KR0149697B1 - Epoxy resin powder coatings - Google Patents

Epoxy resin powder coatings

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Publication number
KR0149697B1
KR0149697B1 KR1019940039941A KR19940039941A KR0149697B1 KR 0149697 B1 KR0149697 B1 KR 0149697B1 KR 1019940039941 A KR1019940039941 A KR 1019940039941A KR 19940039941 A KR19940039941 A KR 19940039941A KR 0149697 B1 KR0149697 B1 KR 0149697B1
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South Korea
Prior art keywords
weight
epoxy resin
parts
powder coating
resin powder
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KR1019940039941A
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Korean (ko)
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KR960022906A (en
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박세동
신무진
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김충세
고려화학주식회사
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Priority to KR1019940039941A priority Critical patent/KR0149697B1/en
Publication of KR960022906A publication Critical patent/KR960022906A/en
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Publication of KR0149697B1 publication Critical patent/KR0149697B1/en

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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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C08K3/00Use of inorganic substances as compounding ingredients
    • 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
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04Condensation polymers of aldehydes or ketones with phenols only
    • 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03Powdery paints
    • C09D5/033Powdery paints characterised by the additives
    • 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
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • 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
    • C09D7/65Additives macromolecular
    • 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
    • C09D7/70Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

Abstract

본 발명은 에폭시 수지 분말 피복물에 관한 것으로, 좀 더 상세하게는 (A) 에폭시 수지 100중량부, (B) 페놀 수지 10 내지 80중량부, (C) 산무수물 20 내지 70중량부 (D) 커플링제 1 내지 20중량부, (E) 무기충진제 50 내지 200중량부 및 기타 첨가제로 이루어진 에폭시 수지 분말 피복물에 관한 것이다.The present invention relates to an epoxy resin powder coating, more specifically, (A) 100 parts by weight of epoxy resin, (B) 10 to 80 parts by weight of phenol resin, (C) 20 to 70 parts by weight of acid anhydride (D) An epoxy resin powder coating comprising 1 to 20 parts by weight of a ring agent, 50 to 200 parts by weight of an inorganic filler (E), and other additives.

Description

에폭시 수지 분말 피복물Epoxy resin powder coating

본 발명은 에폭시 수지 분말 피복물에 관한 것으로, 좀 더 상세하게는 에폭시 봉지재의 내부 응력을 낮추고 수지조성물과 소지와의 박리현상을 최소화하고 내습성을 높여 장기저장성이 좋은 에폭시 수지 분말 피복물에 관한 것이다.The present invention relates to an epoxy resin powder coating, and more particularly, to an epoxy resin powder coating having good long-term storage property by lowering internal stress of the epoxy encapsulant, minimizing peeling between the resin composition and the substrate, and increasing moisture resistance.

일반적으로, 피복조성물에 내부응력이 커지면 소지인 금속재료와의 박리로 인한 권선작업시 내충격성의 저하로 내전압 불량이 발생하는 문제점이 발생한다. 따라서, 기존에는 에폭시 수지에 산무수물을 단독으로 첨가시켜 사용하였으나, 내열성은 좋으나 내습에 약해 장기저장시 문제가 있었다. 한편, 상기 산무수물이 첨가된 수지 조성물의 내부응력을 낮추기 위하여 에폭시 수지에다 부타디엔계고무를 첨가하는 방법이 제안되었으나, 상기 방법은 산무수물이 대부분 융점이 높기 때문에 고무변성 수지와 균일한 분산이 어려워 응력감소에 효과적이지 못하며, 고무자체의 친수성에 기인한 내습성 때문에 산무수물의 장기저장성에 부정적인 영향을 끼친다. 또한, 다른 방법에서 제안된 실리콘 변성 수지는 내부응력을 감소시키는 효과는 있으나 균일한 외관을 얻기가 힘들어 문제가 된다.In general, when the internal stress increases in the coating composition, a problem occurs in that a withstand voltage defect occurs due to a decrease in impact resistance during winding work due to peeling from a metallic material. Therefore, in the past, acid anhydride was added to epoxy resin alone, but heat resistance was good, but there was a problem in long-term storage due to weak moisture resistance. On the other hand, in order to lower the internal stress of the resin composition to which the acid anhydride is added, a method of adding butadiene-based rubber to an epoxy resin has been proposed. It is not effective in reducing stress and has a negative effect on the long-term storage of acid anhydrides due to the moisture resistance due to the hydrophilicity of the rubber itself. In addition, the silicone-modified resin proposed in another method has the effect of reducing the internal stress, but it is difficult to obtain a uniform appearance is a problem.

따라서, 본 발명의 목적은 상기에서 언급된 단점들을 극복하기 위해 외관이 양호하고 내부응력이 낮아 내충격성이 우수하며, 장기저장성을 개선할 수 있는 변성페놀수지를 사용하여 내충격성을 높이며, 수지 조성물과 소지와의 밀착성을 높여 부착력을 향상시키고 산무수물의 산화 반응을 억제하여 장기저장성을 향상시킨 에폭시 수지 분말 피복물을 제공하는데 있다.Accordingly, an object of the present invention is to improve the impact resistance by using a modified phenolic resin that has a good appearance and low internal stress to overcome the above-mentioned disadvantages, low impact and improved long-term storage, resin composition The present invention provides an epoxy resin powder coating having improved long-term storage properties by improving adhesion and increasing adhesion between the base and the base, and inhibiting the oxidation reaction of the acid anhydride.

상기 목적을 달성하기 위한 본 발명의 피복물은 (A) 에폭시 수지 100중량부, (B) 페놀 수지 10 내지 80중량부, (C) 산무수물 20 내지 70중량부 (D) 커플링제 1 내지 20중량부, (E) 무기충진제 50 내지 200중량부 및 기타 첨가제로 이루어진다.The coating of the present invention for achieving the above object is (A) 100 parts by weight of epoxy resin, (B) 10 to 80 parts by weight of phenol resin, (C) 20 to 70 parts by weight of acid anhydride (D) 1 to 20 parts by weight of coupling agent (E) 50 to 200 parts by weight of the inorganic filler and other additives.

이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명에서 사용되는 에폭시 수지로는 하기 식(Ⅰ)로 표시되는 비페닐 에폭시 수지, 노볼락 에폭시 수지, 노볼락 변성 에폭시 수지, 비스페놀 A형 에폭시 수지를 단독 또는 혼용하여 사용한다. 사용되는 에폭시 수지의 당량은 160 내지 350정도, 바람직하게는 170 내지 250인 것이 기계적, 전기적 특성이 우수하다. 또한, V는 반도체 칩표면에 있는 알루미늄등의 금속재료 부식을 방지하기 위하여 가수 분해성 염소이온의 함량이 500ppm 이하인 것을 사용함이 바람직하다.As an epoxy resin used by this invention, a biphenyl epoxy resin, a novolak epoxy resin, a novolak modified epoxy resin, and a bisphenol-A epoxy resin represented by following formula (I) are used individually or in mixture. Equivalent epoxy resin used is about 160 to 350, preferably 170 to 250 is excellent in mechanical and electrical properties. In addition, in order to prevent corrosion of metal materials, such as aluminum, on the surface of a semiconductor chip, it is preferable to use the thing whose content of hydrolysable chlorine ion is 500 ppm or less.

여기서, R은 H2, CH3또는이다.Wherein R is H 2 , CH 3 or to be.

본 발명에 사용되는 산무수물은 상기 에폭시의 경화제로는 사용되며, 예를 들어, 지환족 및 방향족 산무수물, 히드라지드류, 2염기산 중합체와 노볼락페놀, 또는 크레졸노볼락페놀수지를 단독 또는 혼용하여 사용한다. 산무수물(또는 경화제)의 사용량은 에폭시 당량과 경화제의 반응기와 당량비로 조절하는 바, 이들 당량비(에폭시 당량/경화제 반응기)가 0.5 내지 1.5가 되도록 조절하는 것이 좋다. 이를 에폭시 수지 100중량부에 대해 환산하면 20 내지 70중량부이다. 이들 당량비가 상기 범위를 벗어날 경우, 에폭시 수지량이 과량이면 에폭시-카탈리스트의 어덕트(adduct)가 생성되고, 산무수물량이 과량이면 카탈리스트-에폭시의 저분자량 올리고머가 생성되는 등의 내습성 및 내열 충격성이 저하되며, 경화된 후에 강도가 저하되는 문제점이 발생한다.The acid anhydride used in the present invention is used as a curing agent of the epoxy, for example, alicyclic and aromatic acid anhydrides, hydrazides, dibasic acid polymers and novolakphenols, or cresol novolakphenol resins alone or Use in combination. The amount of the acid anhydride (or curing agent) is controlled by the epoxy equivalent and the reactor and the equivalent ratio of the curing agent, so that the equivalent ratio (epoxy equivalent / curing agent reactor) is preferably adjusted to be 0.5 to 1.5. When it converts with respect to 100 weight part of epoxy resins, it is 20-70 weight part. When these equivalent ratios are out of the above ranges, when the amount of epoxy resin is excessive, adducts of epoxy-catalyst are produced, and when the amount of acid anhydride is excessive, low molecular weight oligomers of catalyzed-epoxy are formed, and the like. This decreases, and a problem occurs that the strength decreases after curing.

본 발명에서는 봉지재의 내부 응력을 낮추고 내열충격성을 향상시켜 소지 및 수지 조성물과 밀착성을 높이기 위하여 변성페놀 수지를 에폭시 수지 100중량부에 대하여 10 내지 80중량부 사용한다. 이때, 10중량부 이하이면 내부응력 저하 효과가 없고, 80중량부 이상이면 밀착성이 떨어진다. 본 발명에는 하기 식(Ⅱ)로 표시되는 노볼락 페놀 수지 및 하기 식(Ⅲ)으로 표시되는 페놀 수지를 하기 식(Ⅳ)로 표시되는 산무수물 수지와 반응시켜 얻어진 비닐에스테르 변성페놀수지를 사용한다.In the present invention, a modified phenol resin is used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the epoxy resin in order to lower the internal stress of the encapsulant and improve the thermal shock resistance to increase the adhesion between the base and the resin composition. At this time, if it is 10 parts by weight or less, there is no effect of lowering internal stress, and if it is 80 parts by weight or more, the adhesion is inferior. In this invention, the vinyl ester modified phenol resin obtained by making the novolak phenol resin represented by following formula (II) and the phenol resin represented by following formula (III) react with the acid anhydride resin represented by following formula (IV) is used. .

여기서, R은 H, CH3또는이고, n은 3-10인 정수이다.Where R is H, CH 3 or And n is an integer of 3-10.

여기서, R은 수소 또는 CH3이고, n은 1-3인 정수다.Where R is hydrogen or CH 3 and n is an integer of 1-3.

여기서, n은 4-8인 정수이고, m은 1 내지 4인 정수이며, R은 탄소수가 1 내지 3인 선형 알킬그룹 또는 브렌치된 알킬그룹이다.Wherein n is an integer of 4-8, m is an integer of 1-4, R is a linear alkyl group or branched alkyl group having 1 to 3 carbon atoms.

본 발명에 사용된 변성 페놀수지는 상기 식(Ⅱ)로 표시되는 노볼락 페놀 수지 및 상기 식(Ⅲ)으로 표시되는 페놀 수지 70 내지 95중량부에 상기 식(Ⅳ)로 표시되는 산무수물수지를 5 내지 30중량부를 넣고 120-220℃에서 1 내지 8시간 반응시켜서 얻는다. 이때, 산무수물 수지가 5중량부 미만이면 내부 응력을 낮추는 효과가 없고, 30중량부 이상이면 내습성이 저하된다.The modified phenolic resin used in the present invention is an acid anhydride resin represented by the formula (IV) to 70 to 95 parts by weight of the novolak phenol resin represented by the formula (II) and the phenol resin represented by the formula (III). It is obtained by adding 5 to 30 parts by weight and reacting at 120-220 ° C. for 1 to 8 hours. At this time, if the acid anhydride resin is less than 5 parts by weight, there is no effect of lowering the internal stress, and if it is 30 parts by weight or more, the moisture resistance is lowered.

이 밖에 수지 조성물로는 커플링제로 에폭시 수지 조성물중 유기분과 무기분 및 금속소재와의 결합력을 높여주는 역할을 한다. 상기 커플링제에는 실란계 커플링제, 티타늄계 커플링제, 또는 지르코 알루미네이트 커플링제 등이 있다. 커플링제의 사용량은 에폭시 수지 100중량부에 대하여 1 내지 20중량부가 바람직하며, 1중량부 미만이면 유기분과 무기분의 결합력이 저하되며, 20중량부 이상이면 내습성 및 성형성이 불량해진다.In addition, the resin composition serves as a coupling agent to enhance the bonding strength between the organic component, the inorganic component and the metal material in the epoxy resin composition. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirco aluminate coupling agent, and the like. As for the usage-amount of a coupling agent, 1-20 weight part is preferable with respect to 100 weight part of epoxy resins, and when it is less than 1 weight part, the bonding force of an organic component and an inorganic powder will fall, and if it is 20 weight part or more, moisture resistance and moldability will become bad.

상기 수지 조성물의 무기충진제로서 크게 나누어 용융 실리카, 결정성 실리카, 합성 실리카등의 실리카, 칼슘카보네이트 및 알루미나 등이 있고 형태로서는 파쇄형과 구형이 있다. 이들 무기충진제들은 분말에 따라 2종 이상을 섞어서 사용해도 좋다. 더욱이 구형 충진제를 사용할 경우 구형과 파쇄형을 9:1-1:9의 비율로 혼합해서 사용할 경우 내충격성이 좋아진다. 본 발명에서 사용되는 무기물 충진제의 적절한 사용량은 50 내지 200중량부로서 만일 이보다 적은 양을 사용할 경우 매트릭스 수지에 대한 보강효과가 적어 내충격성의 향상효과가 적으며 이 보다 많은 양을 사용하면 조성물의 점도 상승으로 인하여 외관이 나빠진다.The inorganic fillers of the resin composition are broadly divided into silicas such as fused silica, crystalline silica and synthetic silica, calcium carbonate, alumina, and the like. These inorganic fillers may be used in combination of two or more kinds depending on the powder. Furthermore, when using spherical fillers, the impact resistance is improved when using a mixture of spherical and crushed in a ratio of 9: 1-1: 9. An appropriate amount of the inorganic filler used in the present invention is 50 to 200 parts by weight, if less than this, the reinforcing effect on the matrix resin is small and the impact resistance is not improved. The appearance is worse.

이 밖에 기타 첨가제들이 상기 조성물에 선택적으로 혼합될 수 있는데, 예를 들어 이형제로써 천연왁스의 합성왁스, 에스테르나 금속염, 파라핀, 산 아미드 등이 있고 이들은 2종 이상을 혼용하여 사용하여도 좋다. 이형제의 사용량은 3 내지 20중량부를 사용함이 바람직하다. 또한, 조성물의 난연성을 부여하기 위한 난연제로서 삼산화안티몬, 브롬 크레졸 노볼락 수지, 또는 브롬 비스 페놀 A형 수지등이 있다. 이들의 함량이 15 내지 50중량부가 바람직한데, 이를 벗어나게 되면 난연성이 저하되거나 외관이 불량해지게 된다. 착색제로는 안료를 사용하며 사용량은 1 내지 10중량부가 적당하며, 1중량부 미만이면 착색효과가 저하되고 10중량부 이상이면 전기적 특성이 저하된다. 에폭시 조성물의 경화촉진제로서 포스핀과 포스핀 유도체, 아민계, 또는 이미다졸과 그 유도체 등이 1 내지 10중량부로 사용된다.In addition, other additives may be optionally mixed with the composition. For example, synthetic waxes, esters, metal salts, paraffins, acid amides, etc. of natural waxes may be used as a release agent, and these may be used in combination of two or more kinds. The amount of the release agent is preferably used 3 to 20 parts by weight. Moreover, antimony trioxide, a bromine cresol novolak resin, or a bromine bisphenol-A resin etc. are mentioned as a flame retardant to impart flame retardance of a composition. The content thereof is preferably 15 to 50 parts by weight, but if it is out of flame retardancy or poor appearance. As a coloring agent, a pigment is used and the usage-amount is 1-10 weight part, and when it is less than 1 weight part, a coloring effect falls, and when it is 10 weight part or more, an electrical property falls. As the curing accelerator of the epoxy composition, phosphine and phosphine derivatives, amines, or imidazole and derivatives thereof are used in an amount of 1 to 10 parts by weight.

이하 제조예 및 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Examples, but the scope of the present invention is not limited to the following examples.

[제조예 1][Production Example 1]

노볼락 페놀 수지(TAMANOL-758, ARAKAWA사) 80중량부를 70-180℃에서 완전히 녹인후 분자량이 1200-1900인 산무수물 20중량부를 넣고 160℃에서 8시간동안 반응시켜 변성 페놀(이하 변성페놀 1이라함)를 얻는다.80 parts by weight of a novolak phenol resin (TAMANOL-758, ARAKAWA) is completely dissolved at 70-180 ° C., and 20 parts by weight of an acid anhydride having a molecular weight of 1200-1900 is added and reacted at 160 ° C. for 8 hours for modified phenol (hereinafter modified phenol 1). Is called).

[제조예 2][Production Example 2]

제조예 1에서 노볼락 페놀 수지 대신에 다관능 페놀 수지(MEH-7500, MEIWA사)를 넣고 동일한 방법으로 변성다관능 페놀 수지(이하 변성 페놀 2라함)를 얻는다.In Production Example 1, a polyfunctional phenol resin (MEH-7500, MEIWA) was added instead of the novolak phenol resin to obtain a modified polyfunctional phenol resin (hereinafter referred to as modified phenol 2).

[제조예 3][Manufacture example 3]

제조예 1에서 노볼락 페놀 수지 대신에 나프틸 페놀 수지(MEH-7710, MEIWA사)를 넣고 동일한 방법으로 변성 나프틸 페놀 수지(이하 변성 페놀 3이라함)를 얻는다.Naphthyl phenol resin (MEH-7710, MEIWA) was put in place of the novolak phenol resin in Production Example 1, and a modified naphthyl phenol resin (hereinafter referred to as modified phenol 3) was obtained in the same manner.

[실시예 1 내지 3][Examples 1-3]

하기 표 1에 기재된 비율로 각 성분들의 무게를 재고 이들을 믹서에 넣고 충분히 혼합한 후 70-100℃로 가열된 2축 롤러나 니이더로 용융 혼련시킨후 냉각시켜 에폭시 조성물을 제조하였고, 그 물성치를 측정하여 결과를 하기 표 2에 기재하였다. 측정조건 및 방법은 하기 표 3에 기재하였다.Each component was weighed at the ratio shown in Table 1 below, mixed in a mixer, thoroughly mixed, melt-kneaded with a biaxial roller or kneader heated at 70-100 ° C., and cooled to prepare an epoxy composition. The measurement results are shown in Table 2 below. Measurement conditions and methods are described in Table 3 below.

상기 표 3에서 볼 수 있듯이 본 발명에서 기술한 에폭시 수지 분말 피복물은 내부응력이 낮고, 수지와 소지의 부착성이 대단히 우수하고 내습성이 뛰어남을 알 수 있다.As can be seen in Table 3, the epoxy resin powder coating described in the present invention has a low internal stress, very good adhesion between the resin and the base and excellent moisture resistance.

Claims (6)

에폭시 수지 분말 피복물에 있어서, (A) 하기 식(Ⅰ)로 표시되는 비페닐 에폭시 수지, 노볼락 에폭시 수지, 노볼락 변성 에폭시 수지 및 비스페놀 A형 에폭시 수지로 이루어진 군으로부터 하나 또는 그 이상 선택된 에폭시 수지 100중량부, (B) 하기 식(Ⅱ)로 표시되는 노볼락 페놀 수지 및 하기 식(Ⅲ)으로 표시되는 페놀 수지 70 내지 95중량부에 상기 식(Ⅳ)로 표시되는 산무수물 수지를 5 내지 30중량부를 넣고 120∼220℃에서 1 내지 8시간 반응시켜 제조된 변성페놀 수지 10 내지 80중량부, (C) 산무수물 20 내지 70중량부 (D) 커플링제 1 내지 20중량부, (E) 무기충진제 50 내지 200중량부 및 기타 첨가제로 이루어진 것을 특징으로 하는 에폭시 수지 분말 피복물.Epoxy resin powder coating, wherein (A) at least one epoxy resin selected from the group consisting of a biphenyl epoxy resin, a novolak epoxy resin, a novolak modified epoxy resin and a bisphenol A epoxy resin represented by the following formula (I): 100 parts by weight of the acid anhydride resin represented by the formula (IV) to 5 to 95 parts by weight of the novolak phenol resin represented by the following formula (II) and the phenol resin represented by the following formula (III): 10 to 80 parts by weight of a modified phenol resin prepared by adding 30 parts by weight to 1 to 8 hours at 120 to 220 ° C, (C) 20 to 70 parts by weight of an acid anhydride (D) 1 to 20 parts by weight of a coupling agent, and (E) An epoxy resin powder coating comprising 50 to 200 parts by weight of an inorganic filler and other additives. 여기서, R은 H2, CH3또는이다.Wherein R is H 2 , CH 3 or to be. 여기서, R은 H, CH3또는이고, n은 3∼10인 정수이다.Where R is H, CH 3 or And n is an integer of 3 to 10. 여기서, R은 수소 또는 CH3이고, n은 1∼3인 정수다.Wherein R is hydrogen or CH 3 and n is an integer of 1 to 3; 여기서, n은 4∼8인 정수이고, m은 1 내지 3인 정수이며, R은 탄소수가 1 내지 3인 선형 알킬그룹 또는 브렌치된 알킬그룹이다.Wherein n is an integer of 4 to 8, m is an integer of 1 to 3, and R is a linear alkyl group or branched alkyl group having 1 to 3 carbon atoms. 제1항에 있어서, 상기 산무수물이 지환족 및 방향족 산무수물, 히드라지드류, 2염기산 중합체와 노볼락페놀, 또는 크레졸노볼락페놀수지를 단독 또는 혼용하여 사용함을 특징으로 하는 에폭시 수지 분말 피복물.The epoxy resin powder coating according to claim 1, wherein the acid anhydride is used alone or in combination with alicyclic and aromatic acid anhydrides, hydrazides, dibasic acid polymers and novolakphenols, or cresol novolakphenol resins. . 제1항에 있어서, 상기 커플링제가 실란계 커플링제, 티타늄계 커플링제, 또는 지르코 알루미네이트 커플링제인 것을 특징으로 하는 에폭시 수지 분말 피복물.The epoxy resin powder coating according to claim 1, wherein the coupling agent is a silane coupling agent, a titanium coupling agent, or a zirco aluminate coupling agent. 제1항에 있어서, 상기 무기충진제가 용융 실리카, 결정성 실리카 및 합성 실리카와 같은 실리카, 칼슘카보네이트 또는 알루미나이고, 그 형태가 파쇄형 또는 구형인 것을 특징으로 하는 에폭시 수지 분말 피복물.The epoxy resin powder coating according to claim 1, wherein the inorganic filler is silica, calcium carbonate or alumina, such as fused silica, crystalline silica, and synthetic silica, and is in a crushed or spherical form. 제4항에 있어서, 상기 무기충진제는 구형과 파쇄형을 9:1-1:9의 비율로 혼합해서 사용되는 것을 특징으로 하는 에폭시 수지 분말 피복물.The epoxy resin powder coating according to claim 4, wherein the inorganic filler is used by mixing a spherical form and a crushed form in a ratio of 9: 1-1: 9. 제1항에 있어서, 상기 기타 첨가제가 이형제 3 내지 20중량부, 난연제 15 내지 50중량부, 착색제 1 내지 10중량부 또는/및 경화 촉진제 1 내지 10중량부로 이루어짐을 특징으로 하는 에폭시 수지 분말 피복물.The epoxy resin powder coating according to claim 1, wherein the other additives comprise 3 to 20 parts by weight of a release agent, 15 to 50 parts by weight of a flame retardant, 1 to 10 parts by weight of a colorant, and / or 1 to 10 parts by weight of a curing accelerator.
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