KR20110076374A - Insulation coating material of non-orient electrical steel sheet, method of manufacturing and insulation coating material and method of forming insulation coating layer - Google Patents
Insulation coating material of non-orient electrical steel sheet, method of manufacturing and insulation coating material and method of forming insulation coating layer Download PDFInfo
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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Abstract
Description
본 발명은 무 방향성 전기 강판용 절연코팅제, 절연코팅제 제조방법 및 절연피막의 형성방법에 관한 것으로서, 인체에 유해한 크롬을 포함하지 않으면서 절연피막의 내식성 및 응력제거 소둔 후 밀착성 우수한 절연피막을 형성할 수 있는 무 방향성 전기 강판용 절연코팅제, 절연코팅제 제조방법 및 절연피막의 형성방법을 제공한다. The present invention relates to an insulating coating agent for a non-oriented electrical steel sheet, a method for manufacturing an insulating coating agent and a method for forming an insulating coating, and can be formed to excellent adhesion after annealing corrosion resistance and stress relief annealing without containing chromium harmful to the human body. The present invention provides an insulating coating agent for a non-oriented electrical steel sheet, a method for preparing an insulating coating agent and a method for forming an insulating coating.
일반적으로 소형전동기나 변압기 등과 같은 전기 기기용 철심으로 사용되는 무 방향성 전기 강판은 와전류 발생을 억제하여 전력손실을 적게 하기 위하여 그 표면에 절연피막 처리제를 이용하여 절연피막을 형성시킨다. 이러한 무 방향성 전기 강판에 코팅된 절연피막은 절연성 이외에도 용접성, 응력제거 소둔 전후 밀착성 및 내식성이 우수할 것이 요구된다.In general, non-oriented electrical steel sheets used as iron cores for electric appliances such as small electric motors and transformers form an insulating coating on the surface by using an insulating coating agent on the surface in order to suppress eddy currents and reduce power loss. The insulating coating coated on the non-oriented electrical steel sheet is required to have excellent weldability, adhesiveness before and after stress relief annealing and corrosion resistance in addition to insulation.
상기 절연피막 형성용 절연코팅제는 크게 유기질 조성물, 무기질 조성물 또 는 유무기 하이브리드 조성물의 세 종류로 분류될 수 있다. 최근 들어서는 강판 표면의 품질이 사용특성에 영향을 미치는 것이 알려지면서, 표면 품질이 우수한 전기 강판이 요구되고 있다. 이 중 유무기 하이브리드 조성물은 무기질 피막 조성물의 장점과 유기질 피막 조성물의 장점을 함께 가질 수 있다. 일본특허 소50-15013호에는 무기성분으로 중크롬산 염과 유기성분으로 초산비닐, 부타디엔-스티렌 공중합물, 아크릴 수지 등의 유기수지 에멀젼을 주성분으로 하는 처리액을 이용하여 절연피막을 형성하는 것에 의해 우수한 밀착성 및 펀칭성 등의 피막특성을 부여하고, 또한 응력제거 소둔 후에도 양호한 피막특성을 갖는 절연피막 형성방법이 개시되었다. 하지만, 통상의 유 무기 하이브리드 절연피막 처리제는 내식성등 피막의 요구 특성을 확보하기 위해 크롬산을 포함하기 때문에 상기 예시한 절연피막 처리제 또한 크롬산화물 함유가 필수적이고, 이에 따라 환경규제가 강화되고 있는 현실에 비추어 절연코팅제 조성물을 제조할 때 및 절연코팅제 조성물을 대상물에 도포할 때 크롬산의 피부접촉 등에 의한 인체에의 악영향 및 폐수배출에 따른 환경문제 유발이 되므로 그 용도가 제한적이다. The insulating coating agent for forming an insulating coating may be largely classified into three types of organic composition, inorganic composition or organic-inorganic hybrid composition. In recent years, it is known that the quality of the steel sheet surface affects the use characteristics, and there is a demand for an electric steel sheet having excellent surface quality. Among these, the organic-inorganic hybrid composition may have both the advantages of the inorganic coating composition and the advantages of the organic coating composition. Japanese Patent No. 50-15013 discloses an excellent insulating film by forming an insulating coating using a treatment liquid containing a dichromate salt as an inorganic component and an organic resin emulsion such as vinyl acetate, butadiene-styrene copolymer, and acrylic resin as an organic component. A method of forming an insulating coating having imparting coating characteristics such as adhesion and punching properties and having good coating characteristics even after stress relief annealing has been disclosed. However, since the conventional inorganic hybrid insulating coating agent contains chromic acid in order to secure the required properties of the coating, such as corrosion resistance, the insulating coating agent exemplified above also needs to contain chromium oxide. In view of the above, the use of the insulating coating agent composition and the application of the insulating coating agent composition to the object are limited due to the adverse effects on the human body due to chromic acid and environmental problems due to waste water discharge.
따라서, 크롬을 함유하지 않으면서도 절연성, 응력제거 소둔 전후 밀착성 및 내식성 등의 절연피막 특성을 확보하기 위한 방법으로 크롬산염 대신에 금속인산염을 도입 또는 콜리이달 실리카를 도입하는 방법이 제안되었다. 이러한 예로서, 일본공개특허 제2004-322079에서는 알루미늄, 칼슘 및 아연의 금속염을 사용하여 밀착성과 내식성을 향상시키는 방법에 대하여 기재되어 있고, 일본특허 제3,370,235호에서는 절연피막 처리제로서 콜로이달 실리카를 도입하여 밀착성을 향상시키는 기술이 기재되어 있다. 그러나, 상술한 기술들에서는 예시한 알루미늄, 칼슘 및 아연의 금속인산염을 주성분으로 하는 절연피막 코팅제를 사용하기 때문에 이로 인해 형성된 절연피막은 응력제거소둔 후 밀착성 및 절연피막의 내식성이 취약한 문제점을 갖는다. 또한 콜로이달 실리카를 이용하는 크롬프리 절연피막 코팅제는 내식성이 저하되고 용액의 안정성이 나쁘다는 한계를 각각 가지고 있어 이를 이용하여 크롬산염을 대체하는 것은 아직 어려운 실정이다. Therefore, a method of introducing metal phosphate or colloidal silica in place of chromate has been proposed as a method for securing insulation coating properties such as insulation, adhesion before and after stress relief annealing and corrosion resistance without chromium. As such an example, Japanese Patent Laid-Open No. 2004-322079 describes a method of improving adhesion and corrosion resistance by using metal salts of aluminum, calcium and zinc, and Japanese Patent No. 3,370,235 introduces colloidal silica as an insulating coating agent. To improve adhesion. However, in the above-described techniques, since the insulating coating coating mainly composed of metal phosphates of aluminum, calcium, and zinc is used, the insulating coating formed therein has a problem in that the adhesion and the corrosion resistance of the insulating coating are poor after stress relief annealing. In addition, chromium-free insulating coating using colloidal silica has a limit of corrosion resistance and poor solution stability, so it is still difficult to replace chromate using it.
본 발명의 목적은 크롬산화물을 포함하지 않는 대신 나노입자 크기의 자기가교형 에멀젼 수지와 금속산화물 복합염을 주요성분으로 하는 유무기 하이브리드 혼합 절연피막 처리제인 무 방향성 전기 강판용 절연코팅제를 제공하는데 있다. An object of the present invention is to provide an insulating coating agent for non-oriented electrical steel sheet, which is an organic-inorganic hybrid mixed insulating coating agent containing a chromium oxide and a nanoparticle-sized self-crosslinking emulsion resin and a metal oxide complex salt as main components.
본 발명의 다른 목적은 크롬산화물을 포함하지 않는 대신 나노입자 크기의 자기가교형 에멀젼 수지와 금속산화물 복합염을 주요성분으로 포함하는 무 방향성 전기 강판용 절연코팅제의 제조방법을 제공하는데 있다.It is another object of the present invention to provide a method for preparing an insulating coating agent for an non-oriented electrical steel sheet, which does not include chromium oxide but includes a nanoparticle-sized self-crosslinking emulsion resin and a metal oxide composite salt as main components.
본 발명의 또 다른 목적은 크롬을 포함하지 않으면서도 내식성과 응력제거소둔 후 피막밀착성이 우수한 무 방향성 전기 강판용 절연피막을 형성하는데 있다.Still another object of the present invention is to form an insulating film for non-oriented electrical steel sheet having excellent corrosion-resistance and film adhesion after stress relief annealing without containing chromium.
상술한 목적을 달성하기 위한 본 실시예에 따른 무 방향성 전기 강판용 절연코팅제는 아래와 같은 조성을 갖는다. 상기 무 방향성 전기 강판용 절연코팅제는 무기 금속산화물과 산소산의 반응으로 형성된 금속산화물 복합염 47 내지 57 중량부, 자기가교형 에멀젼 수지 25 내지 35 중량부, 소재 습윤성을 향상시키기 위한 비실리콘계 첨가제 0.1 내지 0.5 중량부, 얼룩을 방지하기 위한 프로필렌글리콜 5 내지 10 중량부, 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 3내지 7 중량부 및 이온 교환수 3 내지 7 중량부를 포함한다. Insulation coating agent for a non-oriented electrical steel sheet according to the present embodiment for achieving the above object has the following composition. The insulation coating agent for non-oriented electrical steel sheet 47 to 57 parts by weight of the metal oxide composite salt formed by the reaction of the inorganic metal oxide and oxygen acid, 25 to 35 parts by weight of the self-crosslinking emulsion resin, 0.1 to 0.5 non-silicone additive for improving the material wettability By weight, 5 to 10 parts by weight of propylene glycol to prevent staining, 3 to 7 parts by weight of phosphate-epoxysilane compound to improve the gloss and adhesion of the insulating film and 3 to 7 parts by weight of ion-exchanged water.
일 예로서, 상기 금속산화물 복합염은 무기 금속산화물과 인산(H3PO4) 및 붕 산(H3BO4)을 포함하는 산소산이 반응함으로서 형성되는 고형분 45 내지 47중량%인 복합 금속산화물 염이다. 상기 무기 금속산화물은 알루미늄(Al)산화물, 마그네슘(Mg)산화물 및 아연(Zn)산화물 등을 적어도 하나이상 포함할 수 있다.As an example, the metal oxide complex salt is a composite metal oxide salt having a solid content of 45 to 47% by weight formed by the reaction of an inorganic metal oxide with an oxygen acid including phosphoric acid (H 3 PO 4 ) and boric acid (H 3 BO 4 ). to be. The inorganic metal oxide may include at least one of aluminum (Al) oxide, magnesium (Mg) oxide and zinc (Zn) oxide.
일 예로서, 상기 자기가교형 에멀젼 수지는 고형분이 42 내지 46중량%이고, pH가 4 내지 4.5이며, 10 내지 100nm의 입자크기를 갖는 에멀젼 수지이다.As an example, the self-crosslinking emulsion resin is an emulsion resin having a solid content of 42 to 46% by weight, a pH of 4 to 4.5, and a particle size of 10 to 100nm.
상술한 본 발명의 다른 목적을 달성하기 위한 무 방향성 전기 강판용 절연코팅제는 아래와 같은 방법으로 제조될 수 있다. 상기 절연코팅제를 제조하기 위해서는 먼저 무기 금속산화물과 산소산의 반응으로 형성된 금속산화물 복합염을 마련한다. 고형분이 42 내지 46중량%이고, pH가 4 내지 4.5이며, 10 내지 100nm의 입자크기를 갖는 자기가교형 에멀젼 수지를 마련한다. 인산-에폭시실란 화합물을 마련한다. 이후 상기 금속산화물 복합염 47 내지 57 중량부, 자기가교형 에멀젼 수지 25 내지 35 중량부, 소재 습윤성을 향상시키기 위한 비실리콘계 첨가제 0.1 내지 0.5 중량부, 얼룩을 방지하기 위한 프로필렌글리콜 5 내지 10 중량부, 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 3 내지 7 중량부 및 이온 교환수 3 내지 7 중량부를 혼합 반응시킨다. 이에 따라, 무 방향성 전기 강판용 절연코팅제가 완성될 수 있다.Insulation coating agent for non-oriented electrical steel sheet for achieving the above another object of the present invention can be prepared by the following method. In order to prepare the insulation coating agent, first, a metal oxide composite salt formed by reaction of an inorganic metal oxide and an oxygen acid is prepared. A self-crosslinking emulsion resin having a solid content of 42 to 46% by weight, a pH of 4 to 4.5 and a particle size of 10 to 100 nm is prepared. A phosphoric acid-epoxysilane compound is prepared. 47 to 57 parts by weight of the metal oxide composite salt, 25 to 35 parts by weight of the self-crosslinking emulsion resin, 0.1 to 0.5 parts by weight of the non-silicone additive to improve the material wettability, 5 to 10 parts by weight of propylene glycol to prevent staining And 3 to 7 parts by weight of a phosphoric acid-epoxysilane compound and 3 to 7 parts by weight of ion-exchanged water to improve the gloss and adhesion of the insulating film. Accordingly, an insulation coating agent for non-oriented electrical steel sheet can be completed.
상술한 본 발명의 또 다른 목적을 달성하기 위한 무 방향성 전기 강판용 절연피막은 아래와 같은 방법으로 형성될 수 있다. 절연피막을 형성하기 위해서는 먼저 무기 금속산화물과 산소산의 반응으로 형성된 금속산화물 복합염 47 내지 57 중 량부, 10 내지 100nm의 입자크기를 갖는 자기가교형 에멀젼 수지 25 내지 35 중량부, 소재 습윤성을 향상시키기 위한 비실리콘계 첨가제 0.1 내지 0.5 중량부, 얼룩을 방지하기 위한 프로필렌글리콜 5 내지 10 중량부, 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 3 내지 7 중량부 및 이온 교환수 3 내지 7 중량부를 혼합 반응시켜 무 방향성 전기 강판용 절연코팅제 마련한다. 상기 무 방향성 전기 강판용 절연코팅제를 강판 상에 코팅하여 코팅막을 형성한다. 상기 코팅막을 530 내지 750℃로 설정된 가열로에서 열처리한다. 그 결과 상기 강판에는 무 방향성 전기 강판용 절연피막이 형성된다.Insulating coating film for non-oriented electrical steel sheet for achieving another object of the present invention described above may be formed by the following method. In order to form an insulating film, 47 to 57 parts by weight of a metal oxide composite salt formed by the reaction of an inorganic metal oxide and an oxygen acid, 25 to 35 parts by weight of a self-crosslinkable emulsion resin having a particle size of 10 to 100 nm, and improve the material wettability 0.1 to 0.5 parts by weight of non-silicone additive, 5 to 10 parts by weight of propylene glycol to prevent staining, 3 to 7 parts by weight of phosphoric acid-epoxysilane compound to improve the gloss and adhesion of the insulating film and 3 to 7 of ion-exchanged water A weight part is mixed and reacted to prepare an insulating coating agent for non-oriented electrical steel sheet. The insulating coating agent for the non-oriented electrical steel sheet is coated on a steel sheet to form a coating film. The coating film is heat-treated in a heating furnace set to 530 to 750 ℃. As a result, an insulating film for non-oriented electrical steel sheet is formed on the steel sheet.
이상에서 설명한 본 발명의 무 방향성 전기 강판용 절연코팅제는 응력제거소둔 전후 밀착성 및 내식성이 우수한 등의 절연피막을 형성할 수 있는 절연피막 형성용 조성물로 인체에 유해한 크롬을 포함하지 않음에도 불구하고 크롬을 포함하는 기존의 전기 강판용 절연피막과 동일한 물성을 갖는 절연피막을 형성할 수 있어 환경 친화적이다. 상술한 방향성 전기 강판용 절연코팅제로 형성된 절연피막은 크롬을 함유하지 않고 절연피막의 밀착성, 절연성, 외관, 내식성 및 광택이 우수한 특성을 갖는다. Insulation coating agent for non-oriented electrical steel sheet of the present invention described above is a composition for forming an insulating film capable of forming an insulating film, such as excellent adhesion and corrosion resistance before and after stress relief annealing, even though it does not contain chromium that is harmful to the human body. It is possible to form an insulating film having the same physical properties as the existing insulating film for electrical steel sheet containing, it is environmentally friendly. The insulating coating formed of the insulating coating agent for a grain-oriented electrical steel sheet described above does not contain chromium and has excellent adhesiveness, insulation, appearance, corrosion resistance and gloss of the insulating coating.
이하, 본 발명에 따른 바람직한 실시예들에 따른 무 방향성 전기 강판용 절연코팅제, 절연코팅제 제조방법 및 절연피막 제조방법을 하기 실시예들을 참조하여 상세히 설명한다. 그러나, 이는 본 발명을 특정한 실시예들의 형태에 대해 한정하 려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 상세한 설명에서 사용되는 다양한 구성요소들은 기재된 용어들에 의해 한정되어서는 안 된다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "이루어진다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Hereinafter, the insulating coating agent for an unoriented electrical steel sheet, the insulating coating agent manufacturing method and the insulating film manufacturing method according to the preferred embodiments of the present invention will be described in detail with reference to the following examples. However, this is not intended to limit the invention to the form of specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. Various components used in the detailed description should not be limited by the terms described. The terms are used only for the purpose of distinguishing one component from another. The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "consist of" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described on the specification, but one or more other features. It is to be understood that the present disclosure does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, or a combination thereof. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.
무 방향성 전기 강판용 절연코팅제Insulation coating agent for non-oriented electrical steel sheet
본 발명의 무 방향성 전기 강판용 절연코팅제는 전기기기에 적용되는 강판 (무 방향성 전기 강판)에 밀착성, 내식성등이 우수한 절연피막을 형성하기 위한 크롬산화물을 포함하지 않는 코팅제이다. 즉, 무 방향성 전기 강판용 절연코팅제는 크롬을 포함하지 않음에도 불구하고 기존의 크롬산화물을 포함하는 전기 강판용 절연코팅제로 형성된 절연피막과 동일 또는 우수한 물성을 갖는 절연피막을 형성할 수 있다.The insulating coating agent for non-oriented electrical steel sheet of the present invention is a coating agent containing no chromium oxide for forming an insulating coating having excellent adhesion, corrosion resistance, and the like on a steel sheet (non-oriented electrical steel sheet) applied to an electric apparatus. That is, although the insulating coating agent for non-oriented electrical steel sheet does not contain chromium, an insulating coating having the same or superior physical properties as the insulating coating formed of the existing insulating coating agent for electrical steel sheet containing chromium oxide may be formed.
무 방향성 전기 강판용 절연코팅제는 금속산화물 복합염, 자기가교형 에멀젼 수지, 소재 습윤성을 향상시키기 위한 비실리콘계 첨가제, 얼룩을 방지하기 위한 프로필렌글리콜, 형성하고자하는 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 및 이온 교환수를 포함한다. 구체적으로 무기 금속산화물과 산소산의 반응으로 형성된 금속산화물 복합염 47 내지 57 중량부, 자기가교형 에멀젼 수지 25 내지 35 중량부, 소재 습윤성을 향상시키기 위한 비실리콘계 첨가제 0.1 내지 0.5 중량부, 얼룩을 방지하기 위한 프로필렌글리콜 5 내지 10 중량부, 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 3 내지 7 중량부 및 이온 교환수 3 내지 7 중량부가 혼합된 조성을 갖는다. Insulating coating agent for non-oriented electrical steel sheet, metal oxide complex salt, self-crosslinking emulsion resin, non-silicone additive to improve material wettability, propylene glycol to prevent staining, phosphoric acid to improve gloss and adhesion of insulating film to be formed An epoxysilane compound and ion exchanged water. Specifically, 47 to 57 parts by weight of the metal oxide composite salt formed by the reaction of the inorganic metal oxide and the oxygen acid, 25 to 35 parts by weight of the self-crosslinking emulsion resin, 0.1 to 0.5 parts by weight of the non-silicone additive to improve the material wettability, preventing stains 5 to 10 parts by weight of propylene glycol, 3 to 7 parts by weight of phosphoric acid-epoxysilane compound and 3 to 7 parts by weight of ion-exchanged water to improve the gloss and adhesion of the insulating film.
금속산화물 복합염은 무기 금속산화물과 인산(H3PO4) 및 붕산(H3BO4)을 포함하는 산소산이 반응함으로서 형성되는 복합 금속산화물 염이다. 일 예로서, 금속산화물 복합염은 45 내지 47중량%의 고형분을 갖는다. 상기 무기 금속산화물은 알루미늄(Al)산화물, 마그네슘(Mg)산화물 및 아연(Zn)산화물 등을 포함하며. 이들은 둘 이상 적용될 수 있다. 금속산화물 복합염은 무 방향성 전기 강판용 절연코팅제에서 피복제의 성분으로 도입될 경우 소재인 전기 강판 표면에 존재하는 규소 및 철 성분과 화학적 결합을 형성함으로써 피복제와 소재와의 밀착성을 향상시킬 뿐만 아니라 내열성이 우수한 절연피막 형성제로서 중요한 역할을 한다.The metal oxide complex salt is a complex metal oxide salt formed by reacting an inorganic metal oxide with an oxygen acid including phosphoric acid (H 3 PO 4 ) and boric acid (H 3 BO 4 ). As one example, the metal oxide composite salt has a solid content of 45 to 47% by weight. The inorganic metal oxide may include aluminum (Al) oxide, magnesium (Mg) oxide, zinc (Zn) oxide, and the like. These may be applied in more than one. When the metal oxide composite salt is introduced as a coating component in an insulating coating agent for non-oriented electrical steel sheet, the metal oxide composite salt not only improves the adhesion between the coating agent and the material by forming a chemical bond with the silicon and iron components present on the surface of the electrical steel sheet. It plays an important role as an insulating film forming agent having excellent heat resistance.
상기 금속산화물 복합염은 금속산화물의 인산염과 붕산염을 포함할 수 있다. 일 예로서, 상기 인산염은 정확하게 인산 수소염으로 명명되고, 화합물 내에서 해리성의 수소원자를 함유하며, 금속원자가 2가 및 3가의 가수를 가진다. 상기 인산 수소염의 형태로는 인산의 해리상태에 따라 제1염, 제2염, 제3염의 형태가 존재하지만, 본 실시예에서는 제1 인산 알루미늄(Al(H2PO4)2), 제1 인산 마그네슘(Mg(H2PO4)2)과 제1 인산 아연(Zn(H2PO4)2) 등이 혼합된 인산 수소염이 사용될 수 있다. 또한, 상기 금속화합물의 붕산염은 전기 강판 절연피막의 내열성을 향상시켜 응력제거소둔 후 소재와의 밀착성을 향상시킨다. 따라서 본 발명의 금속산화물의 붕산염은 제1붕산 알루미늄(Al(H2BO4)2), 제1붕산 마그네슘(Mg(H2BO4)2)과 제1붕산 아연(Zn(H2BO4)2) 형태로 사용된다. 종래의 기술에서는 상기 금속화합물의 염을 각각 제조하여 혼합하는 것을 특징으로 하였지만, 이들 금속염은 장시간 저장할 경우 안정성이 현저히 저하되어 석출에 의한 침전이 발생하여 저장안정성을 확보하기 어렵다. 따라서 본 발명에서는 이러한 단점을 극복하기 위하여 인산 및 붕산이 혼합된 산소산과 여러 금속산화물을 함께 반응시킴으로써 저장안정성을 특히 향상된 금속산화물 복합염을 적용하는 것을 특징으로 하고 있다.The metal oxide composite salt may include phosphate and borate salts of metal oxides. As an example, the phosphate salt is exactly named hydrogen phosphate salt, contains dissociable hydrogen atoms in the compound, and the metal atoms have divalent and trivalent valences. The hydrogen phosphate salt forms a first salt, a second salt, and a third salt depending on the dissociation state of the phosphoric acid, but in the present embodiment, the first aluminum phosphate (Al (H 2 PO 4 ) 2 ), Hydrogen phosphate salt in which magnesium phosphate (Mg (H 2 PO 4 ) 2 ) and first zinc phosphate (Zn (H 2 PO 4 ) 2 ) and the like are mixed may be used. In addition, the borate of the metal compound improves the heat resistance of the electrical steel sheet insulation coating to improve the adhesion to the material after the stress relief annealing. Accordingly, the borate salt of the metal oxide of the present invention may include first aluminum borate (Al (H 2 BO 4 ) 2 ), first magnesium borate (Mg (H 2 BO 4 ) 2 ) and first zinc borate (Zn (H 2 BO 4). 2 ) It is used in the form. In the prior art, the salts of the metal compounds are prepared and mixed, respectively. However, when the metal salts are stored for a long time, the stability of the metal salts is significantly lowered, and precipitation due to precipitation occurs, making it difficult to secure storage stability. Therefore, the present invention is characterized by applying a metal oxide composite salt with a particularly improved storage stability by reacting oxygen metal mixed with phosphoric acid and boric acid and various metal oxides together to overcome this disadvantage.
상기 무방향성 전기 강판용 절연코팅제의 금속산화물 복합염이 절연피막처리 제 조성물중 47중량부 이하이면 절연피막의 유연성등이 우수해 지지만 응력제거소둔 후 유기성분이 제거됨으로 인해 절연피막을 형성하게 되는 무기성분 부족으로 소재와의 밀착성이 현저히 저하되는 문제점이 발생된다. 57중량부를 초과하면 절연코팅제에 의하여 형성된 무 방향성 전기 강판 절연피막의 광택이 현저히 저하되며, 응력제거소둔 후 유기성분인 탄화되는 문제점이 발생된다. 유기성분의 탄화는 절연피막내 무기성분을 증가를 초래하여 형성되는 절연피막의 밀착성 및 굴곡성이 현저하게 저하되는 문제점이 초래된다. 따라서 금속산화물 복합염의 사용량은 47 내지 57 중량부이고, 바람직하게는 49 내지 55 중량부이다.When the metal oxide composite salt of the insulating coating agent for non-oriented electrical steel sheet is 47 parts by weight or less in the insulating coating composition, the flexibility of the insulating coating is excellent, but the inorganic component that forms the insulating coating due to the removal of the organic component after stress removal annealing. There is a problem that the lack of adhesion with the material is significantly reduced. If it exceeds 57 parts by weight, the gloss of the non-oriented electrical steel sheet insulation film formed by the insulating coating agent is significantly lowered, and the problem of carbonization of the organic component after the stress relief annealing occurs. Carbonization of the organic component causes an increase in the inorganic component in the insulating film, resulting in a problem that the adhesion and the bendability of the insulating film formed are significantly reduced. Therefore, the amount of the metal oxide composite salt used is 47 to 57 parts by weight, preferably 49 to 55 parts by weight.
자기가교형 에멀젼 수지는 형성하고 하는 절연피막의 투명성, 밀착성, 내열성 및 내식성을 향상시킬 수 있는 이관능성 모노머가 가교된 자기가교형(self curing) 에멀젼 수지이다. 자기가교형 에멀젼 수지는 상기 무방향성 전기 강판용 절연코팅제의 유기성분으로서 코팅 피막과 피복 대상물(전기 강판) 사이의 밀착성을 높이고 피막에 유연성을 부여한다. 특히, 상기 자기 가교형 에멀젼 수지는 고형분이 42 내지 46중량%이고, pH가 4 내지 4.5이며, 10 내지 100nm의 입자크기를 갖다. The self-crosslinking emulsion resin is a self curing emulsion resin crosslinked with a bifunctional monomer capable of improving the transparency, adhesion, heat resistance and corrosion resistance of the insulating film to be formed. The self-crosslinking emulsion resin is an organic component of the insulating coating agent for non-oriented electrical steel sheet, which improves the adhesion between the coating film and the object to be coated (electric steel sheet) and imparts flexibility to the film. In particular, the self-crosslinked emulsion resin has a solid content of 42 to 46% by weight, a pH of 4 to 4.5, and a particle size of 10 to 100 nm.
절연코팅제 중에서 자기가교형 에멀젼 수지의 함량이 25 중량부 미만이면 형성되는 절연피막의 내식성 및 유연성이 저하되며, 35 중량부를 초과하면 식성 및 응력제거소둔 전의 밀착성은 향상되나 응력제거소둔 후 밀착성이 현저히 저하되는 문제점이 초래된다. 따라서 에멀젼 수지의 함량은 약 25 내지 35 중량부이고, 바람직하게는 약 27 내지 32 중량부이다. If the content of the self-crosslinking emulsion resin in the insulating coating agent is less than 25 parts by weight, the corrosion resistance and flexibility of the formed insulating film is reduced. The problem of deterioration is brought about. Therefore, the content of the emulsion resin is about 25 to 35 parts by weight, preferably about 27 to 32 parts by weight.
또한, 상기 에멀젼 수지 입자의 크기가 100nm를 초과하면 형성되는 절연피막의 투명성이 현저히 저하되어 불투명해지므로 바람직하지 않다. 상기 에멀젼 수지의 pH가 4 미만이거나 4.5를 초과할 경우 코팅제의 안정성 감소 및 형성되는 절연피막의 밀착성은 저하되는 문제점이 발생되기 때문에 바람직하지 않다.In addition, when the size of the emulsion resin particles exceeds 100nm, the transparency of the insulating film formed is significantly lowered and becomes opaque, which is not preferable. When the pH of the emulsion resin is less than 4 or more than 4.5, it is not preferable because problems of reducing the stability of the coating agent and adhesion of the insulating film formed are lowered.
일 실시예에 따른 자기가교형 에멀젼 수지는 전체중량에 대하여 이온교환수 45 내지 55 중량부, 스티렌 12 내지 17 중량부, 메틸메타아크릴레이트 12 내지 17중량부, 부틸 아크릴레이트 3내지 5 중량부, 메타크릴산 0.3 내지 0.5 중량부, 자기가교 성분인 메틸올아크릴아마이드 1 내지 3 중량부, 에멀젼 가교제인 디비닐 벤젠 0.5 내지 1.0 중량부, 개시제인 암모니움퍼설페이트(Ammonium persulfate) 0.1 내지 0.3 중량부, 음이온 계면활성제인 폴리옥시에틸렌알킬페닐에테르암모니움 설페이트계 계면활성제 1 내지 3 중량부, 반응성 계면활성제인 폴리옥시에틸렌알킬에테르계 계면활성제 약 2 내지 4 중량부로 합성되는 것을 특징으로 한다.Self-crosslinking emulsion resin according to an embodiment is 45 to 55 parts by weight of ion-exchanged water, 12 to 17 parts by weight of styrene, 12 to 17 parts by weight of methyl methacrylate, 3 to 5 parts by weight of butyl acrylate, 0.3 to 0.5 parts by weight of methacrylic acid, 1 to 3 parts by weight of methylol acrylamide as a self-crosslinking component, 0.5 to 1.0 parts by weight of divinyl benzene as an emulsion crosslinking agent, 0.1 to 0.3 parts by weight of ammonium persulfate as an initiator, 1 to 3 parts by weight of a polyoxyethylene alkyl phenyl ether ammonium sulfate-based surfactant which is an anionic surfactant, and about 2 to 4 parts by weight of a polyoxyethylene alkyl ether-based surfactant which is a reactive surfactant.
상기 스티렌의 함량이 12 중량부 미만일 경우 형성되는 절연피막의 내식성은 저하된다. 스티렌 함량이 17 중량부를 초과할 경우 에멀젼 수지의 유리전이온도 상승으로 형성되는 절연피막의 밀착성 및 유연성은 저하된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 스티렌은 약 12 내지 17 중량부가 사용되는 것이 바람직하다. If the content of the styrene is less than 12 parts by weight, the corrosion resistance of the insulating film formed is reduced. When the styrene content exceeds 17 parts by weight, the adhesion and flexibility of the insulating film formed by the glass transition temperature of the emulsion resin is lowered. Therefore, about 12 to 17 parts by weight of the styrene applied to the self-crosslinking emulsion resin is preferably used.
상기 메틸메타아크릴레이트의 함량이 12 중량부 미만일 경우 형성되는 절연피막의 투명성이 저하된다. 반면에 메틸메타아크릴레이트의 함량이 17 중량부를 초과할 경우 상기 자기가교형 에멀젼 수지의 유리전이온도 상승으로 형성되는 절연피 막의 밀착성 및 유연성은 저하된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 메틸메타아크릴레이트는 약 12 내지 17 중량부가 사용되는 것이 바람직하다. When the content of the methyl methacrylate is less than 12 parts by weight, the transparency of the insulating film formed is reduced. On the other hand, when the content of methyl methacrylate exceeds 17 parts by weight, the adhesion and flexibility of the insulating film formed by the increase in the glass transition temperature of the self-crosslinking emulsion resin is reduced. Therefore, it is preferable that about 12 to 17 parts by weight of methyl methacrylate applied to the self-crosslinking emulsion resin is used.
상기 부틸 아크릴레이트의 함량이 3중량부 미만일 경우 상기 자기가교형 에멀젼 수지 특성중 하나인 절연성은 감소된다. 반면에 부틸 아크릴레이트의 함량이 5 중량부를 초과할 경우 미 반응에 의하여 형성되는 절연피막의 표면특성은 감소된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 부틸 아크릴레이트는 약 3 내지 5 중량부가 사용되는 것이 바람직하다. When the content of the butyl acrylate is less than 3 parts by weight, the insulation, which is one of the characteristics of the self-crosslinking emulsion resin, is reduced. On the other hand, when the content of butyl acrylate exceeds 5 parts by weight, the surface properties of the insulating film formed by unreacted are reduced. Therefore, about 3 to 5 parts by weight of butyl acrylate applied to the self-crosslinking emulsion resin is preferably used.
상기 메타아크릴산의 함량이 0.3중량부 미만일 경우 상기 에멀젼 수지의 pH가 증가됨으로 인해 코팅제의 경시 안정성 감소 및 형성되는 절연피막의 밀착성은 저하된다. 반면에 메타아크릴산의 함량이 0.5 중량부를 초과할 경우에도 에멀젼 수지의 pH가 증가된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 메타아크릴산은 약 0.3 내지 0.5중량부가 사용되는 것이 바람직하다. When the content of the methacrylic acid is less than 0.3 parts by weight, the pH of the emulsion resin is increased, thereby decreasing the stability of the coating over time and the adhesion of the insulating film formed is reduced. On the other hand, even when the content of methacrylic acid exceeds 0.5 parts by weight, the pH of the emulsion resin is increased. Therefore, it is preferable that about 0.3 to 0.5 parts by weight of methacrylic acid is applied to the self-crosslinking emulsion resin.
상기 메틸올아크릴아마이드의 함량이 1중량부 미만일 경우 절연피막 코팅제의 코팅후 건조시 유기성성분의 가교밀도 저하로 내열성이 저하되어 절연피막의 밀착성은 저하된다. 반면에 메틸올아크릴아마이드의 함량이 3중량부를 초과할 경우 가교밀도의 상승으로 내식성 및 밀착성은 향상되나 광택 및 절연피막의 유연성은 저하된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 메틸올아크릴아마이드 약 1 내지 3중량부가 사용되는 것이 바람직하다. When the content of the methylol acrylamide is less than 1 part by weight, heat resistance decreases due to a decrease in crosslinking density of organic components during drying after coating of the insulating coating agent, thereby decreasing the adhesion of the insulating coating. On the other hand, when the content of methylol acrylamide exceeds 3 parts by weight, the corrosion resistance and adhesion are improved due to the increase in the crosslinking density, but the gloss and the flexibility of the insulating film are reduced. Therefore, about 1 to 3 parts by weight of methylol acrylamide applied to the self-crosslinking emulsion resin is preferably used.
상기 디비닐 벤젠의 함량이 0.5 중량부 미만인 경우에 수지의 표면특성인 내식성은 감소된다. 반면에 그 함량이 1 중량부를 초과할 경우 표면 광택성은 저하된 다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 디비닐 벤젠은 약 0.5 내지 1중량부가 사용되는 것이 바람직하다. When the content of the divinyl benzene is less than 0.5 parts by weight, the corrosion resistance, which is a surface characteristic of the resin, is reduced. On the other hand, if the content exceeds 1 part by weight, the surface glossiness is lowered. Therefore, about 0.5 to 1 parts by weight of divinyl benzene applied to the self-crosslinking emulsion resin is preferably used.
상기 개시제인 암모니움 퍼설페이트 함량이 0.1 중량부 미만일 경우 에멀젼의 분자량의 증가로 인하여 에멀젼 입자의 크기가 100nm 이상으로 제조되는 문제점이 발생한다. 반면에 그 함량이 0.3 중량부를 초과할 경우 에멀젼 입자의 제조시 급격한 발열로 인해 반응물에 슬러지가 생성되는 문제점이 발생하기 때문에 바람직하지 않다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 암모니움 퍼설페이트는 약 0.1 내지 0.3 중량부를 사용하는 것이 바람직하다. When the ammonium persulfate content of the initiator is less than 0.1 part by weight, a problem arises in that the size of the emulsion particles is more than 100 nm due to an increase in the molecular weight of the emulsion. On the other hand, if the content is more than 0.3 parts by weight, it is not preferable because the sludge is generated in the reactants due to the rapid exotherm during the preparation of the emulsion particles. Therefore, it is preferable to use about 0.1 to 0.3 parts by weight of ammonium persulfate applied to the self-crosslinking emulsion resin.
상기 음이온 계면활성제인 폴리옥시에틸렌알킬페닐에테르암모니움 설페이트의 함량이 1 중량부 미만일 경우 에멀젼 입자가 100nm 이상의 크기로 제조되어 절연피막의 투명성 및 에멀젼 입자의 안정성이 저하된다. 반면에 그 함량이 3 중량부를 초과할 경우 에멀젼 수지 입자의 안정성 및 절연피막의 투명성은 확보되나 절연피막의 내습성 및 내수성이 취약해 지는 단점이 초래된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 폴리옥시에틸렌알킬페닐에테르암모니움 설페이트는 1 내지 3 중량부를 사용하는 것이 바람직하다. When the content of the polyoxyethylene alkyl phenyl ether ammonium sulfate as the anionic surfactant is less than 1 part by weight, the emulsion particles are manufactured to a size of 100 nm or more, thereby reducing the transparency of the insulating film and the stability of the emulsion particles. On the other hand, if the content exceeds 3 parts by weight, the stability of the emulsion resin particles and the transparency of the insulating film is secured, but the disadvantage is that the moisture resistance and water resistance of the insulating film becomes weak. Therefore, it is preferable to use 1 to 3 parts by weight of the polyoxyethylene alkylphenyl ether ammonium sulfate applied to the self-crosslinking emulsion resin.
상기 반응성 계면활성제인 폴리옥시에틸렌알킬에테르의 함량이 2 중량부 미만일 경우에 에멀젼 수지의 절연성이 저하된다. 반면에 그 함량이 4 중량부를 초과할 경우 형성되는 절연피막의 내습성 및 내수성이 취약해지는 문제점이 초래된다. 따라서 상기 자기가교형 에멀젼 수지에 적용되는 폴리옥시에틸렌알킬에테르는 약 2 내지 4 중량부를 사용하는 것이 바람직하다. When the content of the polyoxyethylene alkyl ether as the reactive surfactant is less than 2 parts by weight, the insulation of the emulsion resin is lowered. On the other hand, when the content exceeds 4 parts by weight, the problem that the moisture resistance and water resistance of the insulating film formed is weak. Therefore, it is preferable to use about 2 to 4 parts by weight of polyoxyethylene alkyl ether applied to the self-crosslinking emulsion resin.
상기 무방향성 전기 강판용 절연코팅제에 포함된 비실리콘계 첨가제는 약 0.1 내지 0.5 중량부가 사용되며 비실리콘계 첨가제 중에서 불소계 첨가제가 사용될 슈 있다. 상기 비실리콘계 첨가제는 상기 절연코팅제의 표면장력을 낮게 해주어 전기 강판과의 습윤성을 향상시킨다. 일 예로서, 상기 비실리콘계 첨가제는 BYK Chemie(독일)의 BYK-340(제품명)를 사용할 수 있다. 상기 비실리콘계 첨가제의 함량이 0.1 중량부 미만일 경우, 피복 조성물의 습윤성이 낮아지는 문제점이 발생되며 0.5 중량부를 초과할 경우 제조단가의 상승으로 인해 경제성이 떨어진다. 따라서, 상기 무방향성 전기 강판용 절연코팅제에 적용되는 비실리콘계 첨가제는 약 0.1 내지 0.5 중량부를 사용하고, 바람직하게는 0.2 내지 0.4 중량부를 사용한다. The non-silicone additive included in the insulating coating agent for non-oriented electrical steel sheet may be used in an amount of about 0.1 to 0.5 parts by weight, and a fluorine-based additive may be used among the non-silicone additives. The non-silicone additives lower the surface tension of the insulating coating agent to improve wettability with the electrical steel sheet. As an example, the non-silicone additive may use BYK-340 (product name) of BYK Chemie (Germany). If the content of the non-silicone additive is less than 0.1 parts by weight, there is a problem that the wettability of the coating composition is lowered. Therefore, the non-silicone additive applied to the insulating coating agent for non-oriented electrical steel sheet uses about 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight.
상기 무방향성 전기 강판용 절연코팅제에 포함된 프로필렌 글리콜은 절연피막 표면의 얼룩 등을 방지하여 외관 특성을 개선하는 역할을 한다. 일반적으로, 절연코팅제를 대상물에 코팅할 때에는 고속의 연속롤 도포 처리 후 표면에는 얼룩 현상이 나타날 수 있다. 이는 약 530℃이상의 고온에서 단시간 가열시 휘발성분이 과도하게 빠르게 휘발됨으로 인해 발생된다. 따라서, 비점이 물보다 높은 프로필렌 글리콜을 코팅제에 포함될 경우 장시간 안정하게 작업을 할 수 있어서, 얼룩 등이 없고 균일한 외관을 갖는 절연피막을 수득할 수 있게 된다. 상기 무방향성 전기 강판용 절연코팅제에 포함된 프로필렌 글리콜의 함량이 5 중량부 미만인 경우에는 외관특성이 저하될 수 있다. 반면에 프로필렌 글리콜의 함량이 10 중량부를 초과할 경우 상기 프로필렌 글리콜의 일부가 피막에 잔류하여 절연피막의 내식성이 저하되는 문제점이 초래된다. 따라서 상기 무방향성 전기 강판용 절연코팅제에 적용되는 프로필렌 글리콜은 약 5 내지 10 중량부를 사용하고, 바람직하게는 약 6 내지 8 중량부를 사용한다. Propylene glycol contained in the insulating coating agent for non-oriented electrical steel sheet serves to improve appearance characteristics by preventing stains on the surface of the insulating film. In general, when the insulating coating agent is coated on the object, staining may appear on the surface after the high speed continuous roll coating treatment. This is caused by excessive volatilization of volatile components in a short time heating at a high temperature of about 530 ℃ or more. Therefore, when propylene glycol having a boiling point higher than that of water is included in the coating, it is possible to work stably for a long time, thereby obtaining an insulating film having no uniform appearance and no stain. When the content of propylene glycol contained in the insulating coating agent for non-oriented electrical steel sheet is less than 5 parts by weight, the appearance characteristics may be reduced. On the other hand, when the content of propylene glycol exceeds 10 parts by weight, a portion of the propylene glycol remains in the coating, resulting in a problem of lowering the corrosion resistance of the insulating coating. Therefore, about 5 to 10 parts by weight of propylene glycol applied to the insulating coating agent for non-oriented electrical steel sheet is used, and preferably about 6 to 8 parts by weight.
상기 무방향성 전기 강판용 절연코팅제는 응력제거소둔 후 형성된 절연피막의 광택 및 밀착성의 향상을 위하여 인산-에폭시실란 화합물을 3 내지 7 중량부를 포함한다. 인산-에폭시화합물 함량이 3중량부 미만이면 응력제거소둔 후 절연피막의 광택 및 밀착성이 저하되며, 그 함량이 7 중량부를 초과하면 인산함량의 증가로 인하여 절연피막의 내습성이 취약해 지는 단점이 발생된다. 따라서 상기 무방향성 전기 강판용 절연코팅제에 적용되는 인산-에폭시화합물은 약 3 내지 7 중량부를 사용하고, 바람직하게는 약 4 내지 6 중량부를 사용한다. 본 실시예에서 적용되는 인산-에폭시실란 반응화합물은 에폭시-실란 25 내지 40중량부, 이온교환수 40 내지 55 중량부, 초산 0.5 내지 2 중량부 및 85% 인산 수용액 4 내지 10 중량부를 반응시킴으로서 형성될 수 있다.The insulating coating agent for non-oriented electrical steel sheet includes 3 to 7 parts by weight of a phosphoric acid-epoxysilane compound to improve the gloss and adhesion of the insulating film formed after stress relief annealing. If the content of phosphoric acid-epoxy compound is less than 3 parts by weight, the gloss and adhesion of the insulating film is reduced after stress relief annealing, and if the content is more than 7 parts by weight, the moisture resistance of the insulating film becomes weak due to the increase in phosphoric acid content. Is generated. Therefore, the phosphoric acid-epoxy compound applied to the insulating coating agent for non-oriented electrical steel sheet is used in about 3 to 7 parts by weight, preferably about 4 to 6 parts by weight. The phosphoric acid-epoxysilane reaction compound applied in this embodiment is formed by reacting 25 to 40 parts by weight of epoxy-silane, 40 to 55 parts by weight of ion-exchanged water, 0.5 to 2 parts by weight of acetic acid and 4 to 10 parts by weight of an aqueous 85% phosphoric acid solution. Can be.
상기 무방향성 전기 강판용 절연코팅제는 주용제로서 이온교환수 3 내지 7중량부를 포함한다. 상기 이온 교환수는 피복 조성물의 점도를 조정하기 위해 사용되며 그 함량이 3 중량부 미만인 경우 피복 조성물의 저장성이 저하되는 문제점이 발생된다. 반면에 그 함량이 7 중량부를 초과할 경우 피복 조성물의 점도가 과도하게 낮아져 피막의 습윤성이 저하될 수 있다. 따라서 상기 무방향성 전기 강판용 절연코팅제에 적용되는 이온 교환수는 약 3 내지 7 중량부를 사용하고, 바람직하게는 4 내지 6중량부를 사용한다.The insulating coating agent for non-oriented electrical steel sheet contains 3 to 7 parts by weight of ion-exchanged water as a main solvent. The ion exchanged water is used to adjust the viscosity of the coating composition and when the content is less than 3 parts by weight, there is a problem that the storage property of the coating composition is lowered. On the other hand, if the content exceeds 7 parts by weight, the coating composition may have an excessively low viscosity, which may lower the wettability of the coating. Therefore, the ion-exchanged water applied to the insulating coating agent for non-oriented electrical steel sheet is about 3 to 7 parts by weight, and preferably 4 to 6 parts by weight.
상술한 조성을 갖는 무 방향성 전기 강판용 절연코팅제는 인체에 유해한 크 롬을 포함하지 않음에도 불구하고 응력제거 소둔 전후 밀착성 및 내식성이 우수하면서 보다 친환경적인 전기 강판용 절연피막을 형성할 수 있다.Although the insulating coating agent for non-oriented electrical steel sheet having the above-described composition does not contain chromium that is harmful to the human body, it is possible to form an insulating film for electric steel sheet which is more environmentally friendly while having excellent adhesion and corrosion resistance before and after stress relief annealing.
무 방향성 전기 강판용 절연코팅제 제조Insulation coating agent for non-oriented electrical steel sheet
본 발명의 무 방향성 전기 강판용 절연코팅제의 제조방법에 따르면 먼저 무기 금속산화물과 산소산의 반응으로 형성된 금속산화물 복합염을 마련한다. According to the manufacturing method of the insulating coating agent for non-oriented electrical steel sheet of the present invention, first, a metal oxide composite salt formed by the reaction of an inorganic metal oxide and an oxygen acid is prepared.
일 예로서, 본 실시예의 금속산화물 복합염은 알루미늄(Al), 마그네슘(Mg) 및 아연(Zn)으로 이루어진 군에서 선택된 적어도 하나의 금속산화물과 인산(H3PO4) 및 붕산(H3BO4)을 포함하는 산소산이 반응함으로서 형성된다. 상기 금속산화물 복합염에 대한 구체적인 설명은 절연피막 코팅제에서 상세히 설명하였기에 구체적인 설명은 생략한다.As an example, the metal oxide composite salt of the present embodiment may include at least one metal oxide selected from the group consisting of aluminum (Al), magnesium (Mg), and zinc (Zn), phosphoric acid (H 3 PO 4 ), and boric acid (H 3 BO). Oxygen acid containing 4 ) is formed by reaction. Detailed description of the metal oxide composite salt has been described in detail in the insulating coating coating, and thus a detailed description thereof will be omitted.
이어서, 고형분이 42 내지 46중량%이고, pH가 4 내지 4.5이며, 10 내지 100nm의 입자크기를 갖는 자기가교형 에멀젼 수지를 마련한다. Subsequently, a self-crosslinking emulsion resin having a solid content of 42 to 46% by weight, a pH of 4 to 4.5 and a particle size of 10 to 100 nm is prepared.
일 예로서, 본 실시예의 자기가교형 에멀젼 수지는 이온교환수 45 내지 55 중량부, 스티렌 12 내지 17 중량부, 메틸메타아크릴레이트 12 내지 17중량부, 부틸 아크릴레이트 3내지 5 중량부, 메타크릴산 0.3 내지 0.5중량부, 자기가교 성분인 메틸올아크릴아마이드 1 내지 3중량부, 에멀젼 가교제인 디비닐 벤젠 0.5 내지 1.0중량부, 개시제인 암모니움퍼설페이트(Ammonium persulfate) 0.1 내지 0.3, 음이온 계면활성제인 폴리옥시에틸렌알킬페닐에테르암모니움 설페이트계 계면활성제 1 내 지 3 중량부, 반응성 계면활성제인 폴리옥시에틸렌알킬에테르계 계면활성제 2 내지 4중량부로 합성되는 것을 특징으로 한다. 상기 자기가교형 에멀젼 수지에 대한 구체적인 설명은 전기 강판용 절연코팅제에서 상세히 설명하였기에 구체적인 설명은 생략한다.As an example, the self-crosslinking emulsion resin of this embodiment is 45 to 55 parts by weight of ion-exchanged water, 12 to 17 parts by weight of styrene, 12 to 17 parts by weight of methyl methacrylate, 3 to 5 parts by weight of butyl acrylate, methacryl 0.3 to 0.5 parts by weight of acid, 1 to 3 parts by weight of methylol acrylamide as a self-crosslinking component, 0.5 to 1.0 parts by weight of divinyl benzene as an emulsion crosslinking agent, 0.1 to 0.3 as ammonium persulfate as an initiator, anionic surfactant 1 to 3 parts by weight of polyoxyethylene alkyl phenyl ether ammonium sulfate-based surfactant, 2 to 4 parts by weight of a polyoxyethylene alkyl ether-based surfactant which is a reactive surfactant. Detailed description of the self-crosslinking emulsion resin has been described in detail in the insulating coating agent for electrical steel sheet, so a detailed description thereof will be omitted.
이어서, 인산-에폭시실란 화합물을 마련한다. Next, a phosphoric acid-epoxysilane compound is prepared.
일 예로서, 본 실시예의 인산-에폭시실란 화합물은 에폭시-실란 25 내지 40중량부, 이온교환수 40 내지 55 중량부, 초산 0.5 내지 2 중량부 및 85% 인산 수용액 4 내지 10 중량부를 반응시킴으로서 형성되는 것을 특징으로 한다. 상기 인산-에폭시실란 화합물에 대한 구체적인 설명은 전기 강판용 절연코팅제에서 상세히 설명하였기에 구체적인 설명은 생략한다.As an example, the phosphoric acid-epoxysilane compound of this embodiment is formed by reacting 25 to 40 parts by weight of epoxy-silane, 40 to 55 parts by weight of ion-exchanged water, 0.5 to 2 parts by weight of acetic acid and 4 to 10 parts by weight of an aqueous 85% phosphoric acid solution. It is characterized by. Detailed description of the phosphoric acid-epoxysilane compound has been described in detail in the insulating coating agent for electrical steel sheet, and thus the detailed description thereof will be omitted.
이후 상기 금속산화물 복합염 47 내지 57 중량부, 자기가교형 에멀젼 수지 25 내지 35 중량부, 소재 습윤성을 향상시키기 위한 불소계 첨가제 0.1 내지 0.5 중량부, 얼룩을 방지하기 위한 프로필렌글리콜 5 내지 10 중량부, 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 3 내지 7 중량부 및 이온 교환수 3 내지 7 중량부를 혼합 반응시킨다. 47 to 57 parts by weight of the metal oxide composite salt, 25 to 35 parts by weight of the self-crosslinking emulsion resin, 0.1 to 0.5 parts by weight of fluorine-based additives to improve the material wettability, 5 to 10 parts by weight of propylene glycol to prevent stains, 3 to 7 parts by weight of phosphoric acid-epoxysilane compound and 3 to 7 parts by weight of ion-exchanged water are mixed and reacted to improve the gloss and adhesion of the insulating film.
그 결과 인체에 유해한 크롬을 포함하지 않음에도 불구하고 응력제거 소둔 전후 밀착성 및 내식성이 우수하면서 보다 친환경적인 전기 강판용 절연코팅제가 제조된다.As a result, in spite of not containing chromium that is harmful to the human body, an insulation coating agent for electrical steel sheet is prepared, which has excellent adhesion and corrosion resistance before and after stress relief annealing.
무 방향성 전기 강판용 절연피막 형성Insulation film formation for non-oriented electrical steel sheet
본 발명의 무 방향성 전기 강판용 절연피막의 형성방법에 따르면 먼저 무 방향성 전기 강판용 절연코팅제를 준비한다. 본 실시예의 무 방향성 전기 강판용 절연코팅제는 무기 금속산화물과 산소산의 반응으로 형성된 금속산화물 복합염 47 내지 57 중량부, 10 내지 100nm의 입자크기를 갖는 자기가교형 에멀젼 수지 25 내지 35 중량부, 소재 습윤성을 향상시키기 위한 불소계 첨가제 0.1 내지 0.5 중량부, 얼룩을 방지하기 위한 프로필렌글리콜 5 내지 10 중량부, 절연피막의 광택 및 밀착성을 향상시키기 위한 인산-에폭시실란 화합물 3 내지 7 중량부 및 이온 교환수 3 내지 7 중량부를 혼합 반응시킴으로서 형성된다. According to the method for forming an insulating film for non-oriented electrical steel sheet of the present invention, first, an insulating coating agent for non-oriented electrical steel sheet is prepared. Insulating coating agent for non-oriented electrical steel sheet of the present embodiment 47 to 57 parts by weight of the metal oxide composite salt formed by the reaction of the inorganic metal oxide and oxygen acid, 25 to 35 parts by weight of the self-crosslinkable emulsion resin having a particle size of 10 to 100nm, material wettability 0.1 to 0.5 parts by weight of a fluorine-based additive to improve the amount, 5 to 10 parts by weight of propylene glycol to prevent staining, 3 to 7 parts by weight of phosphoric acid-epoxysilane compound to improve the gloss and adhesion of the insulating film and ion exchanged water 3 To 7 parts by weight of a mixed reaction.
이어서, 형성된 무 방향성 전기 강판용 절연코팅제를 전기 강판의 표면에 도포하여 코팅막을 형성한다. 일 예로서, 상기 전기 강판은 모터 등에 사용되는 무방향성 전기 강판일 수 있으며, 상기 코팅막은 약 0.5 내지 약 1.4㎛의 두께로 형성될 수 있다.Subsequently, the formed insulating coating agent for non-oriented electrical steel sheet is applied to the surface of the electrical steel sheet to form a coating film. As an example, the electrical steel sheet may be a non-oriented electrical steel sheet used in a motor or the like, and the coating layer may be formed to a thickness of about 0.5 to about 1.4 μm.
이어서, 상기 전기 강판의 표면에 도포된 코팅막를 열처리한다. 그 결과 상기 전기 강판 상에는 절연특성 뿐만 아니라, 용해성, 안정성, 밀착성, 표면 외관, 내식성, 광택 등이 양호한 무 방향성 전기 강판용 절연피막을 형성된다.Subsequently, the coating film applied to the surface of the electrical steel sheet is heat treated. As a result, an insulating coating film for non-oriented electrical steel sheet having good solubility, stability, adhesion, surface appearance, corrosion resistance, glossiness, etc., is formed on the electrical steel sheet.
상기 코팅막의 열처리는 약 530 내지 약 750℃로 설정된 가열로에서 약 10 내지 48초간 열처리 한다. 상기 절연피막의 외관특성을 결정하는 인자의 하나는 열처리 온도와 시간과의 관계이다. 가열로의 온도를 최고온도인 750℃로 하여 10초 미만으로 유지하면, 피막형성이 미흡하게 되고 흡습성이 남게 된다. 반면, 허용 최 저온도인 530℃에서 48초를 초과하여 유지시키면, 산화층과 화학적으로 결합되어 있는 피복 조성물이 산화되어 절연피막의 색상이 변색될 수 있다.The heat treatment of the coating film is heat-treated for about 10 to 48 seconds in a heating furnace set to about 530 to about 750 ℃. One of the factors that determine the appearance characteristics of the insulating film is the relationship between the heat treatment temperature and time. If the temperature of the heating furnace is kept at the maximum temperature of 750 ° C. for less than 10 seconds, film formation is insufficient and hygroscopicity remains. On the other hand, if the holding temperature is maintained for more than 48 seconds at 530 ° C., the coating composition, which is chemically bonded to the oxide layer, may be oxidized to discolor the insulating film.
이하 본 발명의 절연 코팅제를 하기 합성예, 실시예 및 비교예에 의해 보다 구체적으로 설명한다. 그러나 본 발명의 범위가 이들 실시예에 의해 제한되는 것은 아니다.Hereinafter, the insulating coating of the present invention will be described in more detail by the following Synthesis Examples, Examples and Comparative Examples. However, the scope of the present invention is not limited by these examples.
합성예 1Synthesis Example 1
자기 가교형 에멀젼 수지의 제조Preparation of Self-crosslinked Emulsion Resin
반응용기에 이온교환수 30중량부, 폴리옥시에틸렌알킬페닐에테르암모니움 설페이트 0.1중량부 및 폴리옥시에틸렌알킬에테르 0.3중량부를 투입한 후 교반을 진행하면서 70℃로 승온하였다. 이후, 이온교환수 16 중량부, 폴리옥시에틸렌알킬페닐에테르암모니움 설페이트 2중량부 및 폴리옥시에틸렌알킬에테르 3중량부 혼합물에 스티렌 13 중량부, 메틸메타아크릴레이트 17중량부, 부틸 아크릴레이트 4 중량부, 메타크릴산 0.3중량부 및 메틸올아크릴아마이드 2중량부, 디비닐 벤젠 0.5중량부를 투입하여 프리에멀젼을 제조하였다. 이온교환수 1 중량부 및 암모니움 퍼설페이트 0.2 중량부를 혼합하여 개시제 용액을 준비하였다. 이후, 상기 프리에멀젼과 상기 개시제 용액을 70℃ 반응용기에 각각 3시간에 걸쳐 투입한 후 약 2시간동안 반응을 유지하여 고형분 44%, pH 4.2 및 입자크기 92nm인 자기가교형 에멀젼수지를 수득하였다. 30 parts by weight of ion-exchanged water, 0.1 parts by weight of polyoxyethylene alkylphenyl ether ammonium sulfate, and 0.3 parts by weight of polyoxyethylene alkyl ether were added to the reaction vessel, and the mixture was heated to 70 ° C while stirring. Then, 16 parts by weight of ion-exchanged water, 2 parts by weight of polyoxyethylene alkylphenyl ether ammonium sulfate and 3 parts by weight of polyoxyethylene alkyl ether, 13 parts by weight of styrene, 17 parts by weight of methyl methacrylate, and 4 parts by weight of butyl acrylate. To the mixture was added 0.3 part by weight of methacrylic acid, 2 parts by weight of methylol acrylamide and 0.5 part by weight of divinyl benzene to prepare a preemulsion. An initiator solution was prepared by mixing 1 part by weight of ion-exchanged water and 0.2 part by weight of ammonium persulfate. Thereafter, the pre-emulsion and the initiator solution were added to a 70 ° C. reaction vessel over 3 hours, and then maintained for about 2 hours to obtain a self-crosslinked emulsion resin having a solid content of 44%, a pH of 4.2 and a particle size of 92 nm. .
합성예 2 Synthesis Example 2
금속산화물 복합염 제조Manufacture of metal oxide complex salt
이온교환수 51중량부, 인산 35중량부 및 붕산 2중량부를 반응용기에 투입하고 100℃로 반응물을 가열하였다. 이후, 100℃에서 알루미늄트리하이드록사이드(Al(OH)3) 7중량부, 마그네슘옥사이드(MgO) 1 중량부 및 아연옥사이드(ZnO) 2 중량부를 순차적으로 투입하여 금속산화물 복합염(제1 인산염 및 제1 붕산염)을 제조하였다. 제조된 금속산화물 복합염 고형분 46%, pH 1.2의 특성을 지닌다. 51 parts by weight of ion-exchanged water, 35 parts by weight of phosphoric acid and 2 parts by weight of boric acid were added to the reaction vessel, and the reaction was heated to 100 ° C. Subsequently, 7 parts by weight of aluminum trihydroxide (Al (OH) 3 ), 1 part by weight of magnesium oxide (MgO) and 2 parts by weight of zinc oxide (ZnO) were sequentially added at 100 ° C. to form a metal oxide complex salt (first phosphate). And first borate). The prepared metal oxide complex salt solid content of 46%, pH 1.2 has the characteristics.
합성예 3Synthesis Example 3
인산-에폭시실란 화합물의 제조Preparation of Phosphoric Acid-Epoxysilane Compound
에폭시-실란 32 중량부, 이온교환수 45중량부 및 초산 1.0 중량부를 반응용기에 투입한 70℃로 승온하였다. 이후 85% 인산수용액 7 중량부를 투입하고 3시간 유지 반응시켜 고형분 30%의 인산-에폭시 실란 화합물을 제조하였다.32 parts by weight of epoxy-silane, 45 parts by weight of ion-exchanged water, and 1.0 part by weight of acetic acid were heated up at 70 ° C. in which the reaction vessel was added. Thereafter, 7 parts by weight of an aqueous 85% phosphoric acid solution was added thereto, and the mixture was maintained for 3 hours to prepare a phosphoric acid-epoxy silane compound having a solid content of 30%.
실시예 1 Example 1
합성예 2의 금속산화물 복합염(고형분 46%) 52 중량부, 합성예 1의 자기가교형 에멀젼수지(고형분 44%) 28 중량부, 불소계의 첨가제 0.3 중량부, 프로필렌글리콜 8 중량부 및 합성예 3의 인산-에폭시실란 화합물(고형분 30%) 5 중량부 및 이온교환수 5 중량부를 포함하는 무방향성 전기 강판용 절연코팅제를 제조하였다.52 parts by weight of the metal oxide composite salt of Synthesis Example 2 (46% solids), 28 parts by weight of the self-crosslinkable emulsion resin (44% solids) of Synthesis Example 1, 0.3 parts by weight of fluorine-based additive, 8 parts by weight of propylene glycol, and Synthesis Example An insulating coating agent for a non-oriented electrical steel sheet including 5 parts by weight of phosphoric acid-epoxysilane compound (solid content 30%) and 5 parts by weight of ion-exchanged water was prepared.
실시예 2 Example 2
합성예 2의 금속산화물 복합염(고형분 46%) 47 중량부, 합성예 1의 자기가교형 에멀젼수지(고형분 44%) 32 중량부, 불소계의 첨가제 0.3 중량부, 프로필렌글리콜 8 중량부 및 합성예 3의 인산-에폭시실란 화합물(고형분 30%) 7 중량부 및 이온교환수 7 중량부를 포함하는 무방향성 전기 강판용 절연코팅제를 제조하였다.47 parts by weight of the metal oxide composite salt of Synthesis Example 2 (46% solids), 32 parts by weight of the self-crosslinkable emulsion resin (44% solids) of Synthesis Example 1, 0.3 parts by weight of fluorine-based additive, 8 parts by weight of propylene glycol, and Synthesis Example An insulating coating agent for a non-oriented electrical steel sheet including 7 parts by weight of phosphoric acid-epoxysilane compound (solid content 30%) and 7 parts by weight of ion-exchanged water was prepared.
비교예 1Comparative Example 1
실시예 1에서 인산-에폭시 화합물을 제외하고 실시예1과 동일하게 무 방향성 전기 강판용 절연코팅제를 준비하였다.Except for the phosphoric acid-epoxy compound in Example 1, an insulating coating agent for a non-oriented electrical steel sheet was prepared in the same manner as in Example 1.
비교예 2Comparative Example 2
합성예 2의 금속산화물 복합염(고형분 46%) 35 중량부, 합성예 1의 자기가교형 에멀젼수지(고형분 44%) 37 중량부, 불소계의 첨가제 0.3 중량부, 프로필렌글리콜 8 중량부 및 합성예 3의 인산-에폭시실란 화합물(고형분 30%) 5 중량부 및 이온교환수 5 중량부를 포함하는 무 방향성 전기 강판용 절연코팅제를 준비하였다. 35 parts by weight of the metal oxide composite salt of Synthesis Example 2 (46% solids), 37 parts by weight of the self-crosslinkable emulsion resin (44% solids) of Synthesis Example 1, 0.3 parts by weight of fluorine-based additive, 8 parts by weight of propylene glycol, and Synthesis Example An insulating coating agent for a non-oriented electrical steel sheet including 5 parts by weight of phosphoric acid-epoxysilane compound (solid content 30%) and 5 parts by weight of ion-exchanged water was prepared.
비교예 3Comparative Example 3
합성예 2의 금속산화물 복합염(고형분 46%) 52 중량부, 합성예 1의 자기가 교형 에멀젼수지(고형분 44%) 32 중량부, 불소계의 첨가제 0.3 중량부, 프로필렌글리콜 3 중량부 및 합성예 3의 인산-에폭시실란 화합물(고형분 30%) 5 중량부 및 이온교환수 5 중량부를 포함하는 무 방향성 전기 강판용 절연코팅제를 준비하였다. 52 parts by weight of the metal oxide composite salt of Synthesis Example 2 (46% solids), 32 parts by weight of the self-chaining emulsion resin (44% of the solid content) of Synthesis Example 1, 0.3 parts by weight of fluorine-based additives, 3 parts by weight of propylene glycol, and Synthesis Example An insulating coating agent for a non-oriented electrical steel sheet including 5 parts by weight of phosphoric acid-epoxysilane compound (solid content 30%) and 5 parts by weight of ion-exchanged water was prepared.
절연피막 형성용 성물 및 절연피막의 물성 평가Evaluation of Properties for Forming Insulation Film and Insulation Film
실시예 1, 2 및 비교예 1 내지 3의 각 전기 강판용 절연코팅제를 약 4일간 숙성시킨 다음, 두께가 약 0.5mm인 무방향성 전기 강판(SI:1.2함유)표면에 바코터를 사용하여 약 1㎛의 두께로 상기 무 방향성 전기 강판용 절연코팅막을 형성한 후 약 650℃로 설정된 가열로에서 약 15초간 소둔하여 전기 강판용 절연피막을 각각 형성하였다.Each of the insulating coating agents for electrical steel sheets of Examples 1 and 2 and Comparative Examples 1 to 3 was aged for about 4 days, and then a bar coater was used on the surface of the non-oriented electrical steel sheet (containing SI: 1.2) having a thickness of about 0.5 mm. After forming the insulating coating film for non-oriented electrical steel sheet to a thickness of μm and annealing for about 15 seconds in a heating furnace set to about 650 ℃ to form an insulating film for electrical steel sheet, respectively.
실시예 1, 2 및 비교예 1 내지 3의 각 전기 강판용 절연코팅제로 형성된 각 전기 강판용 절연피막의 밀착성, 절연성, 표면 외관, 내식성 및 광택을 측정한 후, 양호(○), 중간(△),불량(×)으로 판단하여 그 결과를 하기의 표 1에 나타내었다.After measuring the adhesion, insulation, surface appearance, corrosion resistance and gloss of the insulating film for electrical steel sheets formed of the insulating coating agent for electrical steel sheets of Examples 1 and 2 and Comparative Examples 1 to 3, the results were good (○), medium (△), Judgment by the defect (x) is shown in Table 1 below.
표1Table 1
표 1을 참조하면, 실시예 1 및 2의 전기 강판용 절연코팅제 및 이를 이용하여 형성된 절연피막의 특성이 비교예 1내지 3의 절연피막 처리제 및 이를 이용하여 형성된 절연피막에 비하여 우수함을 알 수 있다. 특히, 내식성 및 광택성이 우수한 것으로 나타났다.Referring to Table 1, it can be seen that the characteristics of the insulating coating agent for the electrical steel sheet and the insulating film formed using the same in Examples 1 and 2 compared to the insulating film treatment agent of Comparative Examples 1 to 3 and the insulating film formed using the same. In particular, it appeared to be excellent in corrosion resistance and glossiness.
밀착성을 평가하기 위하여 각 절연피막을 100% N2가스 분위기에서 약 750℃에서 약 2시간 동안 열처리 후 각 절연피막을 약 10mmψ의 원호를 갖는 환봉 주위에 접하여 180° 구부릴 때 피막박리가 없는 상태를 양호로 평가하였다. 절연성을 평가하기 위하여 300psi 압력하에서 0.5V×1.0A의 전류를 통하였을 때의 수납 전류값(Amps)을 측정하고 약 0 내지 0.1Amps를 양호, 약 0.25Amps이상을 불량, 그 사이의 구간을 보통으로 평가하였다. 표면 외관을 평가하기 위하여 색상, 줄무늬 유무 등을 육안으로 관찰하여 전기 강판의 표면이 잘 보일수록, 줄무늬가 나타나지 않을수록 피막 외관이 양호한 것으로 평가하였다. 내식성을 평가하기 위하여 약 35℃의 5% 염화나트륨 용액을 각 절연피막에 분무하고, 약 24시간 후 피막 표면의 녹 발생 유무를 관찰하여 평가하였다. 광택을 평가하기 위하여 BYK 社의 micro-TRI-gloss를 사용하여 각 절연피막의 광택을 측정하고, 광택(60°)이 110°인 경우 ○, 80 내지 110°인 경우 △, 80° 미만인 경우를 × 로 판단하였다. In order to evaluate the adhesion, each insulating film was heat-treated at about 750 ° C. for about 2 hours in a 100% N 2 gas atmosphere, and then each insulating film was contacted around a round bar having an arc of about 10 mm ψ and bent 180 ° when the film was bent 180 °. It evaluated good. In order to evaluate the insulation, the measured current value (Amps) was measured when a current of 0.5 V x 1.0 A was applied under a pressure of 300 psi, and about 0 to 0.1 Amps was good, about 0.25 Amps or more was poor, and the interval between them was normal. Evaluated. In order to evaluate the surface appearance, color, presence of stripes, and the like were visually observed to evaluate the appearance of the film as the surface of the electrical steel sheet was better seen and the appearance of stripes was not good. In order to evaluate the corrosion resistance, 5% sodium chloride solution at about 35 ° C. was sprayed onto each insulating film, and after about 24 hours, rust was observed on the surface of the film. In order to evaluate the gloss, the gloss of each insulating film was measured using BYK's micro-TRI-gloss, and the glossiness (60 °) was 110 °, ○, 80 to 110 °, △, and less than 80 °. It judged by x.
이와 같은 본 발명에 따른 전기 강판용 코팅제는 인체에 유해한 크롬을 포함하지 않음에도 불구하고 크롬을 포함하는 기존의 전기 강판용 절연피막과 동일한 물성을 갖는 절연피막을 형성할 수 있어 환경 친화적이다. 또한, 상기 코팅제로 형성된 전기 강판용 절연피막은 밀착성, 절연성, 외관, 내식성 및 광택이 우수한 특성을 갖는다.Although the coating agent for an electrical steel sheet according to the present invention does not contain chromium, which is harmful to a human body, it is possible to form an insulating coating having the same physical properties as that of an existing insulating coating for electrical steel sheet containing chromium. In addition, the insulating film for electrical steel sheet formed of the coating agent has excellent properties of adhesion, insulation, appearance, corrosion resistance and gloss.
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