KR102165433B1 - Acryl paint for road marking and manufacturing method thereof - Google Patents

Acryl paint for road marking and manufacturing method thereof Download PDF

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KR102165433B1
KR102165433B1 KR1020200023288A KR20200023288A KR102165433B1 KR 102165433 B1 KR102165433 B1 KR 102165433B1 KR 1020200023288 A KR1020200023288 A KR 1020200023288A KR 20200023288 A KR20200023288 A KR 20200023288A KR 102165433 B1 KR102165433 B1 KR 102165433B1
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weight
parts
acrylic
paint
present
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KR1020200023288A
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Korean (ko)
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윤승경
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주식회사 리스아이피
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/541Silicon-containing compounds containing oxygen
    • C08K5/5415Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/41Organic pigments; Organic dyes
    • EFIXED CONSTRUCTIONS
    • E01CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01FADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
    • E01F9/00Arrangement of road signs or traffic signals; Arrangements for enforcing caution
    • E01F9/50Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
    • E01F9/506Road surface markings; Kerbs or road edgings, specially adapted for alerting road users characterised by the road surface marking material, e.g. comprising additives for improving friction or reflectivity; Methods of forming, installing or applying markings in, on or to road surfaces

Abstract

The present invention relates to an acrylic paint for road marking, comprising: 5 to 20 parts by weight of water-dispersible polyurethane; and 3 to 15 parts by weight of a surface-modified heat shielding pigment with respect to 100 parts by weight of acrylic emulsion, wherein the surface-modified heat shielding pigment is surface-modified with a surface modifier comprising an acrylic group or a methacrylic group.

Description

노면 표지용 아크릴 도료 및 그 제조방법{Acryl paint for road marking and manufacturing method thereof}TECHNICAL FIELD [0001] Acrylic paint for road marking and manufacturing method thereof

본 발명은 내구성, 내마모성 및 차열성능이 우수한 노면 표지용 아크릴 도료 및 그 제조방법 에 관한 것이다. The present invention relates to an acrylic paint for road marking excellent in durability, abrasion resistance, and heat shielding performance, and a method of manufacturing the same.

원활한 교통흐름 확보 및 여러 가지 정보를 안내하기 위하여 다양한 종류의 노면 표지가 노면 상에 도색된다. 통상적으로 이런 노면 표지는 차선, 중앙성, 횡단보도, 제한 속도 등의 정보를 표시하며, 이러한 정보를 바탕으로 운전자 및 보행자가 원활히 통행할 수 있다. Various types of road signs are painted on the road to ensure smooth traffic flow and guide various information. Typically, such a road sign displays information such as a lane, a centrality, a crosswalk, and a speed limit, and based on this information, drivers and pedestrians can pass smoothly.

이러한 노면 표지는 통상적으로 태양광이 직접적으로 조사되며, 차량이 통행하는 가혹한 환경에 놓이게 되므로, 물리적 충격에 강한 특성을 확보함으로써 장기정인 내구성을 나타낼 수 있다. 이에 따라 노면 표지의 부착성, 내마모성 및 크랙 형성을 방지하기 위한 연구들이 지속적으로 수행되고 있다. Since such a road sign is usually directly irradiated with sunlight and is placed in a harsh environment in which a vehicle passes, it can exhibit long-term durability by securing a characteristic strong against physical shock. Accordingly, studies to prevent adhesion, abrasion resistance, and crack formation of road surface marks are continuously being conducted.

한편, 태양광에 직접적으로 노출되는 노면 표지의 경우, 여름철 급격한 온도 상승이 수반된다. 특히, 아스팔트 재질상에 형성된 노면 표지의 경우 온도 상승이 더욱 심각하며, 이에 따른 노면 표지의 내구성 저하 또한 일부 수반되고 있어, 노면 표지의 온도 상승에 의한 내구성 저하를 예방하기 위한 수단 또한 필요한 실정이다.On the other hand, in the case of a road surface that is directly exposed to sunlight, a rapid temperature increase in summer is accompanied. In particular, in the case of a road surface mark formed on an asphalt material, the temperature increase is more serious, and thus, the durability of the road surface mark is also partially accompanied, and a means for preventing a decrease in durability due to an increase in the temperature of the road surface mark is also required.

대한민국 등록특허공보 제10-1768081호Korean Patent Publication No. 10-1768081

본 발명의 목적은 차열성이 우수한 노면 표지용 아크릴 도료 및 그 제조방법 을 제공하는 것이다. An object of the present invention is to provide an acrylic paint for road marking having excellent heat shielding properties and a method for producing the same.

본 발명의 다른 목적은 부착성 및 내마모성이 우수한 노면 표지용 아크릴 도료 및 그 제조방법을 제공하는 것이다.Another object of the present invention is to provide an acrylic paint for road marking having excellent adhesion and abrasion resistance, and a method of manufacturing the same.

본 발명의 또 다른 목적은 크랙 방지 효과가 뛰어난 노면 표지용 아크릴 도료 및 그 제조방법을 제공하는 것이다. Another object of the present invention is to provide an acrylic paint for road surface marking excellent in crack prevention effect and a method of manufacturing the same.

본 발명에 의한 노면 표지용 아크릴 도료는 아크릴 에멀전 100 중량부 대비 5 내지 20 중량부의 수분산 폴리우레탄 및 3 내지 15 중량부의 표면개질된 차열안료를 포함하며, The acrylic paint for road surface marking according to the present invention comprises 5 to 20 parts by weight of water-dispersible polyurethane and 3 to 15 parts by weight of a surface-modified heat shielding pigment based on 100 parts by weight of the acrylic emulsion,

상기 표면개질된 차열안료는 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 표면개질된 것을 특징으로 한다.The surface-modified heat-shielding pigment is characterized in that the surface is modified with a surface modifier containing an acrylic group or a methacrylic group.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료에서 상기 노면 표지용 아크릴 도료는 폴리헤드럴 올리고머 실세스퀴옥산을 더 포함할 수 있다. In the acrylic paint for road marking according to an embodiment of the present invention, the acrylic paint for road marking may further include polyhedral oligomer silsesquioxane.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료에서 상기 노면 표지용 아크릴 도료는 상기 아크릴 에멀전 100 중량부 대비 1 내지 5 중량부의 폴리헤드럴 올리고머 실세스퀴옥산을 포함할 수 있다. In the acrylic paint for road marking according to an embodiment of the present invention, the acrylic paint for road marking may contain 1 to 5 parts by weight of polyhedral oligomer silsesquioxane based on 100 parts by weight of the acrylic emulsion.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료에서 상기 수분산 폴리우레탄은 고형분 32 내지 37 중량%를 기준으로 점도가 50 내지 200 cps일 수 있다. In the acrylic paint for road surface marking according to an embodiment of the present invention, the water-dispersible polyurethane may have a viscosity of 50 to 200 cps based on a solid content of 32 to 37% by weight.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료에서 상기 노면 표지용 아크릴 도료는 상기 아크릴 에멀젼 100 중량부 대비 50 내지 110 중량부의 체질안료를 포함할 수 있다. In the acrylic paint for road surface marking according to an embodiment of the present invention, the acrylic paint for road surface marking may include 50 to 110 parts by weight of an extender pigment based on 100 parts by weight of the acrylic emulsion.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료에서 상기 표면개질제는 3-메타크릴옥시프로필 메틸디메톡시실란, 3-메타크릴옥시프로필 트리메톡시실란, 3-메타크릴옥시프로필 메틸디에톡시실란, 3-메타크릴옥시프로필 트리에톡시실란 및 3-아크릴옥시프로필 트리메톡시실란에서 선택되는 하나 또는 둘 이상을 포함할 수 있다. In the acrylic paint for road surface marking according to an embodiment of the present invention, the surface modifier is 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane , 3-methacryloxypropyl triethoxysilane and 3-acryloxypropyl trimethoxysilane may include one or two or more selected from.

본 발명은 또한 노면 표지용 아크릴 도료 제조방법을 제공하며, 본 발명에 의한 노면 표지용 아크릴 도료 제조방법은 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 차열안료를 표면개질하여 표면개질된 차열안료를 제조하는 제 1단계; 및 상기 표면개질된 차열안료, 아크릴 에멀전 및 수분산 폴리우레탄을 혼합하는 제 2단계;를 포함한다. The present invention also provides a method for producing an acrylic paint for road surface marking, and the method for producing an acrylic paint for road surface marking according to the present invention provides a surface-modified heat-shielding pigment by modifying the surface of a heat-shielding pigment with a surface modifier containing an acrylic group or a methacrylic group. A first step of manufacturing; And a second step of mixing the surface-modified heat shielding pigment, acrylic emulsion, and water-dispersible polyurethane.

본 발명에 의한 노면 표지용 아크릴 도료는 아크릴 에멀전 100 중량부 대비 5 내지 15 중량부의 수분산 폴리우레탄 및 3 내지 15 중량부의 표면개질된 차열안료를 포함하며, 상기 표면개질된 차열안료는 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 표면개질된 것을 특징으로 함으로써, 차열안료의 분산성 향상에 의한 우수한 차열성 및 부착성 및 내마모성이 우수하고, 장기간 사용하더라도 노면 표지에서 크랙이 발생을 최소화하는 크랙 방지 효과가 뛰어난 장점이 있다. The acrylic paint for road surface marking according to the present invention comprises 5 to 15 parts by weight of water-dispersible polyurethane and 3 to 15 parts by weight of a surface-modified heat-shielding pigment based on 100 parts by weight of the acrylic emulsion, and the surface-modified heat-shielding pigment is an acrylic group or Characterized by being surface-modified with a surface modifier containing a methacrylic group, it has excellent heat shielding properties, adhesion, and abrasion resistance by improving the dispersibility of heat shielding pigments, and prevents cracks that minimizes the occurrence of cracks on the road surface even when used for a long time. There is a merit of excellent effect.

본 발명의 실시예들에 대한 이점 및 특징, 그리고 그것들을 달성하는 방법은 첨부되는 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있으며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하고, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다. 명세서 전체에 걸쳐 동일 참조 부호는 동일 구성 요소를 지칭한다.Advantages and features of the embodiments of the present invention, and a method of achieving them will become apparent with reference to the embodiments described later in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, and only these embodiments make the disclosure of the present invention complete, and are common knowledge in the art to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same components throughout the specification.

본 발명의 실시예들을 설명함에 있어서 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다. 그리고 후술되는 용어들은 본 발명의 실시예에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 관례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다.In describing the embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout this specification.

본 발명은 아크릴 에멀전 100 중량부 대비 5 내지 15 중량부의 수분산 폴리우레탄 및 3 내지 15 중량부의 표면개질된 차열안료를 포함하며, The present invention includes 5 to 15 parts by weight of a water-dispersible polyurethane and 3 to 15 parts by weight of a surface-modified heat shielding pigment based on 100 parts by weight of an acrylic emulsion,

상기 표면개질된 차열안료는 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 표면개질된 것인 노면 표지용 아크릴 도료에 관한 것으로, 본 발명에 의한 노면 표지용 아크릴 도료은 차열성, 부착성 및 내마모성이 우수하고, 크랙 방지 효과가 뛰어난 장점이 있다. The surface-modified heat-shielding pigment relates to an acrylic paint for road marking that is surface-modified with a surface modifier containing an acrylic group or a methacrylic group, and the acrylic paint for road surface marking according to the present invention has excellent heat shielding properties, adhesion and abrasion resistance. It has the advantage of being excellent in crack prevention effect.

즉, 본 발명에 의한 노면 표지용 아크릴 도료는 아크릴 에멀전 및 수분산 폴리우레탄을 함께 포함함으로써 종래 아크릴 에멀전 단독 또는 수분산 폴리우레탄 단독으로 사용하는 경우 달성하기 어려웠던 높은 부착력 및 크랙방지 성능을 동시에 나타낼 수 있는 장점이 있다. That is, the acrylic paint for road surface marking according to the present invention contains both an acrylic emulsion and a water-dispersible polyurethane, so that it can simultaneously exhibit high adhesion and anti-crack performance, which was difficult to achieve when using the conventional acrylic emulsion alone or water-dispersed polyurethane alone. There is an advantage.

본 발명에 의한 노면 표지용 아크릴 도료는 상기 아크릴 에멀전 100 중량부 대비 5 내지 20 중량부, 좋게는 8 내지 15 중량부의 수분산 폴리우레탄을 포함할 수 있다. 수분산 폴리우레탄이 소량 포함되는 경우 수분산 폴리우레탄 첨가에 의한 크랙 방지 효과가 거의 나타나지 않는 문제점이 있으며, 수분산 폴리우레탄을 다량 첨가하는 경우 내마모성이 저하되는 문제가 발생할 수 있다. The acrylic paint for road surface marking according to the present invention may include 5 to 20 parts by weight, preferably 8 to 15 parts by weight of water-dispersible polyurethane, based on 100 parts by weight of the acrylic emulsion. When a small amount of water-dispersible polyurethane is included, there is a problem that the effect of preventing cracks due to the addition of the water-dispersed polyurethane is hardly observed, and when a large amount of water-dispersed polyurethane is added, a problem of lowering abrasion resistance may occur.

또한, 상기 차열안료는 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 표면개질된 것을 이용함으로써, 아크릴 에멀전과의 관계에서 균일한 혼합을 촉진시킬 수 있으며, 이에 따라 차열안료의 응집에 따라 발생하는 차열성 저하 및 도막의 불균일 문제를 예방할 수 있는 장점이 있다. 이때 차열안료는 상기 아크릴 에멀전 100 중량부 대비 3 내지 15 중량부, 좋게는 5 내지 10 중량부 포함될 수 있으며, 표면개질된 차열안료가 소량 포함되는 경우 유의미한 차열성을 나타내기 어려운 문제점이 있으며, 차열안료가 다량 포함되는 경우 도막의 물성 저하를 유발할 수 있다. In addition, the heat shielding pigment may promote uniform mixing in relation to the acrylic emulsion by using a surface modified with a surface modifier containing an acrylic group or a methacrylic group, and accordingly, differences occurring due to aggregation of the heat shielding pigment There is an advantage of preventing thermal degradation and non-uniformity of the coating film. At this time, the heat shielding pigment may contain 3 to 15 parts by weight, preferably 5 to 10 parts by weight, relative to 100 parts by weight of the acrylic emulsion, and when a small amount of the surface-modified heat shielding pigment is included, there is a problem that it is difficult to exhibit significant heat shielding properties. If a large amount of pigment is included, it may cause a decrease in physical properties of the coating film.

좋게는 상기 표면개질제는 3-메타크릴옥시프로필 메틸디메톡시실란(3-Methacryloxypropyl methyldimethoxysilane), 3-메타크릴옥시프로필 트리메톡시실란(3-Methacryloxypropyl trimethoxysilane), 3-메타크릴옥시프로필 메틸디에톡시실란(3-Methacryloxypropyl methyldiethoxysilane), 3-메타크릴옥시프로필 트리에톡시실란(3-Methacryloxypropyl triethoxysilane) 및 3-아크릴옥시프로필 트리메톡시실란(3-Acryloxypropyl trimethoxysilane)에서 선택되는 하나 또는 둘 이상을 포함할 수 있으며, 이러한 표면개질제를 이용하는 경우 소량 첨가하더라도 표면개질 효과가 우수하며, 표면개질제 다량 첨가에 의한 도막의 물성 저하 등과 같은 문제를 예방할 수 있다. Preferably, the surface modifier is 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-methacryloxypropyl methyldiethoxysilane. (3-Methacryloxypropyl methyldiethoxysilane), 3-methacryloxypropyl triethoxysilane (3-Methacryloxypropyl triethoxysilane), and 3-acryloxypropyl trimethoxysilane (3-Acryloxypropyl trimethoxysilane) may contain one or more selected from In addition, when such a surface modifier is used, the surface modifier effect is excellent even if a small amount is added, and problems such as a decrease in physical properties of the coating film due to the addition of a large amount of the surface modifier can be prevented.

또한 본 발명에 의한 노면 표지용 아크릴 도료에서 상기 차열안료는 차열성을 띠는 금속 산화물 입자인 경우 제한없이 이용이 가능하며, 구체적이고 비한정적인 일예로 상기 차열안료는 이산화티탄, 산화철, 산화크롬, 산화주석, 산화아연, 산화지르코늄, 산화세륨 및 산화안티몬에서 선택되는 하나 또는 둘 이상을 포함할 수 있으나 본 발명이 이에 제한되는 것은 아니다. In addition, in the acrylic paint for road marking according to the present invention, the heat shielding pigment can be used without limitation in the case of metal oxide particles exhibiting heat shielding properties, and as a specific and non-limiting example, the heat shielding pigment is titanium dioxide, iron oxide, chromium oxide. , Tin oxide, zinc oxide, zirconium oxide, cerium oxide, and one or more selected from antimony oxide, but the present invention is not limited thereto.

이때 아크릴 에멀전은 고형분이 약 50 중량%이며, 상술한 고형분 기준 점도가 250 내지 350 cps이고, pH가 9 내지 11일 수 있다. 이러한 범위를 만족함으로써 다른 도료와의 높은 상용성을 담보하면서도 일정 수준 이상의 두께를 갖는 노면 표지 형성이 가능한 장점이 있다. At this time, the acrylic emulsion may have a solid content of about 50% by weight, a viscosity based on the solid content of 250 to 350 cps, and a pH of 9 to 11. By satisfying this range, there is an advantage that it is possible to form a road surface mark having a thickness of a certain level or more while ensuring high compatibility with other paints.

또한 상기 수분산 폴리우레탄은 고형분 32 내지 37 중량%를 기준으로 점도가 50 내지 200 cps일 수 있으며, pH가 6 내지 8일 수 있다. 상술한 고형분함량, 점도 및 pH를 만족함으로써 제조되는 노면 표지용 도료에서 적정 pH를 형성하고, 상술한 아크릴 에멀전과의 균일한 혼합으로 균질한 성질의 도막을 형성할 수 있는 장점이 있다. In addition, the water-dispersible polyurethane may have a viscosity of 50 to 200 cps and a pH of 6 to 8 based on 32 to 37% by weight of solid content. There is an advantage of forming an appropriate pH in the road marking paint prepared by satisfying the above-described solid content, viscosity, and pH, and forming a coating film having a homogeneous property by uniform mixing with the above-described acrylic emulsion.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료는 폴리헤드럴 올리고머 실세스퀴옥산(polyhedral oligomeric silsesquioxane)을 더 포함할 수 있으며, 폴리헤드럴 올리고머 실세스퀴옥산을 포함함으로써, 노면과의 부착성을 향상시킬 수 있는 장점이 있다. 즉, 본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료는 아크릴 에멀전, 수분산 폴리우레탄 및 폴리헤드럴 올리고머 실세스퀴옥산을 포함함으로써, 특히 아스팔트 등과 같은 노면과의 부착력을 현저히 향상시킬 수 있다. The acrylic paint for road surface marking according to an embodiment of the present invention may further include polyhedral oligomeric silsesquioxane, and by including polyhedral oligomeric silsesquioxane, it is attached to the road surface. There is an advantage that can improve sex. That is, the acrylic paint for road surface marking according to an embodiment of the present invention includes acrylic emulsion, water-dispersible polyurethane, and polyhedral oligomer silsesquioxane, so that adhesion to road surfaces such as asphalt can be significantly improved. .

상기 폴리헤드럴 올리고머 실세스퀴옥산은 3차원 구조의 실록산계 화합물로, (RSiO1.5)n으로 표시되며, n은 6 내지 16일 수 있다. 이때 상기 R은 알코올, 아민, 카르복실산 및 에폭시 등의 작용기를 포함할 수 있으나 본 발명이 이에 제한되는 것은 아니다. The polyhedral oligomer silsesquioxane is a siloxane-based compound having a three-dimensional structure, represented by (RSiO1.5)n, and n may be 6 to 16. In this case, R may include functional groups such as alcohol, amine, carboxylic acid, and epoxy, but the present invention is not limited thereto.

더욱 좋게는 상기 폴리헤드럴 올리고머 실세스퀴옥산은 직육면체 구조를 갖는 것을 특징으로 할 수 있으며, 구체적이고 비한정적인 일예로 상기 폴리헤드럴 올리고머 실세스퀴옥산은 TMP 디올이소부틸 POSS(DiolIsobutyl POSS), (TMP(Trimethylolpropane) DiolIsobutyl POSS), 사이클로헥산디올 이소부틸 POSS(Cyclohexanediol Isobutyl POSS), 1,2-프로판디올이소부틸 POSS(1,2-Propanediol Isobutyl POSS), 옥타(3-히드록시-3-메틸부틸디메틸실록시) POSS ((Octa(3-hydroxy-3-methylbutyldimethylsiloxy) POSS), 에폭시 사이클로헥실 이소부틸 POSS(Epoxy Cyclohexyl Isobutyl POSS), 에폭시사이클로헥실 POSS(Epoxycyclohexyl POSS), 글리시딜 POSS(Glycidyl POSS), 글리시딜 에틸 POSS(Glycidyl Ethyl POSS), 글리시딜 이소부틸 POSS(Glycidyl Isobutyl POSS), 글리시딜 이소부틸 POSS(Glycidyl Isooctyl POSS), 아미노프로필 이소부틸 POSS(Aminopropyl Isobutyl POSS), 아미노프로필 이소옥틸 POSS(Aminopropyl Isooctyl POSS), 아미노에틸아미노프로필 이소부틸 POSS(Aminoethylaminopropyl Isobutyl POSS), N-페닐아미노프로필 POSS(N-Phenylaminopropyl POSS), N-메틸아미노프로필 POSS(N-Methylaminopropyl Isobutyl POSS), 옥타 암모늄 POSS(Octa Ammonium POSS), 아미노페닐 사이클로헥실 POSS(Aminophenyl Cyclohexyl POSS) 및 아미노페닐 이소부틸 POSS(Aminophenyl Isobutyl POSS)에서 선택되는 하나 또는 둘 이상일 수 있다. More preferably, the polyhedral oligomer silsesquioxane may be characterized in that it has a rectangular parallelepiped structure, and as a specific and non-limiting example, the polyhedral oligomer silsesquioxane is TMP diolisobutyl POSS (DiolIsobutyl POSS) , (TMP (Trimethylolpropane) DiolIsobutyl POSS), Cyclohexanediol Isobutyl POSS (Cyclohexanediol Isobutyl POSS), 1,2-Propanediol Isobutyl POSS (1,2-Propanediol Isobutyl POSS), Octa (3-hydroxy-3- Methylbutyldimethylsiloxy) POSS ((Octa(3-hydroxy-3-methylbutyldimethylsiloxy) POSS), Epoxy Cyclohexyl Isobutyl POSS (Epoxy Cyclohexyl Isobutyl POSS), Epoxycyclohexyl POSS (Epoxycyclohexyl POSS), Glycidyl POSS (Glycidyl POSS) POSS), Glycidyl Ethyl POSS (Glycidyl Ethyl POSS), Glycidyl Isobutyl POSS (Glycidyl Isobutyl POSS), glycidyl isobutyl POSS (Glycidyl Isooctyl POSS), aminopropyl isobutyl POSS (Aminopropyl Isobutyl POSS), amino Aminopropyl Isooctyl POSS, Aminoethylaminopropyl Isobutyl POSS, N-Phenylaminopropyl POSS, N-Methylaminopropyl Isobutyl POSS, It may be one or two or more selected from Octa Ammonium POSS, Aminophenyl Cyclohexyl POSS, and Aminophenyl Isobutyl POSS.

구체적으로, 본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료는 상기 아크릴 에멀전 100 중량부 대비 1 내지 5 중량부의 폴리헤드럴 올리고머 실세스퀴옥산을 포함할 수 있으며, 폴리헤드럴 올리고머 실세스퀴옥산이 소량 첨가되는 경우 부착성 향상 효과를 나타내기 어려우며, 다량 첨가되는 경우 내마모성이 저하되는 문제가 발생할 수 있다. Specifically, the acrylic paint for road surface marking according to an embodiment of the present invention may contain 1 to 5 parts by weight of polyhedral oligomer silsesquioxane based on 100 parts by weight of the acrylic emulsion, and polyhedral oligomer silsesquioxane When a small amount of oxane is added, it is difficult to exhibit an effect of improving adhesion, and when a large amount is added, a problem of lowering abrasion resistance may occur.

본 발며의 일 실시예에 의한 노면 표지용 아크릴 도료는 상기 아크릴 에멀전 100 중량부 대비 50 내지 110 중량부, 좋게는 65 내지 90 중량부의 체질안료를 포함할 수 있다. 이때 체질안료는 탄산칼슘, 황산바륨 및 탈크에서 선택되는 하나 또는 둘 이상을 포함할 수 있으나, 본 발명이 이에 제한되는 것은 아니다. The acrylic paint for road surface marking according to an exemplary embodiment of the present invention may include 50 to 110 parts by weight, preferably 65 to 90 parts by weight of an extender pigment relative to 100 parts by weight of the acrylic emulsion. At this time, the extender pigment may include one or more selected from calcium carbonate, barium sulfate, and talc, but the present invention is not limited thereto.

본 발명의 일 실시예에 의한 노면 표지용 아크릴 도료는 분산제, 증점제, 소포제, 계면활성제, 방부제 및 가소제 등의 도료용 첨가제를 더 포함할 수 있으며, 본 발명이 이에 제한되는 것은 아니다. The acrylic paint for road surface marking according to an embodiment of the present invention may further include additives for paint such as a dispersant, a thickener, a defoaming agent, a surfactant, a preservative, and a plasticizer, and the present invention is not limited thereto.

구체적으로, 상기 증점제는 수성도료용 증점제를 이용할 수 있으며, 이때 증점제는 카제인, 전분, 레시틴 셀룰로오스, 폴리아크릴레이트 등의 증점제를 이용할 수 있으나, 본 발명이 이에 제한되는 것은 아니다. 상기 증점제는 상기 아크릴 에멀전 100 중량부 대비 0.5 내지 5 중량부 포함될 수 있으며, 증점제의 함량이 낮은 경우 도로 표지의 두께를 확보하기 어렵고, 증점제 함량이 높은 경우 균일한 도포가 어려운 문제점이 있다. Specifically, the thickener may be a thickener for water-based paint, and in this case, the thickener may be a thickener such as casein, starch, lecithin cellulose, and polyacrylate, but the present invention is not limited thereto. The thickener may be included in an amount of 0.5 to 5 parts by weight compared to 100 parts by weight of the acrylic emulsion, and when the content of the thickener is low, it is difficult to secure the thickness of the road sign, and when the content of the thickener is high, uniform application is difficult.

상기 분산제는 통상적으로 도료에 이용되는 분산제인 경우 제한없이 이용이 가능하다. 구체적이고 비한정적인 일예로 상기 분산제는 BYK 社의 DISPERBYK 시리즈 등의 시판 제품을 이용하거나, 폴리알킬에테르계, 폴리실록산 공중합체, 지방족 아민염 등을 이용할 수 있으나, 본 발명이 이에 제한되는 것은 아니다. 이때 분산제는 사용되는 분산제의 종류 등에 따라 첨가량이 달라질 수 있음이 자명하나, 구체적이고 비한정적인 일예로 분산제는 상기 아크릴 에멀전 100 중량부 대비 0.5 내지 5 중량부 첨가될 수 있다. 분산제가 소량 첨가되는 경우 분산효과를 도모하기 어려우며, 분산제가 다량 첨가되는 경우 도료의 건조과정에서 크랙이 형성되는 문제가 발생할 수 있다. The dispersant may be used without limitation if it is a dispersant commonly used in paints. As a specific and non-limiting example, the dispersant may be a commercial product such as BYK's DISPERBYK series, or a polyalkylether-based, polysiloxane copolymer, an aliphatic amine salt, etc., but the present invention is not limited thereto. At this time, it is obvious that the amount of the dispersant may vary depending on the type of dispersant used, but as a specific and non-limiting example, the dispersant may be added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the acrylic emulsion. When a small amount of dispersant is added, it is difficult to achieve the dispersing effect, and when a large amount of dispersant is added, a problem may occur in that cracks are formed during the drying process of the paint.

상기 소포제 또한 통상적으로 도료에 이용되는 것인 경우 제한없이 이용이 가능하다. 구체적이고 비한정적인 일예로 상기 소포제는 글리콜계류 폴리실록산류, 지방산 유도체류 및 계면활성류 등에서 선택되는 하나 또는 둘 이상일 수 있으나, 본 발명이 이에 제한되는 것은 아니다. 소포제는 상기 아크릴 에멀전 100 중량부 대비 0.1 내지 1 중량부 포함될 수 있으며, 소포제가 소량 포함되는 경우 기포의 제거 효과가 충분하지 못하여 도막의 내마모성이 현저히 낮아지는 문제가 발생할 수 있으며, 소포제를 다량 첨가하는 경우 도막 평활성이 저하될 수 있다. If the antifoaming agent is also commonly used for paint, it can be used without limitation. As a specific and non-limiting example, the antifoaming agent may be one or more selected from glycol-based polysiloxanes, fatty acid derivatives, and surfactants, but the present invention is not limited thereto. The antifoaming agent may be included in an amount of 0.1 to 1 parts by weight relative to 100 parts by weight of the acrylic emulsion, and when a small amount of the antifoaming agent is included, the effect of removing air bubbles may not be sufficient, resulting in a problem that the abrasion resistance of the coating film is significantly lowered. In this case, the smoothness of the coating film may decrease.

본 발명은 또한 노면 표지용 아크릴 도료 제조방법을 제공하며, 본 발명에 의한 노면 표지용 아크릴 도료 제조방법은 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 차열안료를 표면개질하여 표면개질된 차열안료를 제조하는 제 1단계; 및 상기 표면개질된 차열안료, 아크릴 에멀전 및 수분산 폴리우레탄을 혼합하는 제 2단계;를 포함한다. The present invention also provides a method for producing an acrylic paint for road surface marking, and the method for producing an acrylic paint for road surface marking according to the present invention provides a surface-modified heat-shielding pigment by modifying the surface of a heat-shielding pigment with a surface modifier containing an acrylic group or a methacrylic group. A first step of manufacturing; And a second step of mixing the surface-modified heat shielding pigment, acrylic emulsion, and water-dispersible polyurethane.

이하, 본 발명을 실시예 및 비교예에 의해 구체적으로 설명한다. 아래 실시예는 본 발명의 이해를 돕기 위한 것일 뿐이며, 본 발명의 범위가 아래 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples and comparative examples. The following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[제조예 1][Production Example 1]

1.표면개질된 차열안료의 제조 1. Manufacture of surface-modified heat shielding pigment

아세톤 1리터에 루틸형 이산화티탄 차열안료 20 g을 첨가하고 교반하면서 3-메타크릴옥시프로필 메틸디메톡시실란 3 g을 첨가하고 30분간 교반하였다. 이후, 건조하고 고형분을 분리하여 표면개질된 차열안료를 제조하였다. To 1 liter of acetone was added 20 g of a rutile type titanium dioxide thermal barrier pigment, and 3 g of 3-methacryloxypropyl methyldimethoxysilane was added while stirring, followed by stirring for 30 minutes. Thereafter, the surface-modified heat-shielding pigment was prepared by drying and separating the solid content.

2. 노면 표지용 아크릴 도료의 제조 2. Manufacture of acrylic paint for road marking

표 1의 조성을 혼합하여 노면 표지용 아크릴 도료를 제조하였다. 아크릴 에멀전은 고형분함량이 약 50중량%이며, 점도가 약 300 cps이고, pH가 약 10인 아크릴 에멀전(이하 AA라 함)인 것을 이용하였으며, 수분산 폴리우레탄(PU)은 고형분함량이 약 30 중량%이며 점도가 약 60 cps이고, pH가 약 7인 수분산 폴리우레탄을 이용하였다. 폴리헤드럴 올리고머 실세스퀴옥산(POSS)은 아미노프로필 이소옥틸 POSS(Aminopropyl Isooctyl POSS)를 이용하였으며, 체질안료는 탄산칼슘을 이용하였다. The composition of Table 1 was mixed to prepare an acrylic paint for road marking. Acrylic emulsion was used as an acrylic emulsion (hereinafter referred to as AA) having a solid content of about 50% by weight, a viscosity of about 300 cps, and a pH of about 10, and the water-dispersible polyurethane (PU) had a solid content of about 30 An aqueous dispersion polyurethane having a weight %, a viscosity of about 60 cps, and a pH of about 7 was used. Aminopropyl Isooctyl POSS (Aminopropyl Isooctyl POSS) was used as the polyhedral oligomer silsesquioxane (POSS), and calcium carbonate was used as an extender pigment.

표 1에 기재된 조성 이외에 아크릴 에멀전 100 중량부 대비 2 중량부의 분산제(Disper BYK-190), 0.625 중량부의 폴리실록산류 소포제, 0.7 중량부의 계면활성제(소듐도데실설페이트) 및 2 중량부의 전분계 증점제를 첨가하여 도료를 제조하였다. In addition to the composition shown in Table 1, 2 parts by weight of a dispersant (Disper BYK-190), 0.625 parts by weight of a polysiloxane antifoaming agent, 0.7 parts by weight of a surfactant (sodium dodecyl sulfate) and 2 parts by weight of a starch-based thickener were added to 100 parts by weight of the acrylic emulsion. Thus, a paint was prepared.

[제조예 2 내지 13][Production Examples 2 to 13]

제조예 1과 같은 방법으로 제조하되, 하기 표 1의 조성을 혼합하여 노면 표지용 도료를 제조하였다. It was prepared in the same manner as in Preparation Example 1, but the composition of Table 1 was mixed to prepare a paint for road marking.

제조예Manufacturing example AAAA PUPU POSSPOSS 차열안료Heat shielding pigment 체질안료Extender pigment 1One 100100 1010 33 77 8080 22 100100 88 1One 33 6565 33 100100 1515 55 1515 9090 44 100100 1010 33 77 8080 표면개질되지 않은 차열안료Heat shielding pigment without surface modification 55 100100 -- 33 77 8080 66 100100 1010 -- 77 8080 77 100100 1010 33 -- 8080 88 100100 22 33 77 8080 99 100100 2525 33 77 8080 1010 100100 1010 0.50.5 77 8080 1111 100100 1010 99 77 8080 1212 100100 1010 33 1One 8080 1313 100100 1010 33 2525 8080

샘플의 제조Sample preparation

아스팔트 시험편 상에 제조예의 노면 표지용 아크릴 도료를 각각 1 두께로 도포하고, 도포 직후 평균입경이 600 ㎛인 글라스비드를 도포한 뒤 24시간 동안 건조하여 샘플을 제조하였다. A sample was prepared by applying the acrylic paint for road surface marking of Preparation Example at a thickness of 1 each on the asphalt test piece, and immediately after application, glass beads having an average particle diameter of 600 µm were applied and dried for 24 hours.

부착강도, 내마모성, 글라스비드 부착력 확인Check adhesion strength, abrasion resistance, and glass bead adhesion

KS F 2561 부착강도시험, KS F 2429 마모저항시험법을 통하여 제조예의 도료로 제조된 노면 표지의 부착강도 및 내마모성을 각각 측정하고 그 결과를 표 2로 나타내었다. Through the KS F 2561 adhesion strength test and KS F 2429 abrasion resistance test method, the adhesion strength and abrasion resistance of road markings made of the coating material of Preparation Example were measured, respectively, and the results are shown in Table 2.

차열성능 확인Check heat shielding performance

아무런 처리도 되지 않은 아스팔트 및 상기 제조예의 도료가 도포된 상기 샘플을 바닥에 설치하고, 27㎝ 높이에 100W 백열등을 설치하였다. 백열등을 점등하고 공시체가 60 ℃가 되는 시점에서 각 시험편의 온도를 측정하고, 각 제조예의 도료로 제조된 노면 표지의 온도를 측정한 뒤, 공시체와 시험편의 온도차이를 계산하고 그 결과를 표 2로 나타내었다. 이때 온도차이가 클수록 시험편의 온도가 낮음을 의미하며, 이에 따라 차열성능이 우수한 것을 의미한다. Asphalt without any treatment and the sample coated with the coating of Preparation Example were installed on the floor, and a 100W incandescent lamp was installed at a height of 27 cm. Turn on the incandescent lamp, measure the temperature of each test piece at the point when the test piece reaches 60 ℃, measure the temperature of the road surface mark made with the paint of each production example, calculate the temperature difference between the test piece and the test piece, and calculate the result in Table 2. Represented by At this time, the larger the temperature difference, the lower the temperature of the test piece, which means that the heat shielding performance is excellent.

내크랙성 확인Crack resistance check

제조예의 도료를 실제 도료에 도포하고, 12개월이 경과한 뒤 크랙이 발생하였는지 여부를 5점 척도로 나타내었다. (5점:크랙이 거의 발생하지 않음~1점:크랙이 다수 발생함)The paint of the preparation example was applied to the actual paint, and whether cracks occurred after 12 months had elapsed was shown on a 5-point scale. (5 points: hardly any cracks ~ 1 point: many cracks)

제조예Manufacturing example 부착강도(N/mm2)Bonding strength (N/mm 2 ) 내마모성(mg/mm2)Wear resistance (mg/mm 2 ) 온도차(℃)Temperature difference (℃) 내크랙성Crack resistance 1One 2.12.1 0.180.18 15.015.0 55 22 2.02.0 0.190.19 14.614.6 55 33 1.91.9 0.210.21 14.414.4 55 44 1.71.7 0.250.25 10.510.5 55 55 1.51.5 0.200.20 13.513.5 22 66 1.41.4 0.230.23 12.412.4 44 77 1.91.9 0.220.22 9.29.2 33 88 1.71.7 0.250.25 12.612.6 33 99 1.81.8 0.380.38 13.313.3 55 1010 1.61.6 0.190.19 14.314.3 44 1111 1.71.7 0.410.41 14.014.0 55 1212 2.02.0 0.240.24 10.710.7 44 1313 1.21.2 0.300.30 14.614.6 33

표 2를 참고하면, 아크릴 에멀전 100 중량부 대비 5 내지 20 중량부의 수분산 폴리우레탄, 3 내지 15 중량부의 표면개질된 차열안료, 1 내지 5 중량부의 폴리헤드럴 올리고머 실세스퀴옥산 및 50 내지 110 중량부의 체질안료를 포함하는 제조예 1 내지 3의 구성이 부착성, 내마모성, 차열성 및 내크랙성이 우수한 것을 확인할 수 있다. Referring to Table 2, 5 to 20 parts by weight of water-dispersible polyurethane, 3 to 15 parts by weight of surface-modified heat-shielding pigment, 1 to 5 parts by weight of polyhedral oligomer silsesquioxane and 50 to 110 parts by weight of 100 parts by weight of acrylic emulsion It can be seen that the configurations of Preparation Examples 1 to 3 including parts by weight of the extender pigment have excellent adhesion, abrasion resistance, heat shielding property, and crack resistance.

Claims (7)

아크릴 에멀전 100 중량부 대비 5 내지 20 중량부의 수분산 폴리우레탄, 3 내지 15 중량부의 표면개질된 차열안료 및 1 내지 5 중량부의 폴리헤드럴 올리고머 실세스퀴옥산을 포함하며,
상기 표면개질된 차열안료는 아크릴기 또는 메타크릴기를 포함하는 표면개질제로 표면개질된 것인 노면 표지용 아크릴 도료.
Including 5 to 20 parts by weight of water-dispersible polyurethane, 3 to 15 parts by weight of a surface-modified heat shielding pigment, and 1 to 5 parts by weight of polyhedral oligomer silsesquioxane, based on 100 parts by weight of acrylic emulsion,
The surface-modified heat-shielding pigment is an acrylic paint for road marking that is surface-modified with a surface modifier containing an acrylic group or a methacrylic group.
삭제delete 삭제delete 제 1항에 있어서,
상기 수분산 폴리우레탄은 고형분 32 내지 37 중량%를 기준으로 점도가 50 내지 200 cps인 노면 표지용 아크릴 도료.
The method of claim 1,
The water-dispersible polyurethane is an acrylic paint for road marking having a viscosity of 50 to 200 cps based on a solid content of 32 to 37% by weight.
제 1항에 있어서,
상기 노면 표지용 아크릴 도료는 상기 아크릴 에멀젼 100 중량부 대비 50 내지 110 중량부의 체질안료를 포함하는 노면 표지용 아크릴 도료.
The method of claim 1,
The acrylic paint for road surface marking includes 50 to 110 parts by weight of an extender pigment based on 100 parts by weight of the acrylic emulsion.
제 1항에 있어서,
상기 표면개질제는 3-메타크릴옥시프로필 메틸디메톡시실란, 3-메타크릴옥시프로필 트리메톡시실란, 3-메타크릴옥시프로필 메틸디에톡시실란, 3-메타크릴옥시프로필 트리에톡시실란 및 3-아크릴옥시프로필 트리메톡시실란에서 선택되는 하나 또는 둘 이상을 포함하는 노면 표지용 아크릴 도료.
The method of claim 1,
The surface modifier is 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3- An acrylic paint for road marking comprising one or two or more selected from acryloxypropyl trimethoxysilane.
삭제delete
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KR102221325B1 (en) * 2020-12-04 2021-03-02 문진호 Non-slip braille block sheet for guiding the disabled
KR102370531B1 (en) * 2021-10-05 2022-03-04 주식회사 아이디엠램프 Water-based paint for interior and exterior of buildings with excellent thermal insulation performance and thermal shock resistance, and manufacturing method thereof

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KR20120134173A (en) * 2011-06-01 2012-12-12 이동복 Marking of road and its construction method
KR101768081B1 (en) 2016-09-28 2017-08-14 주식회사이화정공 Acryl emulsion resin composition for road marking with improved water resisting and bead adhesion and paint composition using the same
KR102046627B1 (en) * 2019-09-03 2019-11-20 주식회사 정석케미칼 Room temperature curing, dual liquid type road marking paint composition with high long term thermal shielding effect and durability

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US5073404A (en) * 1987-03-09 1991-12-17 Minnesota Mining And Manufacturing Company Silica coating composition for reflective sheeting
KR20120134173A (en) * 2011-06-01 2012-12-12 이동복 Marking of road and its construction method
KR101768081B1 (en) 2016-09-28 2017-08-14 주식회사이화정공 Acryl emulsion resin composition for road marking with improved water resisting and bead adhesion and paint composition using the same
KR102046627B1 (en) * 2019-09-03 2019-11-20 주식회사 정석케미칼 Room temperature curing, dual liquid type road marking paint composition with high long term thermal shielding effect and durability

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* Cited by examiner, † Cited by third party
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KR102221325B1 (en) * 2020-12-04 2021-03-02 문진호 Non-slip braille block sheet for guiding the disabled
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KR102370531B1 (en) * 2021-10-05 2022-03-04 주식회사 아이디엠램프 Water-based paint for interior and exterior of buildings with excellent thermal insulation performance and thermal shock resistance, and manufacturing method thereof

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