KR19980051217A - Primer aqueous solution for preparing the lower coating film and a method for producing a double polymer resin coating film having excellent adhesion using the same - Google Patents
Primer aqueous solution for preparing the lower coating film and a method for producing a double polymer resin coating film having excellent adhesion using the same Download PDFInfo
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- KR19980051217A KR19980051217A KR1019960070091A KR19960070091A KR19980051217A KR 19980051217 A KR19980051217 A KR 19980051217A KR 1019960070091 A KR1019960070091 A KR 1019960070091A KR 19960070091 A KR19960070091 A KR 19960070091A KR 19980051217 A KR19980051217 A KR 19980051217A
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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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
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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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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Abstract
본 발명은 하부 도막 제조용 프라이머 수용액 및 이를 이용한 다음 열용사하여 고분자 수지 도막을 제조하는 방법에 관한 것으로, 아크릴산을 15-20% 함유하는 폴리에틸렌 아크릴산 공중합체중 아크릴산 성분과 수산화암모늄중 암모니아 성분이 1:1 당량비가 되도록 상기 공중합체와 수산화암모늄수용액이 혼합된 프라이머 수용액 및 상기 프라이머 수용액을 금속 피도물 표면에 도포하여 수지 하도막을 형성하는 단계, 및 상기 하부 도막상에 폴리올레핀계 고분자 수지를, 열용사하여 올레핀계 상도막을 형성하는 단계, 를 포함하는 접착력이 우수한 이중 고분자 수지 도막 제조 방법이 제공된다.The present invention relates to a primer aqueous solution for preparing a lower coating film and a method for preparing a polymer resin coating film by thermal spraying using the same, wherein the acrylic acid component and the ammonia component of ammonium hydroxide in a polyethylene acrylic acid copolymer containing 15-20% of acrylic acid are 1: 1. Applying an aqueous primer solution mixed with the copolymer and an aqueous ammonium hydroxide solution and an aqueous solution of the primer to a surface of a metal coating to form a resin undercoat, and thermally thermally spraying a polyolefin-based polymer resin on the lower coating film to form an equivalent ratio. Forming a top coat, there is provided a method for producing a double polymer resin coating film having excellent adhesive strength.
본 발명에서는 접착력이 우수한 하도막을 제조한 다음 2중으로 상도막을 제조하여 이중 도막을 형성함으로써 철판에 접착력이 우수하였다.In the present invention, an excellent coating force was prepared, and then a double coat was formed by forming a top coat layer in duplicate, thereby providing excellent adhesion to an iron plate.
Description
본 발명은 하부 도막 제조용 프라이머 수용액 및 이를 이용하여 접착력이 우수한 이중 고분자 수지 도막을 제조하는 방법에 관한 것으로, 보다 상세하게는 프라이머 수용액을 제조한 다음 도포하여 하도막을 형성하고 고분자 수지를 열용사에 의하여 상도막으로 형성하여 접착력이 우수한 이중 고분자 수지 도막을 제조하는 방법에 관한 것이다.The present invention relates to a primer aqueous solution for preparing a lower coating film and a method for producing a double polymer resin coating film having excellent adhesive strength by using the same. More specifically, a primer aqueous solution is prepared and then applied to form a undercoat, and the polymer resin is heated by thermal spraying. The present invention relates to a method for producing a double polymer resin coating film having excellent adhesion by forming a top coat film.
종래에 고분자 물질을 코팅하는 경우 코팅과 피도물 표면과의 접착력은 코팅에 요구되는 물성 중에서 가장 중요한 특성이며, 피도물 표면에서 코팅막이 탈착되는 것을 방지하기 위하여 여러 가지 방법이 개발되어 왔다.Conventionally, when coating a polymer material, the adhesion between the coating and the surface of the coating is the most important property among the properties required for coating, and various methods have been developed to prevent the coating film from being detached from the surface of the coating.
피도물과의 접착력을 증가시키기 위한 방법으로는 샌드 블라스트 혹은 쇼트 블라스트를 이용하여 피도물 표면의 형상을 거칠게 하여 고분자 피막과의 접촉 표면적을 늘리는 방법이 피도물의 표면 전처리에 주로 이용뢰었다.As a method for increasing adhesion to the coating, a method of increasing the surface area of contact with the polymeric coating by roughening the surface of the coating using sand blast or shot blast has been mainly used for surface pretreatment of the coating.
또한 피도물의 표면에 피도물과의 접착력이 우수하며 동시에 후속 코팅제와의 접착성이 우수한 수지를 피도물의 표면에 도포함으로써 피도물 표면을 전처리하여 코팅의 접착력을 크게 하는 프라이머를 도포하는 방법이 사용되고 있다.In addition, a method of applying a primer to increase the adhesive strength of the coating by pretreating the surface of the coating object by applying a resin having excellent adhesion with the coating material to the surface of the coating material and at the same time having excellent adhesion to the coating agent on the surface of the coating material.
올레핀계 고분자 피막재료의 경우 수지 자체의 물성이 피도물과의 접착력이 좋지않으며, 표면 거칠기를 증가시키는 표면 처리 방법은 표면 거칠기가 증가하여 접촉표면적을 크게한 만큼 효과는 있으나 올레핀계 고분자 수지의 접착 특성상 일반적으로 고분자 피막 재료에 요구되는 접착력을 나타내지는 못하는 것이 보통이다.울레핀계 고분자 수지중 일종인 폴리에틸렌을 자체로 피막 성형하는 경우 고분자피막과 피도물이 흔히 박리되었으며 이 경우에는 피도물의 표면 거칠기를 증가시키더라도 폴라에틸렌의 수지 특성상 고분자 피막에 충분한 접착력을 얻을 수 없다. 기존에 올레핀계 고분자 피막의 표면 접착성을 높이기 위하여 피도물의 표면에 유기 용매를 사용하여 고분자 수지를 용해한 형태의 프라이머를 피도물의 표면에 도포하여 프라이머 피막을 형성하여 피도물과 고분자 피막 사이의 접착력을 크게 하는 방법이 개시되었으며 주로 올레핀계 수지의 압출 및 분체 도장에 의한 고분자 피막의 융착에 사용되고 있다.In the case of the olefin polymer coating material, the physical property of the resin itself is poor in adhesion to the coating material, and the surface treatment method for increasing the surface roughness is effective as the surface roughness increases to increase the contact surface area, but due to the adhesive properties of the olefin polymer resin In general, it is not common to exhibit the required adhesion to the polymeric coating material. When the polyethylene film, which is a type of olefin polymer resin, is formed by itself, the polymer coating and the coating are frequently peeled off, and in this case, the surface roughness of the coating is increased. Even if it is made, sufficient adhesive force cannot be obtained to a polymer film by the resin characteristic of polyethylene. In order to improve the surface adhesion of the olefinic polymer film, a primer in the form of a polymer resin dissolved in the surface of the coating object is coated on the surface of the coating material to form a primer coating to greatly increase the adhesion between the coating material and the polymer coating. The method of the present invention has been disclosed, and is mainly used for fusion of polymer films by extrusion of olefin resins and powder coating.
프라이머를 사용하는 종래의 방법은 고분자 수지의 용해를 위하여 유기 용제를 사용함으로써 작업 조건이 열악해지고, 열경화성 고분자 수지를 사용한 프라이머의 경우에는 유기 용제에 의한 유해 물질의 발생 이외에 프라이머 피막 성형시 열경화성 수지의 경화에 시간이 걸리고 프라이머 수지와 올레핀계 코팅재사이에 상용성이좋지 않은 단점이 있다.In the conventional method using a primer, the working conditions are poor by using an organic solvent for dissolving the polymer resin, and in the case of the primer using the thermosetting polymer resin, in addition to the generation of harmful substances by the organic solvent, It takes a long time to cure and has a disadvantage of poor compatibility between the primer resin and the olefinic coating material.
또한 올레핀계 프라이머 수용액에 관한 특허 제 92-18188에서 나타나듯이 염소화폴리올레핀을 사용하는 경우 열용사시 고분자 분말 원료이 부분 연소하여 염산 증기가 발생하며 또한 프라이머용 수지로 사용된 비닐 아세테이트 에틸렌 공중합체중 에틸렌의 중량비가 25-30중량%에 불과하여 고분자 사슬중에서 폴리에틸렌이 차지하는 비율이 상대적으로 낮아 올레핀계 고분자 피막 재료와의 상용성, 코팅후 수분 침투시 안정성 그리고 올레핀계 고분자 재료에 비하여 도막 자체의 기계적 물성이 저하하였다.In addition, as shown in Patent No. 92-18188 for an aqueous solution of an olefin primer, when chlorinated polyolefin is used, the polymer powder raw material is partially burned during thermal spraying to generate hydrochloric acid vapor, and the weight ratio of ethylene in the vinyl acetate ethylene copolymer used as the primer resin. Is only 25-30% by weight, and the proportion of polyethylene in the polymer chain is relatively low, making it compatible with the olefinic polymer coating material, the stability of water penetration after coating, and the mechanical properties of the coating film itself compared to the olefinic polymer material. It was.
이에 본 발명에서는 열용사에 의한 올레핀계 수지로된 도막 제조시 수용성이므로 유기 용제를 사용하지 않아 작업 조건에 간편하며, 열용사 공정상 염산 증기 등 인체에 유해물이 생성되지 않고 피도물 표면과의 접착성이 우수하고 올레핀계 코팅재료와 상용성이 우수하며 수분 접촉시 프라이머 수지의 흡습에 따른 물성의 변화가 없는 프라이머 수용액을 제조하여 도포한 다음 그위에 올레핀계 수지를 열용사하여 피도물과의 접착성이 우수한 이중 고분자 수지 도막을 제조하는 방법에 관한것이다.Therefore, in the present invention, since it is water-soluble in the production of coating film made of olefin resin by thermal spraying, it is easy to work condition without using organic solvent, and it does not produce harmful substances to human body such as steam of hydrochloric acid in the thermal spraying process and adheres to the surface of the workpiece. It is excellent in compatibility with the olefinic coating material, and prepared by applying the aqueous primer solution that does not change the physical properties of the primer resin due to moisture absorption, and then apply thermal coating of the olefinic resin on the surface to adhere to the coating material It is related with the method of manufacturing the outstanding double polymer resin coating film.
본 발명의 일견지에 의하면, 아크릴산을 15-20% 함유하는 폴리에틸렌 아크릴산 공중합체중 아크릴산 성분과 수산화암모늄중 암모니아 성분이 1 : 1 당량비가 되도록 상기 공중합체와 수산화암모늄수용액이 혼합된 프라이머 수용액이 제공된다.According to one aspect of the present invention, there is provided a primer aqueous solution in which the copolymer and the aqueous ammonium hydroxide solution are mixed such that the acrylic acid component in the polyethylene acrylic acid copolymer containing 15-20% of acrylic acid and the ammonia component in ammonium hydroxide are in a 1: 1 equivalent ratio. .
본 발명의 다른 견지에 의하면, 제1견지에 의해 제조된 프라이머 수용액을 금속 피도물 표면에 도포하여 수지 하도막을 형성하는 단계 및 상기 하부 도막상에 폴리올레핀계 고분자 수지를 열용사하여 올레핀계 상도막을 형성하는 단계를 포함하는 접착력이 우수한 이중 고분자 수지 도막을 제조하는 방법이 제공된다.According to another aspect of the present invention, by applying the primer aqueous solution prepared by the first aspect to the surface of the metal coating to form a resin undercoat film and thermally spraying polyolefin-based polymer resin on the lower coating film to form an olefin-based top coat Provided is a method for producing a double polymer resin coating film having excellent adhesive strength comprising the step.
이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
100부의 물에 아크릴산을 15-20% 함유하는 폴리에틸렌 아크릴산 공중합체중 아크릴산 성분과 수산화암모늄중 암모니아 성분이 1 : 1 당량비가 되도록 폴리에틸렌 아크릴산 공중합체와 수산화암모늄 수용액을 혼합한 다음 교반하여 수성 현탁화한 프라이머 수용액을 제조하였다.100 parts of water in the polyethylene acrylic acid copolymer containing 15-20% acrylic acid and the acrylic acrylic component and the ammonium hydroxide ammonia component is mixed so that a 1: 1 equivalent ratio of the polyethylene acrylic acid copolymer and an aqueous solution of ammonium hydroxide, and then stirred and aqueous suspension An aqueous solution was prepared.
아크릴산을 15중량% 미만으로 함유하는 경우 폴리에틸렌 아크릴산 공중합체의 수용성 현탁액을 제조하기가 어렵고, 20중량% 이상으로 함유하는 경우는 고분자 수지중의 아크릴산의 비중이 커서 물에 분산하기는 쉬우나 물에 대한 내수성이 다소 떨어지므로 금속 표면에 도포하고 건조한 다음에 이어서 열용사할 코팅 재료의 프라이머로 사용한 경우에 물이 코팅을 통과하여 금속과 프라이머의 접착면에 도달할 경우 접착력을 저해할 수 있다.When containing less than 15% by weight of acrylic acid, it is difficult to prepare a water-soluble suspension of polyethylene acrylic acid copolymer, when containing more than 20% by weight of acrylic acid is easy to disperse in water due to the high specific gravity of the polymer resin, but water resistance As this slightly falls, when applied to the metal surface and dried and then used as a primer of the coating material to be thermally sprayed, water may pass through the coating and impede adhesion when the metal reaches the adhesive surface of the primer.
상기 아크릴산은 물에 불용성이므로 물에 용해시킬 목적으로 암모니아를 함께 사용하였다. 암모니아가 과량이면 미반응 암모니아가 많아지므로 악취가 나고 경제성이떨어지며 암모니아가 소량이면 중합체를 물에 수화시키기가 어려운 것이다, 따라서첨가하는 암모니아의 함량은 아크릴산에 대하여 1 : 1 당량비가 바람직하다.Since the acrylic acid is insoluble in water, ammonia was used together for the purpose of dissolving in water. If the amount of ammonia is excessive, the amount of unreacted ammonia increases, resulting in bad smell and economical efficiency. If the amount of ammonia is small, it is difficult to hydrate the polymer in water. Therefore, the amount of added ammonia is preferably 1: 1 equivalent to acrylic acid.
상기 프라이머 수용액을 표면 오염이 제거된 상태의 열연 강판 및 알루미늄 피도물상에 도포한 후 건조하여 하도막을 제조하였다. 상기 하도막이 형성된 피도막물의표면 온도를 약 100℃정도로 예열한 다음 폴리올레핀계 수지를 고분자 열용사기를 시용하여 상도막을 형성하였다.The primer solution was applied onto a hot rolled steel sheet and an aluminum coating object in which surface contamination was removed, and then dried to prepare a undercoat. The surface temperature of the coating film on which the undercoating film was formed was preheated to about 100 ° C., and then a polyolefin resin was applied to a polymer thermal sprayer to form a top coating film.
상기 열용사처리할 피도막물로는 11㎝ × 11㎝ 이고 두께 2.0㎜의 열연 강판 및 알루미늄판을 사용 하였다.As the coating material to be thermally sprayed, a hot rolled steel sheet and an aluminum plate having a thickness of 11 cm × 11 cm and a thickness of 2.0 mm were used.
상기 예열 온도는 열용사도막의 물성에 영향을 미치는 요인으로서 온도가 적정온도를 넘어 과열될 경우 용사 불꽃에 의해 불이 옮겨 붙을 수 있으므로 바람직하지 않다.The preheating temperature is not preferable because it may cause a fire by the thermal spray flame when the temperature is overheated as a factor affecting the properties of the thermal sprayed coating film.
상기 열용사용 폴리올레핀계 코팅제로는 입자크기가 60-200미크롱인 기존의 고밀도폴리에틸렌, 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 초고분자량 폴리에틸 및 에틸렌 비닐알콜 공중합체 분말을 사용하였다.As the thermal coating polyolefin-based coating agent, conventional high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylenyl and ethylene vinyl alcohol copolymer powder having a particle size of 60-200 microns were used.
본 발명에서는 접착력이 우수한 하도막을 제조한 다음 열용사에 의하여 상도막을 제조하여 이중 도막을 형성함으로써 철판에 접착력이 우수하였다.In the present invention was prepared by the excellent coating film and then the top coat by thermal spraying to form a double coating film was excellent in adhesion to the iron plate.
[실시 예 ]EXAMPLE
본 실시예에서는 100부의 물에 아크릴산 20중량%를 함유하는 폴리에틸렌 아크릴산공중합체 25부를 28% 수산화암모늄 수용액 13부와 혼합하여 아크릴산과 암모니아의 당량비가 1 : 1이 되도록 하고 90℃에서 교반하여 수성현탁한 프라이머 수용액을 제조하였다.In this embodiment, 25 parts of polyethylene acrylic acid copolymer containing 20 parts by weight of acrylic acid in 100 parts of water are mixed with 13 parts of aqueous 28% ammonium hydroxide solution so that the equivalence ratio of acrylic acid and ammonia is 1: 1 and stirred at 90 ° C. for aqueous suspension. One primer aqueous solution was prepared.
상기 프라이머 수용액에 100부의 물을 가하여 회석한 용액을 유기 용매로 세척하여 표면 오염이 제거된 상태의 열연 강판 및 알루미늄 피도물상에 액상으로 도포한 다음 건조하여 하도막을 형성하였다.100 parts of water was added to the primer solution to wash the solution, which was then rinsed with an organic solvent, applied to the hot rolled steel sheet and aluminum coated object in a state where surface contamination was removed, and then dried to form a undercoat.
11㎝×11㎝, 두께 2.0㎜인 열연 강판 및 알루미늄판을 시편으로 사용하였으며 작업시에 피도물의 표면 온도는 약 100℃ 정도로 예열하여 성형하여 상도막을 형성하였다.A hot rolled steel sheet and an aluminum sheet having a thickness of 11 cm × 11 cm and a thickness of 2.0 mm were used as specimens. The surface temperature of the workpiece was preheated to about 100 ° C. to form a top coat.
미리 제조된 하도막상에 폴리올레핀계 수지를 사용하여 코팅하였다.It coated on the previously prepared undercoat using polyolefin resin.
상기 코팅은 불꽃형 용사에 의하여 실시하였으며, 열용사하는 폴리올레핀계 코팅제로는 입자 크기가 60-200 미크롱의 고밀도 폴리에틸렌, 저밀도 폴리에틸렌, 선형저밀도 폴리에틸렌, 초고분자량 폴리에틸렌 및 에틸렌 비닐알콜 공중합체 분말을사용하였다.The coating was performed by flame spraying, and the thermally sprayed polyolefin-based coating agent used was 60-200 microns of high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, and ethylene vinyl alcohol copolymer powder. It was.
상기한 방법으로 이중 도막을 형성한 시편에 폭 1㎝의 흠집을 내고 지그에 물려 필(peel) 시험을 거쳐 인장 강도를 측정하였다.The specimen which formed the double coating film by the above-mentioned method was made the width | variety 1cm of the scratch, and was bitten by the jig, and the tensile strength was measured through the peel test.
상기 측정한 시편을 90°로 박리하여 측정한 접착력 시험의 결과를 하기표 1에 나타내였다.Table 1 shows the results of the adhesion test measured by peeling the measured specimen at 90 °.
상기표에서 보듯이 프라이머 수용액으로 하도막을 형성한 박리시편은 모두 접착력이 도막의 인장 강도보다 커서 도막이 찢겨서 박리 현상이 관찰되지 않았으며 하도막을 형성하지 않은 무처리 시편의 경우에는 시편 성형후 고분자 괴막 재료의 열수축에 의하여 자연 박리되었다. 특히 에틸렌 비닐알콜 공중합체의 경우 열용사한 시편에서 자연 박리되지는 않았으나 박리 시험에서 박리되었다.As shown in the table above, all the peeled specimens formed with the primer film in aqueous solution were larger than the tensile strength of the coating film, so that the peeling was not observed due to the tearing of the coating film. It naturally peeled off by the heat shrink of the material. In particular, the ethylene vinyl alcohol copolymer was not spontaneously peeled off from the thermally sprayed specimen, but was peeled off in the peel test.
따라서 본 발명의 방법에 의하여 2중으로 도막을 형성한 경우 도막의 접착력이 우수하였다.Therefore, when the coating film was formed by the method of the present invention in double, the adhesion of the coating film was excellent.
본 발명에서는 접착력이 우수한 하도막을 제조한 다음 열용사에 의해 상도막을 제조하여 이중 도막을 형성함으로써 철판에 접착력이 우수하였다.In the present invention, the undercoating film having excellent adhesive strength was prepared, and then the top coating film was prepared by thermal spraying to form a double coating film.
Claims (2)
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|---|---|---|---|
| KR1019960070091A KR100264981B1 (en) | 1996-12-23 | 1996-12-23 | Primer solution and film menufacturing method |
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| KR1019960070091A KR100264981B1 (en) | 1996-12-23 | 1996-12-23 | Primer solution and film menufacturing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190108693A (en) * | 2018-03-15 | 2019-09-25 | 조용래 | Coating method of spray surface |
| KR20210079843A (en) * | 2019-12-20 | 2021-06-30 | 주식회사 포스코 | Adhesive coating composition for electrical steel sheet, electrical steel sheet laminate, and method for manufacturing the electrical steel sheet product |
| WO2021125859A3 (en) * | 2019-12-20 | 2021-08-05 | 주식회사 포스코 | Electrical steel sheet adhesive coating composition, electrical steel sheet laminate, and method for manufacturing same |
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1996
- 1996-12-23 KR KR1019960070091A patent/KR100264981B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190108693A (en) * | 2018-03-15 | 2019-09-25 | 조용래 | Coating method of spray surface |
| KR20210079843A (en) * | 2019-12-20 | 2021-06-30 | 주식회사 포스코 | Adhesive coating composition for electrical steel sheet, electrical steel sheet laminate, and method for manufacturing the electrical steel sheet product |
| WO2021125859A3 (en) * | 2019-12-20 | 2021-08-05 | 주식회사 포스코 | Electrical steel sheet adhesive coating composition, electrical steel sheet laminate, and method for manufacturing same |
| WO2021125860A3 (en) * | 2019-12-20 | 2021-08-05 | 주식회사 포스코 | Adhesive coating composition for electrical steel sheet, electrical steel sheet laminate, and method for manufacturing same |
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