KR20170032747A - Paint composition for dry plating of automobile aluminum wheel - Google Patents
Paint composition for dry plating of automobile aluminum wheel Download PDFInfo
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- KR20170032747A KR20170032747A KR1020150130526A KR20150130526A KR20170032747A KR 20170032747 A KR20170032747 A KR 20170032747A KR 1020150130526 A KR1020150130526 A KR 1020150130526A KR 20150130526 A KR20150130526 A KR 20150130526A KR 20170032747 A KR20170032747 A KR 20170032747A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- C09D7/12—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
- B60B2360/00—Materials; Physical forms thereof
- B60B2360/10—Metallic materials
- B60B2360/104—Aluminum
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Abstract
Description
The present invention relates to a luminescent, semi-luminous and semi-luminous intermediate coating composition for dry plating applied to a sputtering process, which is a dry process for producing high-brightness aluminum wheels for automobiles.
As a method for plating automobile parts, wet plating methods such as electroless plating and electrolytic plating are mainly used. In the wet plating method, electroless plating of nickel (Ni) or copper (Cu) is performed on a product which has been subjected to an etching process and an activating process, followed by electrolytic plating using chromium (Cr). The surface coating by the wet plating method is widely applied to decorative materials such as automobiles, furniture, household appliances, etc. In particular, since the surface of a plastic molded article is activated by a chemical agent, a plating film having excellent adhesion can be obtained.
Despite these advantages, however, the wet plating method has the disadvantage that most of the various chemical agents used for wet plating contain heavy metal substances, and the discharge of industrial wastewater containing such heavy metal substances provides a direct cause of environmental pollution In addition, it causes problems such as overpayment of indirect capital for purification of wastewater.
Therefore, it is necessary to study the technology for manufacturing automobile parts, especially aluminum wheels by the dry plating method.
Korean Patent No. 10-0971290 (Patent Document 1) discloses an aluminum wheel dry plating method in " a method of manufacturing a sputtering wheel by a hot coating. &Quot; However, the above-mentioned patent discloses a method of coating a polyester-based liquid paint with an air-spraying method using a heavy-weight coating composition, which is applied to a wheel as a result of a defect in coating film during long-term property tests such as salt water repellency, water resistance, In addition, there are difficulties in mass production due to problems such as rainbow and white light in mass production.
The present invention provides a coating composition suitable for a mid layer coating of automotive aluminum wheels, which is applicable to the dry plating method and which improves the adhesion between the undercoating layer (powder coating) and the metal sputtering layer during the metal sputtering process, To provide a coating composition which improves smoothness to give a high brightness appearance and which improves mechanical properties such as water resistance, salt water repellency, scrubbing resistance, moisture resistance and heat resistance.
Further, it is intended to provide an environmentally friendly coating composition containing no heavy metal.
In order to accomplish the above object, the present invention provides a thermosetting coating composition capable of dry plating with a coating composition used for middle layer coating of an automobile aluminum wheel, wherein the undercoat layer, the intermediate layer, the metal sputtering layer and the top layer are sequentially In a laminated aluminum wheel, a coating composition for forming the intermediate layer is provided. More specifically, the present invention provides a mid layer coating composition for dry plating of automobile aluminum wheels, which comprises a polyurethane resin, a drying agent, a storage stabilizer, a leveling agent and a curing agent.
In the intermediate layer coating composition for dry plating of automobile aluminum wheels according to an embodiment of the present invention, the polyurethane resin is prepared by reacting a (meth) acrylate compound having a polyisocyanate, a polybutadiene-based polyol and a hydroxyl group ≪ / RTI >
The polyurethane resin may have a weight average molecular weight ranging from 7,000 to 12,000 g / mol. The intermediate layer coating composition for dry plating of automobile aluminum wheels according to an embodiment of the present invention may be a polyurethane resin.
According to an embodiment of the present invention, there is provided an intermediate layer coating composition for dry coating of an automobile aluminum wheel, wherein the drying agent is selected from the group consisting of copper-naphthanate, zirconium-naphthanate, manganese-naphthanate, manganese- -Laurate and manganese-naphthalene, or a mixture of two or more thereof.
In the intermediate layer coating composition for dry plating of automotive aluminum wheels according to an embodiment of the present invention, the storage stabilizer may be selected from hydroquinone, hydroquinone monomethyl ether, and mixtures thereof.
The leveling agent may be at least one selected from the group consisting of ethylene glycol, polyethylene glycol, monolauryl ether, polyimine, ethylenediamine, polyether-modified polysiloxane, acrylonitrile, A polymer and a polydimethylsiloxane, or a mixture of two or more thereof.
In the intermediate layer coating composition for dry plating of an automobile aluminum wheel according to an embodiment of the present invention, the curing agent may be selected from benzoyl peroxide, di-methylperoxide and mixtures thereof.
The intermediate layer coating composition for dry plating of automobile aluminum wheels according to an embodiment of the present invention may further comprise a liquid quencher containing a silica compound, a dispersant and an anti-settling agent. At this time, the silica compound may be a silica quencher or silica treated with a hydrophilic polyolefin wax.
In the intermediate layer coating composition for dry plating of automobile aluminum wheels according to an embodiment of the present invention, the dispersant may be selected from DISPERBYK-103, DISPERBYK-110, DISPERBYK-161 and mixtures thereof.
In the intermediate layer coating composition for dry plating of an automobile aluminum wheel according to an embodiment of the present invention, the anti-settling agent may be selected from fumed silica, modified urea, polyhydroxycarboxylic acid amide, and mixtures thereof.
The intermediate layer coating composition for dry-painting of a car aluminum wheel according to an embodiment of the present invention may be cured at a temperature ranging from 200 to 300 ° C for 10 to 60 minutes.
The present invention provides an aluminum wheel comprising a mid layer coating composition for dry plating of the automobile aluminum wheel described above.
The intermediate layer coating composition for dry plating of automobile aluminum wheels according to the present invention can be coated through a dry plating process and can be applied with excellent adhesion, water resistance, salt water repellency, scratch corrosion resistance, moisture resistance, acid resistance and alkali resistance In addition, there is an advantage that an environmentally friendly aluminum wheel can be manufactured because it does not contain heavy metals.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a film structure of an aluminum wheel. Fig.
Hereinafter, preferred embodiments of the intermediate coating composition for dry plating of automobile aluminum wheels of the present invention will be described in detail. However, this is not intended to limit the scope of protection defined by the claims. In addition, technical terms and scientific terms used in the description of the present invention have the meanings as commonly understood by those of ordinary skill in the art to which the present invention belongs, unless otherwise defined.
The inventors of the present invention are characterized by using an intermediate layer coating composition for dry-painting aluminum wheels containing a polyurethane resin, a drying agent, a storage stabilizer, a leveling agent and a curing agent.
Specifically, the intermediate layer coating composition for dry plating of the present invention is for forming an intermediate coat layer of an aluminum wheel. As can be seen in Fig. 1, the aluminum wheel is layered on top of the aluminum sequentially with a sublayer, a middle layer, a metal sputtering layer and a top layer. For example, the aluminum wheel forms an undercoating layer of epoxy or epoxy polyester powder coating on top of aluminum and forms a mid layer on top of the undercoating layer. In addition, a metal sputtering layer formed of sputtering metal such as aluminum, chromium, nickel, or sulfur is formed on the upper part of the intermediate layer, and a top layer using powder transparent coating material is formed on the metal sputtering layer.
The present invention relates to a coating composition for forming the intermediate layer, wherein the adhesion between the primer layer and the metal sputtering layer and the surface smoothness of the polyurethane resin are controlled by a combination of specific components including a drying agent, a storage stabilizer, a leveling agent, It is possible to provide a middle layer coating composition capable of realizing excellent mechanical properties at the same time as being applicable to a dry plating method and further realizing an environmentally friendly effect, thus completing the present invention .
Specifically, the intermediate layer coating composition for dry painting of automobile aluminum wheels according to the present invention comprises 30 to 80% by weight of a polyurethane resin, 0.01 to 1% by weight of a desiccant, 0.01 to 1% by weight of a storage stabilizer, 0.01 to 1% 0.01 to 1% by weight of a hardening agent, and a residual amount of a solvent. Examples of the solvent include, but are not necessarily limited to, one or more components selected from
In the present invention, the polyurethane resin acts as a base for forming a coating film. The polyurethane resin reacts with a polyisocyanate, a polybutadiene-based polyol and a reactive group, preferably a (meth) acrylate compound having a hydroxyl group (-OH group) Respectively. This is excellent in adhesion to the metal film and improves physical properties such as salt water resistance, water resistance and corrosion resistance.
As the polyisocyanate compound, Diisocyanato-diphenylmethane, Toluene diisocyanate, or the like can be used, but the present invention is not limited thereto.
Examples of the (meth) acrylate compound having a reactive group (-OH group) include 2-hydroxypropylmethacrylate, 2-hydroxyethylmethacrylate, 2- ethyl (2-Ethylhydroxyacrylate), and the like, but the present invention is not limited thereto.
The diene compound is not particularly limited, but polybutadiene-based polyols can be used. For example, polybutadieneglycol, polybutadienedicarbonic acid, and the like can be used.
In the present invention, it is more preferable that the polyurethane resin has a weight average molecular weight of 7,000 to 12,000 g / mol, and preferably 8,000 to 10,000 g / mol. In the above range, excellent physical properties such as salt water repellency, water resistance, moisture resistance, and corrosion resistance can be exhibited. Here, the weight average molecular weight is measured by a GPC-MALS (Multi Angle Light Scattering) system (Wyatt), and is a conventional method.
The content of the polyurethane resin is preferably 30 to 80% by weight based on the total weight of the intermediate layer coating composition. When the content is less than 30% by weight, the thickness of the coating film becomes thin and the brightness is poor. When the content is used in excess of 80% by weight, leveling may be poor during coating, more preferably 40 to 60% by weight It is better to do it.
In the present invention, the liquid quencher is used to control the gloss of the semi-light and the moon, and is characterized by including a silica compound, a dispersant, a precipitation inhibitor and a solvent. In case of glossy, no liquid quencher is added. In case of semi-gloss and matte, a liquid quencher may be added to the glossy coating to adjust the desired gloss. In this case, the liquid quencher may be contained in an amount of 0.01 to 20% by weight.
Although the silica compound is not particularly limited, it is preferable to use a silica quencher, more preferably a hydrophilic polyolefin wax. At this time, it is more preferable to use silica having a particle diameter of 2 to 20 mu m. The content of the silica compound is preferably 10 to 20% by weight.
DISPERBYK-103, DISPERBYK-110 and DISPERBYK-161 of BYK Additives & Instruments Co., Ltd. are preferably used, and the content thereof may be 10 to 20% by weight.
The precipitation inhibitor may be fumed silica, modified urea solution, polyhydroxycarboxylic acid amide solution or the like, and the content thereof may be 0.5 to 2% by weight. The solvent is not particularly limited, but for example, 30 to 60 wt% of xylene or 10 to 30 wt% of diacetone alcohol may be used.
In the present invention, the desiccant is used to accelerate the curing, and is preferably a copper-naphthanate, zirconium-naphthenate, manganese-naphthenate, manganese naphthenate (CAS No. 1336-93-2) And metal drying agents such as stearate, manganese-laurate, manganese-naphthalene and the like can be used. In this case, the drying agent may be used in an amount of 0.01 to 1% by weight in the whole composition. The amount of the metal to be added is preferably 0.0001 to 0.5% by weight. When the metal content is less than 0.0001 wt%, the curing is slowed, resulting in poor appearance during metal sputtering due to the intermediate uncured curing. When the metal content exceeds 0.5 wt%, there is a problem in storage stability of the coating.
In the present invention, the curing agent is used for promoting internal curing of the coating material, and a peroxide type curing agent such as benzoyl peroxide or dicumyl peroxide may be used, but not always limited thereto. The content thereof may be 0.001 to 0.01% by weight. When it is used in an amount of less than 0.001% by weight, the curing is slowed to cause a serious uncured state. When the amount is used in excess of 0.01% by weight, there is a problem in storage stability of the coating material.
In the present invention, the storage stabilizer is used for improving storage stability and storage stability, and may be selected from hydroquinone, hydroquinone monomethyl ether, and mixtures thereof. The content thereof is 0.001 to 0.01% by weight. If it is used in an amount less than 0.001% by weight, the effect of storage stability will not increase, and if it is used in an amount exceeding 0.01% by weight, it may adversely affect the drying of the coating material.
In the present invention, the leveling agent used for increasing the surface smoothness may be any one or more selected from ethylene glycol, polyethylene glycol, monolauryl ether, polyimine, ethylenediamine, polyether-modified polysiloxane and polyacrylate copolymer Mixtures may be used. The content thereof may be 0.006% by weight. When it is used in an amount less than 0.002% by weight, surface wettability is insufficient and creta ring is generated or leveling becomes poor. When it is used in excess of 1.0% by weight, adherence to metal sputtering becomes poor.
The process for manufacturing an automotive aluminum wheel using the intermediate coating composition for dry plating according to the present invention is as follows.
1) Aluminum surface smoothing process by mechanical polishing
Aluminum wheels are manufactured through casting and the surface is partially oxidized to form rough and pitted holes. Therefore, the aluminum wheel is mechanically polished to smooth the surface of the aluminum wheel.
2) Pretreatment process
Next, by removing contaminants such as foreign matter and oil on the aluminum wheel surface and etching the surface of the aluminum wheel, it is possible to remove the oxide film on the surface of the aluminum wheel and to neutralize the surface of the aluminum wheel And a pretreatment step comprising a coating step for improving the corrosion resistance and adhesion and a water reducing step for completely removing moisture remaining on the aluminum wheel.
3) Undercoating process
Thereafter, a powder primer coating process is carried out. A polyester or epoxy type gray or black powder coating material is coated on the surface of the aluminum wheel subjected to the pretreatment step to a thickness of about 150 탆 by corona electrostatic painting and then dried at 190 캜 for 40 minutes to form a lower coating layer.
4) Medium Coating Process
The intermediate coating process forms an intermediate coating layer by applying the intermediate coating composition according to the present invention and thermosetting it.
The intermediate layer coating composition for dry plating according to the present invention can be cured by heat treatment at 200 to 300 ° C for 10 to 60 minutes.
5) Metal sputtering process
In the metal sputtering process, an alloy such as chromium, nickel, SUS, aluminum or the like is used to put a wheel into a vacuum chamber, and then argon, which is an inert gas, is injected in a vacuum state. The emitted electrons collide with argon gas to ionize argon, A metal thin film of about 0.1 탆 is formed on the surface of the aluminum wheel by exchanging momentum with atoms protruding from the wheel surface.
6) Top coating process
In the top coating process, an acrylic type transparent powder coating material is coated in a thickness of 40 to 50 탆 and dried at 180 캜 for 70 minutes to form a top coat layer.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.
The following physical properties were measured by the following measurement methods. At this time, the evaluation method is indicated as ○, 80 to 99% when it satisfies the condition (Hyundai, Kia Automobile standard) in each physical property evaluation item, but less than 80% when it is not proper, and × when it is not.
(1) Water resistance
After immersing in a water bath at 40 DEG C for 120 hours,
① There should be no noticeable film softening, whitening, swelling
② Secondary adhesion should be M-2.5 or higher.
(2) Flushing with salt water
After 720 hours after salt spray,
① There should be no rust and swelling on the side of 3mm or more from one side from scratch.
② Tape peel test was conducted after 1 hour after removing the specimen, and peeling should not occur at a position more than 3mm on one side from the scratch portion
(3) Intrinsic corrosion
Apply the equilibrium water (soil: 1% NaCl aqueous solution = 1: 2 solution) uniformly over the entire surface of the test specimen and leave it in the room for 24 hours and then put it in a holding chamber of temperature 50 ℃ and humidity 85% RH for 500 hours. After completion of the test, the sample is cleaned and evaluated.
The soil to be used is made of rust soot (particle size less than 100), which is commercially available for bonsai, and deionized water is used for water.
Condition: Not to be broadcast in 500 hours
(4) Moisture resistance
After 120 hours of charging in a constant-temperature and constant-humidity chamber at 40 캜 and a humidity of 90%, 1 hour after taking out, the occurrence of softening, whitening and swelling of the coating film was visually observed.
① There should be no noticeable film softening, whitening, discoloration, swelling
② Secondary adhesion should be M-2.5 or higher.
(5) Acid resistance
0.2 liters of a test solution (0.5% sulfuric acid solution) was spotted on the surface of the coating film and allowed to stand at room temperature for 2 hours at 25 DEG C, to visually observe softening, whitening and swelling of the coating film.
Condition: There should be no noticeable film softening, whitening, discoloration, swelling, etc.
(6) Alkalinity
After immersing in a 5% sodium carbonate solution at room temperature for 8 hours and 1 hour after taking out, the occurrence of softening, whitening, and swelling of the coating film was visually observed.
Condition: There should be no noticeable film softening, whitening, discoloration, swelling, etc.
(7) Heavy metal content (ppm)
Lead: IEC 62321 Ed.1 (ICP)
Cernium: IEC 62321 Ed.1 (ICP)
Mercury: IEC 62321 Ed.1 (CV-AAS)
Meat chrome: IEC 62321 Ed.1 (UV / Vis)
Conditions: Lead, cadmium, mercury, hexavalent chromium should not be detected.
(8) Film thickness
The average value of film thickness was determined using an electronic film thickness meter (CHECK-LINE, DCN-900, USA). At this time, the corner portion and the non-wetting were measured using a microscope.
(9) Adhesiveness
Measure the degree of peeling after tape peel test in 2mm interval checkerboard scale
Condition: The standard specified in 6.8.1 of MS600-35 of the Kia Motors Technical Standard
(Examples and Comparative Examples)
1) Undercoating process
The composition for the undercoat layer was coated on the aluminum wheel to a thickness of 150 mu m by corona electrostatic coating and then dried at 190 DEG C for 40 minutes to form a subbing layer. As the composition for the undercoat layer, an epoxy polyester paint was used.
2) Medium Coating Process
Thereafter, the coating composition for a middle layer was coated in a thickness of 40 탆 by electrostatic spray coating, and then thermally cured at 250 캜 for 40 minutes to form a middle layer. At this time, the coating composition for the intermediate layer was prepared and used in the following manner.
Middle floor Preparation of Coating Composition
Examples 1, 2, and Comparative Examples were prepared in the compositions shown in Table 1 below.
Specifically, in Example 1, 50 wt% of a polyurethane resin (trade name: RAU-100, product of Kumegang Paint Co., Ltd., weight average molecular weight: 9,000 g / mol), a desiccant (5% manganese- 0.001% by weight of a hardening agent (benzoyl peroxide), 0.005% by weight of a storage stabilizer (hydroquinone) and 0.07% by weight of a polyether-modified polysiloxane, 10% by weight of coke sol # 10 wt% of diacetone alcohol, and 24.815 wt% of toluene were mixed to prepare a middle layer glossy coating composition. Example 2 was also prepared by mixing 12 parts by weight of a liquid quencher with 100 parts by weight of the luminescent coating composition of Example 1 as an intermediate layer semi-gloss coating composition. The liquid quencher was composed of 18% by weight of silica (SiO 2 , average particle size 6 μm), 14% by weight of dispersing agent (DISPERBYK-103), 1% by weight of modified urea solution, 54% by weight of xylene and 13% by weight of diacetone alcohol will be.
3) Metal sputtering process
Thereafter, aluminum was deposited on the surface by a metal sputtering method to form a metal thin film with a thickness of 0.1 mu m.
4) Top coating process
Thereafter, the composition for the upper layer was coated to a thickness of 50 탆 by an electrostatic spray coating method and dried at 180 캜 for 70 minutes to form an upper layer. At this time, an acrylic type transparent powder coating material was used as the composition for the upper layer layer.
As shown in the following Table 1, the intermediate layer coating composition was prepared by varying the components of the composition, and the physical properties of the aluminum wheel were measured and shown in Table 2 below. The components used are as follows.
* Acrylic resin (R-1): Acrylic resin Thermosetting acrylic resin SW-50
* Acrylic resin (R-2): Acrylic resin Thermosetting acrylic resin AA-1556
* Alkyd resin (R-3): Acryl-modified alkyd resin RAJ-200
* Polyurethane resin (R-4): Geumgang paint industry RAU-100
* Melamine resin (M-1): Dahlung Enterprise DR4910
* Benzoguanamine Resin (M-2): Hitach Chemical (Japan) MELAN X-81
* Acrylic copolymer (A-1): BYK Chemie BYK-358N
* Blocked acid catalyst (A-2): KING INDUSTRIES NACURE2530
* Manganese naphthenate (A-3): Mn-Naphthenate
[Table 1]
[Table 2]
As can be seen from Table 2, it can be seen that Examples 1 and 2 according to the present invention can exert excellent effects in dry plating applied to automotive high-luminance wheels. On the other hand, Comparative Examples 1 to 8 have different compositions from the composition according to the present invention, and thus are unsatisfactory in appearance, adhesion, water resistance, salt water repellency, corrosion resistance, and moisture resistance.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
100: aluminum wheel, 200: underlayer, 300: intermediate layer
400: sputtering layer, 500: upper layer
Claims (13)
Wherein the polyurethane resin is produced by reacting a polyisocyanate, a polybutadiene-based polyol and a (meth) acrylate compound having a hydroxy group.
Wherein the polyurethane resin has a weight average molecular weight of 7,000 to 12,000 g / mol.
The desiccant may be any one or a mixture of two or more selected from among copper-naphthanate, zirconium-naphthanate, manganese-naphthanate, manganese-stearate, manganese- Layer coating composition for plating.
Wherein the storage stabilizer is selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, and mixtures thereof.
The leveling agent is used for dry-painting an automobile aluminum wheel, which is any one or a mixture of two or more selected from ethylene glycol, polyethylene glycol, monolauryl ether, polyimine, ethylenediamine, polyether-modified polysiloxane, acrylic copolymer and polydimethylsiloxane The intermediate layer coating composition.
Wherein the curing agent is selected from benzoyl peroxide, di-methylperoxide and mixtures thereof.
Wherein the coating composition further comprises a liquid quencher consisting of a silica compound, a dispersant and an anti-settling agent.
Wherein the silica compound is silica treated with a hydrophilic polyolefin wax.
Wherein the dispersant is selected from DISPERBYK-103, DISPERBYK-110, DISPERBYK-161, and mixtures thereof.
Wherein the precipitation inhibitor is selected from fumed silica, modified urea, polyhydroxycarboxylic acid amide, and mixtures thereof.
Wherein the dry coating intermediate layer coating composition is cured at a temperature in the range of 200 to 300 캜 for 10 to 60 minutes.
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KR100971290B1 (en) | 2008-03-06 | 2010-07-20 | 승현창 | Sputtering wheel manufacturing method with thermosetting paint |
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