KR101263169B1 - Solventless flame-retardant, conductive coating compund - Google Patents

Solventless flame-retardant, conductive coating compund Download PDF

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KR101263169B1
KR101263169B1 KR1020110086188A KR20110086188A KR101263169B1 KR 101263169 B1 KR101263169 B1 KR 101263169B1 KR 1020110086188 A KR1020110086188 A KR 1020110086188A KR 20110086188 A KR20110086188 A KR 20110086188A KR 101263169 B1 KR101263169 B1 KR 101263169B1
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epoxy resin
weight
flame retardant
solvent
retardant
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KR20130023439A (en
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이범철
이대수
이범석
고상진
김광복
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이스켐주식회사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

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  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

본 발명은 전도성 등 전기적 성질이 우수하고, 난연성이 우수하여 화학공장, 반도체 생산라인, 탄약고, 병원수술실 등에서 정전기 방지 및 화재의 위험을 줄일 수 있는 무용제형 난연성 전도성 도료수지에 관한 것으로서, 에폭시수지와 액상고무로 이루어진 주제에 전도성 충전제 및 인계난연제가 혼합하여 이루어지고, 상기 에폭시수지는 페놀계 에폭시수지와 브롬계 에폭시수지가 혼합되어 이루어진 것을 특징으로 한다.The present invention relates to a solvent-free flame-retardant conductive paint resin that can reduce the risk of static electricity and prevent fire in chemical plants, semiconductor production lines, ammunition, hospital surgery room, etc. is excellent in electrical properties, such as electrical conductivity and excellent flame retardancy. Conductive fillers and phosphorus-based flame retardants are mixed on the subject of liquid rubber, and the epoxy resin is characterized in that the phenol-based epoxy resin and bromine-based epoxy resin are mixed.

Description

무용제형 난연성 전도성 도료수지{Solventless flame-retardant, conductive coating compund}Solventless flame-retardant, conductive coating compund

본 발명은 전도성 등 전기적 성질이 우수하고, 난연성이 우수한 무용제형 난연성 전도성 도료수지에 관한 것이다.
The present invention relates to a solvent-free flame retardant conductive paint resin having excellent electrical properties such as conductivity and excellent flame retardancy.

일반적으로, 인간이 생활하고 있는 환경 대부분에 사용되고 있는 도료(Paint)는 미관적인 효과를 위해 건축물마감재나 자동차 외관을 도색하는 데 이용되고 있다. 도료원액에 혼합하여 사용하는 용제(Solvent)는 도색작업의 용이함을 위해 일정비율 혼합하여 사용한다. 용제(Solvent)로 사용하는 물질은 대부분 휘발성 유기화합물(VOCs)를 포함하고 있으며, 이러한 휘발성 유기화합물은 인체에 해를 주거나 환경오염의 원인이 되어 세계적으로 그 사용량을 제한하고 있는 상황이다. 우리나라의 경우 친환경정책 추진과정에서 2005년 이후 매년 휘발성 유기화합물에 대한 기준을 강화하고 있는 상황이며, 기존 도료제조업체의 경우 용제의 사용량을 줄인 친환경적인 제품을 개발하여 판매가 진행되고 있다. 하지만, 정부규제 및 제조업체의 자발적인 노력에도 불구하고 휘발성 유기화합물의 배출량의 감소는 극히 미미하게 진행되고 있는 것 또한 사실이다. 해외기술과 국내기술을 비교하여 볼 때 전체 도료량 중 용제가 차지하는 비중은 외국의 경우 9%이내이나 국내의 경우 43%이상으로 도료의 절반정도를 차지하고 있으며 외국제품에 비해 약 5배정도 높다.
In general, paint, which is used in most of the environment in which humans live, is used to paint building finishes and exteriors of automobiles for aesthetic effects. Solvent used in the paint stock is mixed in a fixed ratio for ease of painting. Solvents include most volatile organic compounds (VOCs), and these volatile organic compounds are used around the world because they cause harm to humans or cause environmental pollution. Korea has been strengthening the standards for volatile organic compounds every year since 2005 in the process of promoting eco-friendly policies, and existing paint manufacturers have been developing and selling eco-friendly products with reduced solvent usage. However, despite government regulations and voluntary efforts by manufacturers, it is also true that the reduction of volatile organic compounds emissions is extremely small. Compared with foreign technology and domestic technology, solvents account for less than 9% of the total paint volume and 43% or more in Korea, accounting for about half of the paint and about 5 times higher than foreign products.

특수 도료란 특수 목적을 위해 생산되는 도료로 방염/내염 도료, 전자파 차폐(또는 흡수) 도료, 전도성 도료, Pre-coating 도료, 광촉매 초미분체 도료, 난연 도료, 발열 도료, 항균 도료, 자기 세정성 도료 등 기능성이 부여된 도료이다.Special paints are paints produced for special purposes. Flame retardant / flame retardant paint, electromagnetic shielding (or absorption) paint, conductive paint, pre-coating paint, photocatalytic ultra fine powder paint, flame retardant paint, exothermic paint, antibacterial paint, self-cleaning paint It is the coating to which functionality was given.

이중 전도성 도료는 대전방지를 목적으로 하는 도료로 화학공장, 반도체 생산라인, 탄약고 등 정전기 발생에 의해 화재의 위험이나 제품생산의 방해요인을 제거하기 위해 사용한다. 전도성 도료의 가장 중요한 특징은 표면저항이며 이 표면저항이 104~107Ω/□ 사이의 값을 가질 경우 가장 뛰어난 대전방지능력을 나타내는 것으로 알려져 있다. 현재 국내에서 사용되고 있는 대전방지용 도료는 대부분 수입에 의존하고 있으며, 국내 제조기술의 경우 도료 내에 전기적 특성을 나타낼 수 있는 물질 즉, 전도성 충전제를 일부분 혼합하여 전도성을 부여하고 있다.Double conductive paint is used to prevent the risk of fire or disturbance of product production by static electricity generation such as chemical factory, semiconductor production line, and ammunition warehouse. The most important feature of conductive paints is surface resistance, which is known to exhibit the best antistatic performance when the surface resistance is between 10 4 and 10 7 Ω / □. The antistatic paints currently used in Korea depend mostly on imports, and in the case of domestic manufacturing technology, some materials that can exhibit electrical properties in the paint, that is, conductive fillers are partially mixed to give conductivity.

이러한 전도성 충전제는 금속화합물, 흑연, 카본블랙 등이 사용되고 있다.Such conductive fillers include metal compounds, graphite, carbon black, and the like.

한편, 전도성 도료와 관련하여 공개특허 제1997-7007250호(도전성 도료), 일본국 특개평10-168502(고열전도율복합재) 등이 제안된 바 있다. 공개특허 제1997-7007250호의 도전성 도료의 경우 유기용제를 사용함에 따라 작업환경이 좋지 못하고 인체에 유해하며 환경오염을 유발할 수 있는 문제가 있다. 그리고 일본국 특개평10-168502의 고열전도율 복합재에는 유기용제 등이 사용되지 않으나 핫 프레스 성형함에 따라 제조공정이 복잡하고 제조비용이 높은 문제가 있다.
On the other hand, in connection with conductive paints, Patent Publication No. 1997-7007250 (conductive paints), Japanese Patent Application Laid-open No. Hei 10-168502 (high thermal conductivity composites) and the like have been proposed. In the case of the conductive paint of Korean Patent No. 1997-7007250, there is a problem in that the working environment is not good, it is harmful to the human body, and environmental pollution can be caused by using the organic solvent. In addition, although the organic solvent is not used in the high thermal conductivity composite material of Japanese Patent Laid-Open No. 10-168502, there is a problem in that the manufacturing process is complicated and the manufacturing cost is high due to hot press molding.

본 발명은 전도성 등 전기적 성질이 우수하고, 난연성이 우수하여 화학공장, 반도체 생산라인, 탄약고, 병원수술실 등에서 정전기 방지 및 화재의 위험을 줄일 수 있는 무용제형 난연성 전도성 도료수지를 제공함에 목적이 있다.
An object of the present invention is to provide a solvent-free flame-retardant conductive paint resin that is excellent in electrical properties such as conductivity, and excellent flame retardancy to reduce the risk of static electricity and fire in chemical plants, semiconductor production lines, ammunition, hospital surgery room.

상기와 같은 목적을 달성하기 위한 본 발명은, The present invention for achieving the above object,

에폭시수지와 액상고무로 이루어진 주제에 전도성 충전제 및 인계난연제가 혼합하여 이루어진 것을 특징으로 하는 무용제형 난연성 전도성 도료수지를 제공한다.It provides a solvent-free flame retardant conductive paint resin, characterized in that the conductive filler and the phosphorus-based flame retardant is mixed on the subject consisting of epoxy resin and liquid rubber.

상기 주제 100중량부에 전도성 충전제 0.1~10중량부, 인계난연제 10~30중량부가 혼합되는 것이 좋다.0.1 to 10 parts by weight of the conductive filler, 10 to 30 parts by weight of the phosphorus-based flame retardant may be mixed to 100 parts by weight of the main ingredient.

상기 주제는 에폭시수지 60~70중량%와 액상고무 30~40중량%로 이루어진 것이 바람직하다.The subject is preferably made of 60 to 70% by weight of epoxy resin and 30 to 40% by weight of liquid rubber.

아울러, 상기 에폭시수지는 페놀계 에폭시수지와 브롬계 에폭시수지가 혼합되어 이루어지고, 상기 액상고무는 CTBN(carboxyl-terminated acrylonitrile copolymer)으로 이루어진 것이 좋다.In addition, the epoxy resin is made of a mixture of phenol-based epoxy resin and bromine-based epoxy resin, the liquid rubber is preferably made of CTBN (carboxyl-terminated acrylonitrile copolymer).

그리고 상기 인계난연제는 인산에스테르, 축합인산에스테르, 인-질소계 난연제, 적인, 포스파젠(phosphazene) 중 선택된 1종 이상으로 이루어진 것이 바람직하다.
The phosphorus-based flame retardant is preferably made of one or more selected from phosphate ester, condensed phosphate ester, phosphorus-nitrogen flame retardant, red, phosphazene.

이하, 본 발명의 무용제형 난연성 전도성 도료수지에 대해 상세히 설명하면 다음과 같다.Hereinafter, the solvent-free flame retardant conductive paint resin of the present invention will be described in detail.

본 발명의 무용제형 난연성 전도성 도료수지는 에폭시수지와 액상고무로 이루어진 주제에 전도성 충전제 및 인계난연제가 혼합하여 이루어진다.The solvent-free flame retardant conductive paint resin of the present invention is formed by mixing a conductive filler and a phosphorus-based flame retardant on a subject composed of an epoxy resin and a liquid rubber.

상기 에폭시수지는 비스페놀에이 에폭시수지, 비스페놀에프 에폭시수지 등의 페놀계 에폭시수지, 브롬화에폭시수지 등의 브롬계 에폭시수지를 혼합하여 사용한다. The epoxy resin is used by mixing a phenol epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, bromine epoxy resin such as brominated epoxy resin.

페놀계 에폭수지를 단독으로 사용할 경우 난연제의 과량 투입으로도 난연성이 좋지 못하나, 페놀계 에폭수지와 브롬계 에폭시수지를 혼합하여 사용할 경우 할로겐계와 난할로겐계간의 상승작용에 의해 때문에 난연성이 우수하다.
In case of using phenolic epoxy resin alone, the flame retardancy is not good even when excessive amount of flame retardant is added.However, when phenolic epoxy resin and bromine epoxy resin are mixed, the flame retardancy is excellent because of the synergy between halogen-based and halogen-based halogen resins. .

그리고 상기 액상고무는 도막의 충격강도를 향상시키기 위한 것으로서, 에폭시수지와 하이브리드화를 통해 난연화가 가능하고 충격강도를 향상시키기 위하여 CTBN(carboxyl-terminated acrylonitrile copolymer)을 사용하는 것이 좋다.
And the liquid rubber is to improve the impact strength of the coating film, flame retardant is possible through the hybridization with epoxy resin, it is preferable to use CTBN (carboxyl-terminated acrylonitrile copolymer) to improve the impact strength.

상기 주제는 상기 에폭시수지 60~70중량%와 액상고무 30~40중량%로 이루어지는 것이 좋다. 상기 에폭시수지가 60중량% 미만으로 혼합되는 경우 접착력이 저하되고, 70중량% 초과로 혼합되는 경우 도막의 충격강도가 저하된다.
The subject is preferably made of 60 to 70% by weight of the epoxy resin and 30 to 40% by weight of the liquid rubber. When the epoxy resin is mixed at less than 60% by weight, the adhesive strength is lowered, and when the epoxy resin is mixed at more than 70% by weight, the impact strength of the coating film is lowered.

상기 전도성 충전제는 탄소나노튜브, 그라펜, 전도성 카본블랙 등을 사용한다. 상기 전도성 충전제는 상기 주제 100중량부에 대해 0.5~10중량부가 혼합되는 것이 좋다. 상기 전도성 충전제가 0.5중량부 미만으로 혼합될 경우 전도성이 저하되고, 10중량부 초과로 혼합되면 제조비용이 상승하고 분산도가 저하되며 접착력이 저하된다.
The conductive filler may be carbon nanotubes, graphene, conductive carbon black, or the like. The conductive filler is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the main ingredient. When the conductive filler is mixed at less than 0.5 parts by weight, the conductivity is lowered. When the conductive filler is mixed at more than 10 parts by weight, the manufacturing cost is increased, the dispersion degree is lowered, and the adhesive strength is lowered.

그리고 상기 인계난연제는 전도성 도료수지에 난연성수지를 부여하기 위한 것이다. 상기 인계난연제로서는 인산에스테르, 축합인산에스테르, 인-질소계 난연제, 적인, 포스파젠(phosphazene) 중 선택된 1종 이상으로 이루어진다.And the phosphorus-based flame retardant is for imparting a flame-retardant resin to the conductive paint resin. The phosphorus flame retardant is composed of at least one selected from phosphate ester, condensed phosphate ester, phosphorus-nitrogen flame retardant, red, phosphazene.

상기 인계난연제는 상기 주제 100중량부에 10~30중량부가 혼합되는 것이 바람직하다. 인계난연제가 10중량부 미만으로 혼합되면 할로겐계와 난할로겐계간의 상승작용이 일어나지 않아 난연성이 좋지 못하고, 30중량부 초과로 혼합되면 에폭시와 전도성 충전제의 함량이 낮아져 전도성이 저하되고 충격강도가 저하되는 문제가 있다.The phosphorus flame retardant is preferably mixed 10 to 30 parts by weight to 100 parts by weight of the main body. If the phosphorus-based flame retardant is mixed at less than 10 parts by weight, the synergy between halogen-based and halogen-based halogens does not occur, and thus the flame retardancy is not good. There is a problem.

상기 인산에스테르와 축합인산에스티르계는 산소를 다량 함유하고있는 고분자 물질에 우수한 난연효과를 가지고 열분해에 의하여 폴리인산이 생성되고 이것은 에스테르화 및 탈수소화하여 숯을 생성하며 이렇게 생성된 숯이 산소와 열을 차단하는 메카니즘을 가진다.The phosphate ester and the condensed phosphate ester have excellent flame retardant effect on the polymer material containing a large amount of oxygen, and polyphosphoric acid is produced by pyrolysis, which is esterified and dehydrogenated to generate charcoal. Has a mechanism to block

상기 인-질소계 난연제는 요소나 질소화합물이 폴리인산의 열축중합을 촉진시켜 고분자 폴리인산을 생성하여 이것이 탈수소촉매로 작용하여 숯형성을 유도한다. The phosphorus-nitrogen-based flame retardant is a urea or nitrogen compound to promote the polycondensation of polyphosphoric acid to produce a polymer polyphosphoric acid, which acts as a dehydrogenation catalyst to induce charcoal formation.

그리고 상기 적인계 난연제는 응축상에서의 분해를 방해하고 탄화율을 높이는데 사용되어 난연작용을 한다.In addition, the flame retardant is used to hinder the decomposition in the condensation phase and to increase the carbonization rate is flame retardant.

한편, 포스파젠은 탄소층을 형성시켜 산소 및 잠열을 차단하여 열분해 반응을 감소시키며 숯 형성에 도움을 준다.
On the other hand, phosphazene forms a carbon layer to block the oxygen and latent heat to reduce the pyrolysis reaction and help to form charcoal.

본 발명의 무용제형 난연성 전도성 도료수지는 전도성 등 전기적 성질이 우수하고, 난연성이 우수하여 화학공장, 반도체 생산라인, 탄약고, 병원수술실 등에서 정전기 방지 및 화재의 위험을 줄일 수 있는 효과가 있다.
The solvent-free flame retardant conductive paint resin of the present invention has excellent electrical properties such as conductivity, and has excellent flame retardancy, which can reduce the risk of static electricity prevention and fire in chemical plants, semiconductor production lines, ammunition warehouses, hospital surgery rooms, and the like.

이하, 본 발명의 무용제형 난연성 전도성 도료수지를 실시예를 들어 상세히 설명하면 다음과 같고, 본 발명의 권리범위는 하기의 실시예에 한정되는 것은 아니다.
Hereinafter, the solvent-free flame retardant conductive paint resin of the present invention will be described in detail with reference to Examples. The scope of the present invention is not limited to the following Examples.

[실시예 1]Example 1

에폭시수지 70중량%와 액상고무로서 CTBN 30중량%를 혼합하여 주제를 얻었다. 에폭시수지는 페놀계 에폭시수지와 브롬계 에폭시수지를 50:20의 비율로 혼합하여 사용하였다.The main body was obtained by mixing 70% by weight of epoxy resin and 30% by weight of CTBN as a liquid rubber. Epoxy resin was used by mixing phenolic epoxy resin and bromine epoxy resin in a ratio of 50:20.

상기 주제 100중량부에 전도성 충전제 5중량부, 혼합 인계난연제 5중량부를 혼합하여 실시예 1인 무용제형 난연성 전도성 도료수지를 제조하였다. 이때 상기 전도성 충전제는 탄소나노튜브, 그라펜 및 전도성 카본블랙을 동일한 비율로 혼합하여 사용하였고, 상기 혼합 인계난연제는 인산에스테르계, 축합인산에스테르계, 인-질소계난연제, 적인계 난연제, 포스파젠을 동일한 비율로 혼합하여 사용하였다.
The solvent-free flame retardant conductive paint resin of Example 1 was prepared by mixing 5 parts by weight of the conductive filler and 5 parts by weight of the mixed phosphorus flame retardant. At this time, the conductive filler was used by mixing carbon nanotubes, graphene and conductive carbon black in the same ratio, and the mixed phosphorus flame retardant is phosphate ester, condensed phosphate ester, phosphorus-nitrogen flame retardant, phosphorus flame retardant, phosphazene Was used by mixing in the same ratio.

[실시예 2][Example 2]

실시예 1과 달리 상기 혼합 인계난연제를 상기 주제 100중량부에 25중량부를 혼합하여 실시예 2인 무용제형 난연성 전도성 도료수지를 제조하였다.
Unlike Example 1, 25 parts by weight of the mixed phosphorus-based flame retardant was mixed with 100 parts by weight of the main ingredient to prepare a solvent-free flame retardant conductive paint resin of Example 2.

[실시예 3][Example 3]

실시예 1과 달리 페놀계 에폭시수지와 브롬계 에폭시수지를 65:5의 비율로 혼합한 에폭시수지를 사용하여 실시예 3인 무용제형 난연성 전도성 도료수지를 제조하였다.
Unlike Example 1, a solvent-free flame-retardant conductive paint resin of Example 3 was prepared using an epoxy resin mixed with a phenolic epoxy resin and a bromine epoxy resin in a ratio of 65: 5.

[실시예 4]Example 4

실시예 1과 달리 상기 주제를 에폭시수지 60중량%와 CTBN 40중량%를 혼합하여 사용하였고, 상기 에폭시수지는 폐놀계 에폭시수지와 브롬계 에폭시수지를 20:40의 비율로 혼합한 것을 사용하여 실시예 4인 무용제형 난연성 전도성 도료수지를 제조하였다.
Unlike Example 1, the main material was mixed with 60% by weight of epoxy resin and 40% by weight of CTBN, and the epoxy resin was carried out using a mixture of waste epoxy resin and bromine epoxy resin in a ratio of 20:40. A solvent-free flame retardant conductive paint resin of Example 4 was prepared.

[실시예 5][Example 5]

실시예 4와 달리 상기 혼합 인계난연제를 주제 100중량부에 60중량부를 혼합하여 실시예 5인 무용제형 난연성 전도성 도료수지를 제조하였다.
Unlike Example 4, by mixing 60 parts by weight of the mixed phosphorus-based flame retardant to 100 parts by weight of the main ingredient to prepare a solvent-free flame-retardant conductive paint resin of Example 5.

[비교예 1]Comparative Example 1

폐놀계 에폭시수지 100중량부에 전도성 충전제 5중량부를 혼합하여 비교예 1인 전도성 도료수지를 제조하였다. 이때 상기 전도성 충전제는 탄소나노튜브, 그라펜 및 전도성 카본블랙을 동일한 비율로 혼합하여 사용하였다.
The conductive paint resin of Comparative Example 1 was prepared by mixing 5 parts by weight of the conductive filler with 100 parts by weight of the wasteol-based epoxy resin. In this case, the conductive filler was used by mixing carbon nanotubes, graphene and conductive carbon black in the same ratio.

[비교예 2]Comparative Example 2

페놀계 에폭시수지 70중량%, CTBN 30중량%를 혼합하여 주제를 얻었다. 상기 주제 100중량부에 전도성 충전제 5중량부, 인산에스테르계 인산난연제 40중량부를 혼합하여 비교예 2인 전도성 도료수지를 제조하였다. 이때 상기 전도성 충전제는 탄소나노튜브, 그라펜 및 전도성 카본블랙을 동일한 비율로 혼합하여 사용하였다.
The main body was obtained by mixing 70 weight% of phenolic epoxy resins, and 30 weight% of CTBN. The conductive paint resin of Comparative Example 2 was prepared by mixing 5 parts by weight of the conductive filler and 40 parts by weight of the phosphate ester phosphate flame retardant. In this case, the conductive filler was used by mixing carbon nanotubes, graphene and conductive carbon black in the same ratio.

[비교예 3][Comparative Example 3]

에폭시수지 70중량%와 CTBN 30중량%를 혼합하여 주제를 얻었다. 상기 에폭시수지는 페놀계 에폭시수지와 브롬계 에폭시수지를 20:50의 비율로 혼합한 것을 사용하였다. 상기 주제 100중량부에 전도성 충전제 5중량부를 혼합하여 비교예 3인 전도성 도료수지를 제조하였다. 이때 상기 전도성 충전제는 탄소나노튜브, 그라펜 및 전도성 카본블랙을 동일한 비율로 혼합하여 사용하였다.
The main body was obtained by mixing 70 weight% of epoxy resins and 30 weight% of CTBN. The epoxy resin used was a mixture of phenol epoxy resin and bromine epoxy resin in a ratio of 20:50. 5 parts by weight of the conductive filler was mixed with 100 parts by weight of the main ingredient to prepare a conductive paint resin of Comparative Example 3. In this case, the conductive filler was used by mixing carbon nanotubes, graphene and conductive carbon black in the same ratio.

[난연성 시험][Flame retardancy test]

실시예 1 내지 5의 무용제형 난연성 전도성 도료수지 및 비교예 1~3의 전도성 도료수지에 대해 UL 94V-0의 방법으로 난연성을 시험하였다. 이때 UL 94V-0이 방법에 의한 난연성 시험은 상기 실시예 1~5의 무용제형 난연성 전도성 도료수지 10개의 시편과, 상기 비교예 1~3의 전도성 도료수지 10개의 시편을 대상으로 실시한 후 평균값을 측정하였다. The flame retardance of the solvent-free flame retardant conductive paint resins of Examples 1 to 5 and the conductive paint resins of Comparative Examples 1 to 3 were tested by the method of UL 94V-0. In this case, the UL 94V-0 flame retardancy test was performed on ten specimens of the solvent-free flame retardant conductive paint resins of Examples 1 to 5 and ten specimens of the conductive paint resins of Comparative Examples 1 to 3, and then averaged. Measured.

실시예 1 내지 5 및 비교예 1~3에 대한 UL 94V-0의 난연시험결과는 표 1로 나타냈고, 평균값을 측정하여 UL 94V-0의 난연시험을 만족하면 '○'으로 표시하고, 만족하지 못하면 '×'로 표시하였다.
Flame retardant test results of UL 94V-0 for Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1, if the average value is measured to satisfy the flame retardant test of UL 94V-0, marked with "○", satisfactory If not, 'x' is indicated.

난연시험Flame retardant test 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3
UL 94V-0
UL 94V-0

○
○
○
○
○
○
○
○
○
○
×
×
×
×
×
×

표 1과 같이 실시예 1 내지 5의 무용제형 난연성 전도성 도료수지는 모두 UL 94V-0의 난연시험을 만족하였으나, 비교예 1 내지 3은 모두 UL 94V-0의 난연시험을 만족하지 못하였다.As shown in Table 1, all of the solvent-free flame retardant conductive paint resins of Examples 1 to 5 satisfied the flame retardancy test of UL 94V-0, but Comparative Examples 1 to 3 did not satisfy the flame retardant test of UL 94V-0.

특히, 페놀계 에폭시수지와 브롬계 에폭시수지를 혼합한 에폭시수지를 사용한 실시예 1 내지 5의 경우 모두 난연성이 우수한 반면, 비교예 1과 같이 페놀계 에폭시수지를 단독으로 사용한 경우 난연성이 좋지 못하였다.
In particular, in the case of Examples 1 to 5 using the epoxy resin mixed with phenol-based epoxy resin and bromine-based epoxy resin was excellent in flame retardancy, when using a phenol-based epoxy resin alone as in Comparative Example 1 was not good flame retardancy .

Claims (7)

에폭시수지와 액상고무로 이루어진 주제에 전도성 충전제 및 인계난연제가 혼합하여 이루어지고, 상기 에폭시수지는 페놀계 에폭시수지와 브롬계 에폭시수지가 혼합되어 이루어진 것을 특징으로 하는 무용제형 난연성 전도성 도료수지.
A solvent-free flame-retardant conductive paint resin, characterized in that the epoxy resin and the liquid rubber made of a conductive filler and a phosphorus flame retardant is mixed, the epoxy resin is a mixture of phenolic epoxy resin and bromine epoxy resin.
제1항에 있어서,
상기 주제 100중량부에 전도성 충전제 0.1~10중량부가 혼합되는 것을 특징으로 하는 무용제형 난연성 전도성 도료수지.
The method of claim 1,
Solvent-free flame-retardant conductive paint resin, characterized in that 0.1 to 10 parts by weight of the conductive filler is mixed to 100 parts by weight of the subject.
제2항에 있어서,
상기 주제 100중량부에 인계난연제 10~30중량부가 혼합되는 것을 특징으로 하는 무용제형 난연성 전도성 도료수지.
The method of claim 2,
A solvent-free flame-retardant conductive paint resin, characterized in that 10 to 30 parts by weight of the phosphorus-based flame retardant is mixed to 100 parts by weight of the subject.
제1항 내지 제3항 중 어느 한 항에 있어서,
상기 주제는 에폭시수지 60~70중량%와 액상고무 30~40중량%로 이루어진 것을 특징으로 하는 무용제형 난연성 전도성 도료수지.
4. The method according to any one of claims 1 to 3,
The subject is a solvent-free flame-retardant conductive paint resin, characterized in that consisting of 60 to 70% by weight of epoxy resin and 30 to 40% by weight of liquid rubber.
제4항에 있어서,
상기 액상고무는 CTBN(carboxyl-terminated acrylonitrile copolymer)으로 이루어진 것을 특징으로 하는 무용제형 난연성 전도성 도료수지.
5. The method of claim 4,
The liquid rubber is a solvent-free flame retardant conductive paint resin, characterized in that consisting of CTBN (carboxyl-terminated acrylonitrile copolymer).
제3항에 있어서,
상기 인계난연제는 인산에스테르, 축합인산에스테르, 인-질소계 난연제, 적인, 포스파젠(phosphazene) 중 선택된 1종 이상으로 이루어진 것을 특징으로 하는 무용제형 난연성 전도성 도료수지.The method of claim 3,
The phosphorus flame retardant is a solvent-free flame retardant conductive paint resin, characterized in that consisting of one or more selected from phosphate ester, condensed phosphate ester, phosphorus-nitrogen flame retardant, red, phosphazene (phosphazene). 삭제delete
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