured using a thermal analysis system manufactured by Parkin Elma Inc. The heat balance was measured by heating at a heating rate of 10 / min from 125 to 200 and the heat transfer rate was measured, and the temperature at the midpoint between the two inflection points observed was defined as the glass transition temperature. .
- the preheating temperature of the object to be coated in the case of using this powder coating is higher than 45 and higher than 150.
- a 0.8 mm thick zinc phosphate treated steel sheet is coated with a polyurethane aqueous paint (VD100N manufactured by Mitsui Toatsu Chemicals, Inc.) at a thickness of 10 / zm.
- the object to be coated was prepared by painting on the surface.
- the object to be coated is heated to loot and immediately placed in a bush of a corona-type powder coating gun (GX330, manufactured by Onoda Cement Co., Ltd.).
- the powder coating was electrostatically coated at an applied voltage of 60 kV.
- the coating efficiency (%) [ (total coating amount (g) effective discharge amount of Z powder coating (g)) XI00] was 75%.
- a The surface of the coating film is smooth without any irregularities.
- Example 1 Using the coating materials shown in the following table, and setting the heating temperature of the coating materials to the temperature shown in Table 1, the electrostatic coating and baking were performed in the same manner as in Example 1. The coating efficiency and the properties of the coating film were examined. Table 1 shows the results.
- Example 2 The phosphoric acid-treated steel sheet used in Example 1 before urethane coating.
- Example 3 A steel sheet that has not been subjected to any treatment.
- Comparative Examples 1 and 2 Same urethane coated steel sheet as in Example 1.
- the efficiency of coating per coating is increased, so that the number of coatings required to obtain a target film thickness can be reduced. As a result, productivity is improved. Further, since the obtained coating film has excellent smoothness, it is possible to provide a coated product having a good appearance.
Abstract
A method for applying a thermosetting fluororesin powder coating by electrostatic coating, characterized in that the substrate to be coated is preheated at a temperature which is higher than the glass transition temperature of the powder coating and is not higher than the temperature higher by 10°C than the starting temperature for curing of the coating. This method of applying the coating allows reducing the number of repeat of applying for obtaining a desired film thickness due to its high application efficiency, thus leading to the improvement of productivity. Further, the method can be used for providing a coated article having good appearance, since it imparts excellent smoothness to a coated surface.
Description
明 糸田 熱硬化 型 フ ッ 素 樹脂粉体 塗料 の 塗装方 法 技術 分 野 Akira Itoda Thermosetting type fluororesin powder paint coating method technology field
本発 明 は熱硬化 型 フ ッ 素 樹脂粉体 塗料 を 静電 塗 装 す る 際 の 被 塗装物 の 予 備 処 理 に 特徴 を 有 す る 塗装 方 法 に 関 す る 。 背 景 技術 The present invention relates to a coating method which is characterized by a preparatory treatment of an object to be coated when a thermosetting fluororesin powder coating is electrostatically applied. Background technology
粉体塗料 は一 般 の 溶剤 型 塗料 と 比 較 し て 、 揮発 性 溶 剤 の 排 出 が な く 無 公 害 で あ る こ と 、 塗装 ラ イ ン の 管理 が容 易 で あ る こ と な ど と い っ た 多 く の 利 点 か ら 、 近 年 、 金 属 の 塗装 全般 に 広 く 採用 さ れ て い る 。 粉体 塗料 に は 熱 可 塑 性樹脂 を 用 い る 熱可塑型粉体塗料 （ 特 開 平 9 — 3 0 2 3 0 6 号公 報 な ど ） と 熱硬化性樹脂 を 用 い る 熱硬 化 型粉体 塗料 が あ り 、 さ ら に 熱硬化 型粉体 塗料 ί:： は ポ リ エ ス テ ル 、 ア ク リ ル 樹脂 、 エ ポ キ シ 樹脂 な ど の 汎用 樹脂 を 樹脂 成分 と す る も の と 熱硬 化 型 フ ッ 素 樹脂 を 樹脂 成 分 と す る も の ( 特公 平 6 一 1 0 4 7 9 2 号公 報 な ど )が知 ら れ て い る 。 粉体塗料 の 塗装 方法 と し て は 流 動浸漬法 と 静電 塗装 法 が知 ら れ て い る 。 流動浸漬 法 は 加 熱 し た 基材 を 粉体塗料 中 に 漬 け て 塗装 を 行 な う 方 法 で あ り 、 熱 可 塑型 粉体 塗料 の 厚膜塗装 に 多 く 採 用 さ れ て い る 。 静電 塗装 法 は静電気 を 帯 びた 粉体塗料 を 基 材 に 吹 き 付 け る 方 法 で あ り 、 熱硬 化 型粉体塗料 に 多 く 採 用 さ れ て い る 。 Compared with general solvent-based paints, powder paints do not emit volatile solvents and are pollution-free, making it easier to manage paint lines. Due to its many advantages, it has been widely adopted in recent years for metal coatings in general. Thermoplastic resins using thermoplastic resin (for example, published in Japanese Patent Application Laid-Open No. 9-32023) and thermosetting resin using thermosetting resin. There are mold powder coatings, and thermosetting powder coatings. The resin component is a general-purpose resin such as polyester, acrylic resin, epoxy resin, etc. Known are those in which a thermosetting fluororesin is used as a resin component (Japanese Patent Publication No. Hei 6-1104792, etc.). Known methods of coating powder coatings include the fluid immersion method and the electrostatic coating method. The fluid immersion method is a method in which a heated base material is immersed in powder coating to perform coating, and is widely used for thick film coating of thermoplastic powder coating. . The electrostatic coating method is a method of spraying a powder coating charged with static electricity onto a base material, and is widely used in thermosetting powder coatings.
熱硬 化 型 粉体 塗料 の う ち 熱硬 化 型 フ ッ 素 樹脂粉体 塗料 は 汎用 樹脂粉体 塗料 と 異 な り 、 フ ッ 素 樹脂 特有 の 高 い 帯
電率が故 に粉体塗料粒子間 に電気的反発 が生 じ やす く 、 塗着効率が低下す る 。 こ う し た 熱硬化型 フ ッ 素樹脂粉体 塗料 に お け る 問 題 に つ い て の具体的解決手段 は知 ら れ て い な い 。 た と え ば特公平 6 _ 1 0 4 7 9 2 号公報 に 熱硬 化型 フ ッ 素樹脂粉体塗料 の 静電塗装法が 開 示 さ れて い る が 、 塗着効率や塗装方法 の改善 と い っ た 観点か ら の 示唆 はな い 。 Among the thermosetting powder coatings, the thermosetting fluororesin powder coatings are different from general-purpose resin powder coatings. Because of the electric conductivity, electric repulsion easily occurs between the powder coating particles, and the coating efficiency is reduced. There is no known specific solution to the problem of such a thermosetting fluororesin powder coating material. For example, Japanese Patent Publication No. 6_1047972 discloses an electrostatic coating method for a thermosetting fluororesin powder coating, but the coating efficiency and the coating method are not disclosed. There is no suggestion from the viewpoint of improvement.
本発 明 は、 熱硬化型 フ ッ 素樹脂粉体塗料 の 塗着効率お よ び平滑性な ど の 塗膜外観 の両者 を 共 に 改善す る 静電塗 装方法 を提供す る こ と を 目 的 と す る 。 発 明 の 開 示 The present invention provides an electrostatic coating method that improves both the coating efficiency and the smoothness of a thermosetting fluororesin powder coating, such as coating efficiency, and the like. The purpose is. Disclosure of the invention
すな わ ち 本発 明 は 、 熱硬化型 フ ッ 素樹脂粉体塗料 を 静 電塗装す る 際 、 被塗装物 を 該粉体塗料 の ガ ラ ス 転移温度 よ り も 高 く かつ硬化 開始温度よ り も 1 o : 高 い 温度以下 の 温度範囲 に予 め 加熱 し てお く こ と を特徴 と す る 熱硬化 型 フ ッ 素樹脂粉体塗料 の塗装方法 に 関す る 。 In other words, the present invention discloses that when a thermosetting fluororesin powder coating is electrostatically coated, the object to be coated is higher than the glass transition temperature of the powder coating and the curing start temperature. More than 1 o: A method of applying a thermosetting fluororesin powder coating characterized by heating in advance to a high temperature range or lower.
本発 明 に お い て 、 被塗装物 の 塗装面 は 、 金属 に化成処 理が施 さ れて い る 面で あ る か 、 ま た は金属 に プ ラ ス チ ッ ク コ ー テ ィ ン グ処理 ま た は塗料 に よ る 被覆処理が施 さ れ て い る 面で あ る こ と が好 ま し く 、 特 に 水性型塗料 に よ る 被覆処理が施 さ れて い る 面で あ る こ と が好 ま し い 。 発 明 を実施す る た め の 最 良 の 形態 本発 明 の塗装方法 は 、 被塗装物 を 熱硬化型 フ ッ 素樹脂 粉体塗料の ガ ラ ス 転移温度 よ り も 高 く か つ硬化 開始温度 よ り も 1 o t: 高 い 温度以下 の温度範 囲 に 予 め 加熱 し て お く こ と 以外 は 、 従来公知 の 静電塗装方法 に お け る 装置 、
条 件 が採用 で き る 。 In the present invention, the painted surface of the object to be coated is a surface on which a chemical treatment has been applied to a metal, or a plastic coating on a metal. It is preferred that the surface be coated with a coating or a coating with a water-based paint. Is preferred. Best form for carrying out the invention The coating method of the present invention is based on the fact that the object to be coated is cured at a temperature higher than the glass transition temperature of the thermosetting fluororesin powder coating and starts to cure. 1 ot above temperature: Except for pre-heating to a temperature range not higher than the high temperature, equipment used in the conventionally known electrostatic coating method, Conditions can be adopted.
本発 明 に お い て 、 ガ ラ ス 転移 温度 と は粉体 塗料 の 樹脂 成 分 と し て 使 用 さ れ る 熱硬化 型 フ ッ 素 樹脂 の ガ ラ ス 転移 温度 を 言 い 、 熱硬 化 型 フ ッ 素 樹脂 に 固 有 の 物 性 で あ る 。 熱硬化 型 フ ッ 素 樹脂 粉体塗料 に 使用 さ れ る 熱硬化 型 フ ッ 素 樹脂 で は 、 室温 よ り も 高 い 温度 で 通 常 3 0 〜 7 O t で あ る 。 ま た硬 化 開 始 温度 と は 、 粉体塗料 を 加 熱 し て い く と 粉体 塗料 に 配 合 さ れ て い る 硬 化 剤 の 働 き に よ り 硬化 反 応 が始 ま る が 、 そ の 硬化 反 応 が始 ま る 温度 を 言 い 、 熱硬 化 型 フ ッ 素樹脂 と 硬化 剤 の 組合せ に よ っ て 決 ま る 温度 で あ っ て ガ ラ ス 転移 温度 よ り も 高 い 温度 で あ る 。 現在使 用 さ れて い る 熱硬 化 型 フ ッ 素樹脂粉体塗料 で は通 常 1 2 0 〜 1 5 0 で の 範 囲 で あ る 。 In the present invention, the glass transition temperature refers to the glass transition temperature of a thermosetting fluororesin used as a resin component of a powder coating, and is referred to as thermosetting. It is a property inherent to the mold fluororesin. Thermosetting fluororesin The thermosetting fluororesin used in powder coatings usually has a temperature of 30 to 7 Ot at a temperature higher than room temperature. The curing start temperature means that when the powder coating is not heated, the curing reaction starts due to the action of the hardener incorporated in the powder coating. The temperature at which the curing reaction starts, which is determined by the combination of the thermosetting fluororesin and the curing agent, and is higher than the glass transition temperature It is. For the thermosetting fluororesin powder coatings currently used, the range is usually from 120 to 150.
静電塗装 時 に 被 塗装 物 が熱硬化 型 フ ッ 素樹脂粉体 塗料 の ガ ラ ス 転移温度以下 の 場合 、 粉体塗料 の 被塗装物 へ の 付着が不 充 分 と な り 、 塗着効率 が 向 上 し な い 。 被塗装物 の加 熱温度 の下 限 は、好 ま し く はガ ラ ス 転移温度 よ り 5 : 高 い 温度 、 さ ら に 好 ま し く は 1 0 高 い 温度 で あ る 。 If the object to be coated is lower than the glass transition temperature of the thermosetting fluororesin powder coating during electrostatic coating, the adhesion of the powder coating to the object will not be sufficient and the coating efficiency will be low. Does not improve. The lower limit of the heating temperature of the object to be coated is preferably 5: higher than the glass transition temperature, and more preferably 10 higher.
被 塗 装 物 の 加 熱 温 度 の 上 限 は 硬 化 開 始 温 度 よ り も 1 0 高 い 温度 で あ る 。 こ の 温度 よ り も 高 く な る と 硬 化反 応 が急速 に 進 み 、 付着 し た 粉体塗料 が流 動す る 前 に 硬化 が始 ま り 、 得 ら れ る 塗膜 の 表面 が平滑 で な く な る 。 加 熱 温度 の 上 限 は 、 好 ま し く は硬化 開 始温度 よ り 5 高 い 温 度 、 さ ら に 好 ま し く は硬化 開 始 温度 で あ る 。 The upper limit of the heating temperature of the object to be coated is 10 degrees higher than the temperature at which hardening starts. If the temperature is higher than this temperature, the hardening reaction proceeds rapidly, and the hardening starts before the attached powder paint flows, and the surface of the obtained coating film is smooth. It will disappear. The upper limit of the heating temperature is preferably a temperature 5 higher than the curing start temperature, and more preferably the curing start temperature.
熱硬化 型 フ ッ 素 樹脂粉体塗料 は 一般 に 、 汎用 樹脂 粉体 塗料 に 比 べ て 被 塗装 物 、 特 に 金 属 基材 に 対す る 密着性 が 弱 い 。 そ こ で 本 発 明 の 効 果 を よ り 一 層 高 め る た め に は 、 被 塗装 物 の 塗 装 面 に 特 定 の 処 理 を 施す こ と が好 ま し い 。
金 属 基材 の 塗装 面 の 処 理 と し て は 、 化 成処 理 ま た は プ ラ ス チ ッ ク コ 一 テ ィ ン グ 処 理 ま た は塗料 に よ る 被覆処 理 が好 ま し い 。 特 に 水性 型 塗料 に よ る 被覆処 理 が 、 金 属 基 材 へ の 密 着性 が 向 上 し 、 し か も 環 境 の 保護 に 優 れ る 点 か ら 好 ま し レ 。 In general, thermosetting fluororesin powder coatings have weaker adhesion to coated objects, especially to metal substrates, than general-purpose resin powder coatings. Therefore, in order to further enhance the effect of the present invention, it is preferable to apply a specific treatment to the painted surface of the object to be coated. As the treatment of the painted surface of the metal base material, a chemical treatment, a plastic coating treatment, or a coating treatment with paint is preferred. No. In particular, coating treatment with water-based paint is preferred because it improves the adhesion to metal bases and is superior in protecting the environment.
ィ匕 成 処理 と し て は 、 リ ン 酸 亜鉛 、 リ ン 酸鉄 、 ク ロ メ ー ト 、 ク ロ ム 酸 、 ク ロ ム 酸 リ ン 酸 へ の 浸漬 、 ス プ レ ー 処 理 な ど が好 ま し く あ げ ら れ る 。 The dani-forming treatment includes, for example, immersion in zinc phosphate, iron phosphate, chromate, chromic acid, chromic linoleic acid, and spraying. It is preferred.
プ ラ ス チ ッ ク コ ー テ ィ ン グ処 理 と し て は 、ポ リ ア ミ ド 、 ポ リ オ レ フ ィ ン 、 ポ リ エ ス テ ル 、 ポ リ ビ エ ル ク ロ ラ イ ド 、 ポ リ ビ ニ リ デ ン フ ル オ ラ ィ ド な ど に よ る コ ー テ ィ ン グ な ど が あ げ ら れ る 。 The plastic coating processing includes polyamid, polyrefin, polyester, polyviel chloride, and the like. Coating by POLYVINYLIDEN FULL OID etc. is performed.
塗料 に よ る 被覆処 理 と し て は 、 熱硬化性 の ア ク リ ル樹 脂 、 ポ リ エ ス テ ル 樹脂 、 ウ レ タ ン 樹脂 、 エ ポ キ シ樹脂 な ど か ら な る 水性塗料 を 厚 さ 1 〜 5 0 で 被覆す る 処 理 な ど が あ げ ら れ る 。 The coating treatment with a paint is a water-based paint made of a thermosetting acrylic resin, a polyester resin, a urethane resin, an epoxy resin, or the like. , Etc., with a thickness of 1 to 50.
本発 明 で使用 さ れ る 熱硬化 型 フ ッ 素樹脂粉体 塗料 は 、 基本 的 に 熱硬化 型 フ ッ 素 樹脂粉体 と 硬化剤 と 、 さ ら に 要 すれ ば顔料や 各 種添加 剤 と か ら な る 通 常 の 熱硬化 型 フ ッ 素 樹脂粉体塗料 で あ る 。 The thermosetting fluororesin powder coating used in the present invention is basically composed of a thermosetting fluororesin powder and a curing agent, and if necessary, a pigment and various additives. It is a usual thermosetting fluorine resin powder coating.
樹脂 成分 と し て の 熱硬化型 フ ッ 素樹脂 と し て は含 フ ッ 素 単量体単位 と 架橋性 反 応基 を 必 須成分 と し て 有 す る 重 合体で あ れ ば特 に 制 限 は な い 。 The thermosetting fluororesin as a resin component is particularly restricted if it is a polymer having a fluoromonomer unit and a crosslinkable reactive group as essential components. There is no limit.
含 フ ッ 素単量体 と し て は 、 た と え ばテ ト ラ フ ル ォ ロ ェ チ レ ン 、 ク ロ 口 ト リ フ ル ォ ロ エ チ レ ン 、 ト リ フ ル ォ ロ ェ チ レ ン 、 ビ ニ リ デ ン フ リレ オ ラ イ ド 、 へ キ サ フ ル ォ ロ プ ロ ピ レ ン 、 ペ ン 夕 フ ル ォ ロ プ ロ ピ レ ン 、 パ ー フ ル ォ ロ ビ ニ ル エ ー テ ル 、 モ ノ フ ル ォ ロ エ チ レ ン な ど の 1 種 ま た は 2
種以 上 が あ げ ら れ る 。 さ ら に 要 す れ ば 、 非 フ ッ 素 系 の 単 量体 を 共重 合 さ せ た も の で も よ い 。 Examples of the fluorine-containing monomer include tetrafluoroethylene, black mouth trifluoroethylene, and trifluorene. Len, vinylidene fluoride, hexafluoropropylen, pen fluorfluoropropylen, perfluorovinyl One or two such as ether, monofluoroethylene, etc. More than one species. If necessary, a non-fluorinated monomer may be copolymerized.
架 橋 性反 応基 と し て は 、 た と え ば水酸 基 、 カ ル ボ キ シ ル 基 、 ア ミ ノ 基 、 ア ミ ド 基 、 エ ポ キ シ 基 、 イ ソ シ ァ ネ ー ト 基 な ど の ほ か 、 臭 素 や ヨ ウ 素 な ど の ハ ロ ゲ ン 原子 な ど が あ げ ら れ る 。 The bridging reactive groups include, for example, a hydroxyl group, a carboxyl group, an amino group, an amide group, an epoxy group, and an isocyanate. In addition to bases, halogen atoms such as bromine and iodine are exposed.
粉体樹脂 成 分 と し て 前 記 の 熱硬 化 型 フ ッ 素 樹脂 に 加 え て 、 要す れ ば非 フ ッ 素 系 の 前記 の 汎用 の 熱硬化 型 樹 脂 、 た と え ばエ ポ キ シ 樹脂 、 ア ク リ ル 樹脂 、 ポ リ エ ス テ ル樹 脂 な ど を 配合 し て も よ い 。 In addition to the above-mentioned thermosetting fluororesin as a powder resin component, if necessary, the above-mentioned general-purpose thermosetting resin of non-fluorocarbon type, for example, epoxy resin It may contain a mixture of xyl resin, acrylic resin, and polyester resin.
硬化 剤 と し て は 、 従 来 よ り 熱硬 化 型 粉体塗料 に 使 用 さ れて い る も の が使 用 で き 、 た と え ば ブ ロ ッ ク 化 イ ソ シ ァ ネ ー ト 化合物 、 酸 無 水 物 、 ポ リ ア ミ ン 化 合物 、 グ リ シ ジ ル化 合物 、 イ ソ シ ァ ヌ レ ー ト 化 合 物 、 多塩基酸 な ど が あ げ ら れ る 。 As the curing agent, those which have been conventionally used in thermosetting powder coatings can be used. For example, a blocked isolating agent can be used. Examples include compounds, acid anhydrides, polyamine compounds, glycidyl compounds, isocyanurate compounds, polybasic acids, and the like.
顔 料 と し て は 、 縮合 ァ ゾ化合 物 、 イ ソ イ ン ド リ ノ ン 、 キ ナ ク リ ド ン 、 ジ ケ 卜 ピ ロ 口 ピ ロ 一リレ 、 ア ン ト ラ キ ノ ン 、 ジ ォ キ サ ン な ど の 有 機 顔料 ； 酸化 チ タ ン 、 酸化鉄 、 カ ー ボ ン ブ ラ ッ ク 、 酸 化 ク ロ ム 、 ク ロ ム 酸鉛 、 白 鉛 、 モ リ ブ デ ン オ レ ン ジ な ど の 無 機酸化 物 顔 料 ； ア ル ミ ニ ウ ム 粉 、 ス テ ン レ ス ス チ ー ル粉 な ど の 金 属 粉 な ど が あ げ ら れ る 。 Cosmetic agents include condensed azo compounds, isoindolinone, quinacridone, dike pillow mouth pillow, antraquinone, and zeolide. Organic pigments such as xanthane; titanium oxide, iron oxide, carbon black, chromium oxide, lead chromate, white lead, molybden oren Organic oxide paints such as diene; metal powders such as aluminum powder and stainless steel powder are removed.
そ の ほ か 、 粉体塗料 で 通 常使 用 さ れ て い る 各 種 の 添 加 剤 、 た と え ば充 填剤 、 紫 外線 吸 収剤 、 レ べ リ ン グ剤 、 流 動 調 整剤 、 酸化 防 止 剤 、 熱 劣化 防 止 剤 、 艷調 整剤 、 電 荷 制御 剤 な ど も 適 宜 配 合 し て も よ い 。 In addition, various additives commonly used in powder coatings, such as fillers, UV absorbers, leveling agents, and flow regulation Agents, antioxidants, thermal degradation inhibitors, gloss adjusters, charge control agents, etc., may be appropriately combined.
本 発 明 の 方 法 で 特 に 好適 に 使 用 で き る 熱硬化 型 フ ッ 素 樹脂粉体塗料 と し て は 、 た と え ば特 公 平 6 — 1 0 4 7 9 2 号 公報 、 特 開 平 5 — 3 3 1 3 8 8 号 公 報 、 特 許第 2 7
8 2 7 2 6 号 明 細書な ど に 記載 さ れて い る 比較的低 ガ ラ ス 転移温度 の 熱硬化性 フ ッ 素樹脂 を 使用 す る 粉体塗料が あ げ ら れ る 。 As a thermosetting fluororesin powder coating which can be particularly suitably used by the method of the present invention, for example, Japanese Patent Publication No. 6-107492, Kaihei 5 — 3 3 1 3 8 8 No. 2 Powder coatings using thermosetting fluororesin with a relatively low glass transition temperature, such as those described in the specification of No. 8 2 7 2 6, etc., are required.
本発 明 に お い て 静電電荷 の 付与 な ど の 方法や条件 は通 常 の も の で よ い 。 た と え ば静電塗装 に お け る 静電塗装時 の静電気付与 の 方法 に は摩擦帯電方式 と コ ロ ナ帯電方式 が あ る が、 フ ッ 素樹脂が負電荷 を 帯びやす い こ と か ら コ ロ ナ帯電方式が好適で あ る 。印加電圧 は 2 0 〜 8 0 k V 、 さ ら に 4 0 〜 6 0 k V が適 当 で あ る 。 電圧が高す ぎ る と 塗膜表面 に荒れが生 じ やす く な り 、 電圧が低す ぎる と 塗 着効率が低下す る 。 In the present invention, the method and conditions such as the application of an electrostatic charge may be normal. For example, in electrostatic coating, there are two methods of applying static electricity during electrostatic coating: triboelectric charging and corona charging.However, is it easy for fluorocarbon resin to be negatively charged? The corona charging method is more suitable. Applied voltage is 20 to 80 kV, and more preferably 40 to 60 kV. If the voltage is too high, the surface of the coating film tends to be roughened, and if the voltage is too low, the coating efficiency decreases.
つ ぎ に本発 明 を 実施例 に し た が っ て 説明す る が、 本発 明 はか か る 実施例 の み に 限定 さ れ る も の で はな い 。 Next, the present invention will be described with reference to examples, but the present invention is not limited to only such examples.
実施例 1 Example 1
(熱硬化型 フ ッ 素樹脂粉体塗料 の調製） (Preparation of thermosetting fluororesin powder coating)
ク ロ 口 卜 リ フ ル ォ ロ エチ レ ン シ ク ロ へ キ シル ビ ニル エー テル /ィ ソ ブチル ビ二ルェ一 テル ヒ ド ロ キ シ プチ ル ビニルエー テル （重量比 ： 約 5 0 / 1 6 / 9 / 2 5 ) 共重合体 （水酸基価 ： 1 2 0 m g K O H Z g 、 ガ ラ ス 転 移温度 ： 4 5 T： 、 加熱減量 ： 2 重量 ％ 以下、 テ ト ラ ヒ ド 口 フ ラ ン 中 で 3 0 に て測定 し た 固有粘度 〔 η〕 ： 0 . 2 1 ) を衝撃式ハ ン マ ー ミ ルで粉枠 し て 熱硬化型 フ ッ 素樹 脂粉体 を作製 し た 。 こ の フ ッ 素樹脂粉体 4 4 重量部、 充 填剤 （二酸化チ タ ン） 3 0 重量部お よ び硬化剤 （ ヒ ュ ル ス 社製 の ァ ダ ク ト Β — 1 5 3 0 ) 2 6 重量部 を ド ラ イ ブ レ ン ダー （三井化工機械 （株） 製 の ヘ ン シ ェ ル ミ キサー ） で約 1 分間均一 に混合 し た の ち 8 0 〜 1 0 0 の温度で 押出 混練機 （ ブ ス 社製 の ブス コ ニ ー ダ一 P R — 4 6 ) に
よ り 溶融混練 し 、 冷却後ハ ン マ ー 式衝撃粉砕機で微粉砕 し 、 さ ら に 1 5 0 メ ッ シ ュ の 金網 で粗粉砕物 を 除 い て 、 実施例 に使用 す る 熱硬化型 フ ッ 素樹脂粉体塗料 を 調 製 し た 。 Black mouth trifluoroethylene cyclohexyl vinyl ether / isobutyl vinyl ether hydroxyl hydroxy vinyl ether (weight ratio: about 50/16) / 9/25) Copolymer (hydroxyl value: 120 mg KOHZ g, glass transfer temperature: 45 T:, loss on heating: 2% by weight or less, in tetrahedral franc The intrinsic viscosity [η]: 0.21) measured at 30 in the above was powder-framed with an impact-type hammer mill to produce a thermosetting fluorine resin powder. 44 parts by weight of this fluororesin powder, 30 parts by weight of a filler (titanium dioxide) and a curing agent (Hads' adduct: 1503) 26 parts by weight were uniformly mixed for about 1 minute with a drive blender (Henschel Mixer manufactured by Mitsui Chemicals, Ltd.), and then extruded at a temperature of 80-100. Kneading machine (Bus Conveyor PR-46 made by Bus) The mixture was further melt-kneaded, cooled, pulverized finely with a hammer impact pulverizer, and further coarsely pulverized using a 150 mesh wire mesh to remove the heat-cured heat used in the examples. Molded fluororesin powder coating was prepared.
なお 、 熱硬化型 フ ッ 素樹脂 の ガ ラ ス 転移温度 は、 パ ー キ ン エルマ 一社製 のサー マ ル · ア ナ リ シ ス · シ ス テ ム を 使用 し 、 1 O m g の試料 を 一 2 5 力 ら 2 0 0 ま で 1 0 で /分の 昇温速度で加熱 し て 熱収支 を測定 し 、 観測 さ れる 2 つの変極点 の 中 点 の温度 を ガ ラ ス転移温度 と し た。 The glass transition temperature of the thermosetting fluororesin was measured using a thermal analysis system manufactured by Parkin Elma Inc. The heat balance was measured by heating at a heating rate of 10 / min from 125 to 200 and the heat transfer rate was measured, and the temperature at the midpoint between the two inflection points observed was defined as the glass transition temperature. .
得 ら れた粉体塗料 の硬化 開始温度 を オ リ ェ ン テ ツ ク コ 一ポ レ ー シ ヨ ン社製 の振子型粘弾性測定器 （ D D V — O P A ) で測定 し た と こ ろ 、 1 4 0 で あ っ た 。 When the curing start temperature of the obtained powder coating was measured by a pendulum type viscoelasticity meter (DDV-OPA) manufactured by Orientec Co., Ltd., 1 It was 40.
し た が っ て 、 こ の粉体塗料 を 用 い る 場合 の被塗装物 の 予備加熱処理温度 は、 4 5 で よ り も 高 く 1 5 0 以下の 温度範囲で あ る 。 Therefore, the preheating temperature of the object to be coated in the case of using this powder coating is higher than 45 and higher than 150.
(静電塗装 と 粉体塗料 の 回収） (Recovery of electrostatic coating and powder coating)
厚 さ 0 . 8 m m の リ ン酸亜鉛処理 を 施 し た鋼鈑 に ポ リ ウ レ タ ン水性塗料 （三井東圧化学 （株） 製 の V D 1 0 0 N ) を 厚 さ 1 0 /z m に 塗装 し て被塗装物 を 作製 し た 。 こ の 被塗装物 を l o o t に加熱 し 、 直 ち に コ ロ ナ式粉体塗 装 ガ ン （小野 田 セ メ ン ト （株） 製 の G X 3 3 0 0 ) の ブ ー ス に設置 し 、 前記の粉体塗料 を 印加電圧 6 0 k V で静 電塗装 し た 。 A 0.8 mm thick zinc phosphate treated steel sheet is coated with a polyurethane aqueous paint (VD100N manufactured by Mitsui Toatsu Chemicals, Inc.) at a thickness of 10 / zm. The object to be coated was prepared by painting on the surface. The object to be coated is heated to loot and immediately placed in a bush of a corona-type powder coating gun (GX330, manufactured by Onoda Cement Co., Ltd.). The powder coating was electrostatically coated at an applied voltage of 60 kV.
こ の と き の 塗着効率 （ ％ ) [ = (塗着総量 （ g ) Z粉 体塗料 の有効 吐 出 量 （ g ) ) X I 0 0 ] は 7 5 % で あ つ た 。 At this time, the coating efficiency (%) [= (total coating amount (g) effective discharge amount of Z powder coating (g)) XI00] was 75%.
つ い で塗装 し た鋼鈑 を 2 0 0 で 1 5 分間焼 き 付 けて 塗板 を作製 し 、 次 の性質 を 調べ た 。 結果 を 表 1 に 示す。
塗膜外観 Then, the coated steel plate was baked at 200 for 15 minutes to prepare a coated plate, and the following properties were examined. Table 1 shows the results. Coating appearance
目 視 で 観察 し 、 つ ぎ の 基準 で 評価 す る 。 Observe visually and evaluate according to the following criteria.
A 塗膜表 面 に 凹 凸 が な く 平 滑 で あ る 。 A The surface of the coating film is smooth without any irregularities.
B 緩や か な 歪 み が わ ず か に あ る 。 B There is a slight distortion.
C 柚 子 肌 で あ る （ 明 ら か に 凹 凸 が あ る ） C It has citron skin (there are concavities and convexities evidently).
密 着性 Adhesion
J I S D 0 2 0 2 8 . 1 2 に 準 じ て 碁 盤 目 試験 を 行 な う Perform a grid test in accordance with J IS D 0 2 0 2 8.
実施例 2 〜 3 お よ び 比 較例 1 〜 2 Examples 2 to 3 and Comparative Examples 1 to 2
つ ぎ に 示す被 塗 装 物 を 使 用 し 、 被 塗装 物 の 加 熱温度 を 表 1 に 示す温度 と し た ほ か は実施 例 1 と 同 様 に し て 静電 塗装 お よ び焼 き 付 け を 行 な い 、 塗着効 率 お よ び塗膜特性 を 調 べ た 。 結 果 を 表 1 に 示す 。 Using the coating materials shown in the following table, and setting the heating temperature of the coating materials to the temperature shown in Table 1, the electrostatic coating and baking were performed in the same manner as in Example 1. The coating efficiency and the properties of the coating film were examined. Table 1 shows the results.
( 被 塗装 物 ） (Object to be painted)
実施例 2 ： 実施例 1 で 使用 し た ウ レ タ ン 塗装 前 の リ ン 酸 化 成 処 理鋼 鈑。 Example 2: The phosphoric acid-treated steel sheet used in Example 1 before urethane coating.
実施例 3 ： 何 の 処 理 も さ れ て い な い 鋼 鈑。 Example 3: A steel sheet that has not been subjected to any treatment.
比較例 1 お よ び 2 ： 実施例 1 と 同 じ ウ レ タ ン 塗 装鋼 鈑。 Comparative Examples 1 and 2: Same urethane coated steel sheet as in Example 1.
被塗装物加熱温度塗着効率 膜厚 塗膜特性 Workpiece heating temperature Coating efficiency Thickness Film properties
(°C) (%) ( M m) 外観（平滑性） 密着性 実施例 1 100 75 50 A 100/100 実施例 2 100 65 53 A 100/100 実施例 3 100 65 52 A 95/100 比較例 1 35 50 55 B 100/100 比較例 2 160 75 55 C 20/100
産業上 の 利用 可能性 (° C) (%) (M m) Appearance (Smoothness) Adhesion Example 1 100 75 50 A 100/100 Example 2 100 65 53 A 100/100 Example 3 100 65 52 A 95/100 Comparative Example 1 35 50 55 B 100/100 Comparative example 2 160 75 55 C 20/100 Industrial applicability
本発 明 の塗装方法 に よ れ ば、 1 回 あ た り の 塗着効 率 が 高 く な る の で 目 的 と す る 膜厚 を 得 る ま で の 塗装 回数 を 減 少 さ せ る こ と がで き 、 生産性が向 上す る 。 ま た 、 得 ら れ る 塗膜表面 の 平滑性 に も 優れ る の で 、 外観が良好な 塗装 品 が提供で き る 。
According to the coating method of the present invention, the efficiency of coating per coating is increased, so that the number of coatings required to obtain a target film thickness can be reduced. As a result, productivity is improved. Further, since the obtained coating film has excellent smoothness, it is possible to provide a coated product having a good appearance.
Claims
言青 求 の 範 囲 . 熱硬ィ匕型 フ ッ 素 樹脂粉体塗料 を 静電塗装す る 際 、 被 塗装物 を 該粉体塗料 の ガ ラ ス 転移温度 よ り も 高 く か つ 硬化 開 始温度 よ り も 1 0 高 い 温度以下 の 温度範 囲 に 予 め加熱 し て お く こ と を 特徴 と す る 熱硬化型 フ ッ 素樹 脂粉体塗料 の塗装方法 When the thermosetting fluorinated resin powder coating is electrostatically coated, the object to be coated is cured at a temperature higher than the glass transition temperature of the powder coating. A method of applying a thermosetting fluororesin powder coating characterized by being preheated to a temperature range of not higher than the starting temperature by 10 or more.
2 . 被塗装物 の 塗装面が、 金属 に化成処理が施 さ れて い る 面で め る 求 の 範 囲第 1 項記載 の 方法。 2. The method according to claim 1, wherein the painted surface of the object to be coated is a surface on which a chemical treatment has been applied to a metal.
3 . 被塗装物 の 塗装 面が 、 金属 に プ ラ ス チ ッ ク コ 一 テ ィ ン グ処理 ま た は塗料 に よ る 被覆処理が施 さ れて い る 面 で あ る 請求 の範 囲第 1 項記載の方法。 3. Claims in which the painted surface of the object to be coated is a surface on which the metal has been subjected to a plastic coating treatment or a coating treatment with a paint. The method of paragraph 1.
4. 被塗装物 の 塗装面が、 水性型塗料 に よ る 被覆処理が 施 さ れて い る 面 で あ る 請求 の 範囲第 3 項記載 の方法。
4. The method according to claim 3, wherein the coated surface of the object to be coated is a surface that has been coated with a water-based paint.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1999/005461 WO2001024944A1 (en) | 1999-10-04 | 1999-10-04 | Method for applying thermosetting fluororesin powder coating |
| AU60026/99A AU6002699A (en) | 1999-10-04 | 1999-10-04 | Method for applying thermosetting fluororesin powder coating |
| EP99974085A EP1230986A1 (en) | 1999-10-04 | 1999-10-04 | Method for applying thermosetting fluororesin powder coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1999/005461 WO2001024944A1 (en) | 1999-10-04 | 1999-10-04 | Method for applying thermosetting fluororesin powder coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001024944A1 true WO2001024944A1 (en) | 2001-04-12 |
Family
ID=14236902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1999/005461 WO2001024944A1 (en) | 1999-10-04 | 1999-10-04 | Method for applying thermosetting fluororesin powder coating |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1230986A1 (en) |
| AU (1) | AU6002699A (en) |
| WO (1) | WO2001024944A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10139971A1 (en) * | 2001-08-21 | 2003-03-27 | Rodenstock Optik G | Optical lens or glass with a marking and / or marking on the front and / or back surface |
| WO2017111541A3 (en) * | 2015-12-24 | 2017-08-10 | 엘지전자 주식회사 | Method of manufacturing dew formation preventing member, and refrigerator and evaporator having dew formation preventing member |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61111335A (en) * | 1984-11-05 | 1986-05-29 | Dainippon Toryo Co Ltd | Molding of plastic |
| JPH06114321A (en) * | 1991-01-10 | 1994-04-26 | John Lysaght Australia Ltd | Method and device for continuous coating to moving strip-like metal body |
| JPH07148458A (en) * | 1993-09-17 | 1995-06-13 | Nippon Paint Co Ltd | Coating method |
-
1999
- 1999-10-04 WO PCT/JP1999/005461 patent/WO2001024944A1/en not_active Application Discontinuation
- 1999-10-04 EP EP99974085A patent/EP1230986A1/en not_active Withdrawn
- 1999-10-04 AU AU60026/99A patent/AU6002699A/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61111335A (en) * | 1984-11-05 | 1986-05-29 | Dainippon Toryo Co Ltd | Molding of plastic |
| JPH06114321A (en) * | 1991-01-10 | 1994-04-26 | John Lysaght Australia Ltd | Method and device for continuous coating to moving strip-like metal body |
| JPH07148458A (en) * | 1993-09-17 | 1995-06-13 | Nippon Paint Co Ltd | Coating method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10139971A1 (en) * | 2001-08-21 | 2003-03-27 | Rodenstock Optik G | Optical lens or glass with a marking and / or marking on the front and / or back surface |
| WO2017111541A3 (en) * | 2015-12-24 | 2017-08-10 | 엘지전자 주식회사 | Method of manufacturing dew formation preventing member, and refrigerator and evaporator having dew formation preventing member |
| US10801774B2 (en) | 2015-12-24 | 2020-10-13 | Lg Electronics Inc. | Method of manufacturing dew formation preventing member and refrigerator and evaporator having dew formation preventing member |
| US11340009B2 (en) | 2015-12-24 | 2022-05-24 | Lg Electronics Inc. | Method of manufacturing dew formation preventing member and refrigerator and evaporator having dew formation preventing member |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1230986A1 (en) | 2002-08-14 |
| AU6002699A (en) | 2001-05-10 |
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