KR100577920B1 - Coating Composition for Corrosion Proofing - Google Patents
Coating Composition for Corrosion Proofing Download PDFInfo
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- KR100577920B1 KR100577920B1 KR1019997012470A KR19997012470A KR100577920B1 KR 100577920 B1 KR100577920 B1 KR 100577920B1 KR 1019997012470 A KR1019997012470 A KR 1019997012470A KR 19997012470 A KR19997012470 A KR 19997012470A KR 100577920 B1 KR100577920 B1 KR 100577920B1
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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
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/02—Copolymers of mineral oil hydrocarbons
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C09D5/08—Anti-corrosive paints
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
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Abstract
에폭시수지(A), 경화제, 바람직하게는 아민계 경화제(B) 및 인덴류 함유율 60∼90중량%의 분해유 분류분을 페놀류의 공존하에 프리델-크라프트 촉매에 의해 중합하여 얻어지는, 페놀성 수산기를 1분자당 1.0개 미만 함유하는 방향족성 석유수지(C)를 배합하고, 상기 방향족성 석유수지(C)의 함유량을 에폭시수지 100중량부에 대하여 1∼500중량부로 하므로써, 타르를 포함하지 않고, 해수에 접촉하는 부위에 적용가능한 방식용의 에폭시 도료조성물을 얻는다.Phenolic hydroxyl group obtained by polymerizing an epoxy resin (A), a curing agent, preferably an amine curing agent (B), and a cracked oil fractionation fraction having an indenes content of 60 to 90% by weight in the presence of phenols with a Friedel-Craft catalyst. By containing less than 1.0 aromatic petroleum resin (C) per molecule and making the content of the aromatic petroleum resin (C) 1 to 500 parts by weight based on 100 parts by weight of epoxy resin, no tar is included. Epoxy paint compositions for anticorrosion applicable to the site of contact with seawater are obtained.
도료, 방식성, 에폭시수지, 석유수지Paint, anticorrosive, epoxy resin, petroleum resin
Description
본 발명은 타르계 에폭시도료의 대체도료로서, 특히 해수와 접촉하는 부위, 예컨대 선박의 밸러스트 탱크내의 도장에 유용한 방식도료 조성물에 관한 것이다.The present invention relates to an anticorrosive coating composition useful as a substitute for tar-based epoxy paints, in particular for coating in areas in contact with sea water, such as in ballast tanks of ships.
종래, 선박, 강 구조물 등의 방식도료로서 타르계 에폭시도료가 사용되고 있다. 이 도료는 방식성, 내수성, 내약품성 등이 우수하지만, 타르를 함유하기 때문에 위생상의 문제가 염려될 뿐만 아니라, 흑색이기 때문에 유지관리가 곤란하며, 밀폐된 장소에서는 어두워지므로 작업에 위험이 수반되는 등의 문제가 있었다.Conventionally, tar-based epoxy paints have been used as anticorrosive paints for ships and steel structures. This paint is excellent in corrosion resistance, water resistance, chemical resistance, etc., but because it contains tar, it is not only concerned with hygiene problems, but because it is black, it is difficult to maintain and darkened in a closed place. There was a problem.
근래, 타르 대신에 석유계의 수지를 사용한 비타르계의 에폭시 도료도 개발되어 있다. 예컨대, 일본국 특공소 59-52656호 공보나, 특개평 9-263713호 공보등에 제안이 되어 있다. 즉, 특공소 59-52656호 공보에 기재된 수지는 수산기를 포함하는 것이며, 실시예에서 나프타의 크랙킹으로부터 얻어진 불포화성분을 포함하는 분류분을 페놀공존하에 중합하여 연화점 93℃의 수지를 얻고 있다. 또, 특개평 9-263713호 공보에는 실시예에서 1분자중의 수산기 함유량이 1∼1.1몰인 디비닐톨루엔-인덴 공중합체(연화점 100℃)를 사용한 에폭시 수지계의 방식도료가 개시되어 있다.In recent years, non-tar epoxy coatings using petroleum resins in place of tar have also been developed. For example, it is proposed by Japanese Unexamined-Japanese-Patent No. 59-52656, Unexamined-Japanese-Patent No. 9-263713. That is, the resin of Unexamined-Japanese-Patent No. 59-52656 contains a hydroxyl group, In the Example, the fractionation fraction containing the unsaturated component obtained from the cracking of naphtha was superposed | polymerized in phenol coexistence, and resin of softening point 93 degreeC is obtained. Japanese Patent Application Laid-Open No. 9-263713 discloses an epoxy resin anticorrosive coating using a divinyltoluene-indene copolymer (softening point 100 DEG C) having a hydroxyl group content of 1 to 1.1 mol in one molecule in Examples.
그러나, 상기 공보기재의 에폭시 도료에 관해서는 에폭시 수지, 경화제, 특 히 아민경화제로 이루어지는 경화수지와 석유계의 수지와의 상용성에 문제가 있고, 특히 고도의 방식성, 내수성 등이 요구되는 해수에 직접 접촉하는 부위의 도장, 예컨대 선박의 밸러스트 탱크내에 적용하는 데는 불충분하다. However, regarding the epoxy paint of the present material, there is a problem in compatibility between the curable resin composed of an epoxy resin, a curing agent, especially an amine curing agent and a petroleum resin, and especially in seawater where high corrosion resistance and water resistance are required. Insufficient coating in areas of direct contact, such as in ballast tanks of ships.
발명의 개시Disclosure of the Invention
본 발명자는 상기한 문제를 해결하고자 예의 검토한 결과, 인덴류 함유율을 특정한 방향족 분류분(fraction)을 원료로 하는 수지를 사용하는 동시에, 페놀성 수산기의 함유량을 비교적 저감한 수지를 사용하므로써 에폭시 수지나 경화제, 특히 아민경화제와의 상용성이 우수하며, 그 결과 위생상 문제가 없으며, 방식성, 내수성, 부착성 등이 우수하고, 게다가 밝은 색의 도막을 형성할 수 있는 방식도료 조성물이 얻어지는 것을 발견하여 본 발명을 완성하였다.As a result of earnestly examining in order to solve the above-mentioned problem, the inventors have found that epoxy resin can be obtained by using a resin having an indene content as a specific aromatic fraction as a raw material and using a resin having a relatively low content of phenolic hydroxyl groups. It is excellent in compatibility with the curing agent, especially the amine curing agent, and as a result, there is no hygiene problem, and the anticorrosive coating composition which is excellent in anticorrosiveness, water resistance, adhesion, etc., and which can form a bright color coating film is obtained. Discovered to complete the present invention.
즉, 본 발명의 제1은 에폭시수지(A), 경화제, 바람직하게는 아민계 경화제(B) 및 석유류의 열분해에 의해 얻어지는 분해유중, 주로 140∼220℃의 비점범위에 있는 성분을 포함하는 분류분으로부터 증류에 의해 얻어지는 인덴류 함유율 60∼90중량%의 분해유 분류분을 페놀류의 공존하에 프리델-크라프트(Friedel-Crafts) 촉매에 의해 중합하여 이루어지는 페놀성 수산기를 1분자당 0.1개 이상, 1.0개 미만 함유하는 방향족성 석유수지(C)로 이루어지고, 방향족성 석유수지(C)를 에폭시수지 100중량부에 대하여 1∼500중량부 함유하는 것을 특징으로 하는 방식도료 조성물에 관한 것이다.That is, the 1st of this invention contains the component in the boiling range of 140-220 degreeC mainly in the decomposition oil obtained by the thermal decomposition of an epoxy resin (A), a hardening | curing agent, Preferably an amine-type hardening | curing agent (B), and petroleum. 0.1 or more phenolic hydroxyl groups formed per polymer by polymerizing a cracked oil fraction containing 60 to 90% by weight of the indene content obtained by distillation from fractionated fractions in the presence of phenols, using a Friedel-Crafts catalyst. It consists of aromatic petroleum resin (C) containing less than 1.0, and it contains an aromatic petroleum resin (C) 1-500 weight part with respect to 100 weight part of epoxy resins.
본 발명의 제2는, 본 발명의 제1에 있어서, 분해유 분류분의 공액 디엔 함유 율이 5중량% 이하인 방식도료 조성물에 관한 것이다.The second aspect of the present invention relates to the anticorrosive coating composition according to the first aspect of the present invention, wherein the conjugated diene content of the decomposed oil fractional component is 5% by weight or less.
이하, 본 발명에 관하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용되는 에폭시수지(A)는 1분자중에 적어도 2개 이상의 에폭시기를 갖는 것이며, 에폭시 당량 150∼600의 것이 적당하며, 바람직하게는 180∼500이다. 이와 같은 에폭시수지로서는, 예컨대 비스페놀형 에폭시수지, 지방족 에폭시수지, 글리시딜에스테르계 에폭시수지, 글리시딜 아민계 에폭시수지, 페놀노볼락형 에폭시수지, 크레졸형 에폭시수지, 다이머산 변성 에폭시수지 등의 종래 공지의 것을 들 수 있고, 이것들은 1종 만으로, 또는 2종 이상 혼합하여 사용할 수 있다.The epoxy resin (A) used in the present invention has at least two or more epoxy groups in one molecule, and an epoxy equivalent of 150 to 600 is appropriate, preferably 180 to 500. Examples of such epoxy resins include bisphenol epoxy resins, aliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, phenol novolac epoxy resins, cresol epoxy resins, dimer acid modified epoxy resins, and the like. The conventionally well-known thing of these is mentioned, These can be used only by 1 type or in mixture of 2 or more types.
본 발명에서 사용되는 경화제(B)는 에폭시수지의 경화제로서 종래 공지의 것이 사용된다. 예컨대, 각종 지방족 또는 방향족 아민류, 폴리아미드 수지, 산무수물류, 페놀수지, 폴리이소시아네이트 등이 예시된다. 이것들은 1종 만으로, 또는 2종 이상 혼합하여 사용할 수 있다. The hardening | curing agent (B) used by this invention is a conventionally well-known thing as a hardening | curing agent of an epoxy resin. For example, various aliphatic or aromatic amines, polyamide resins, acid anhydrides, phenol resins, polyisocyanates and the like are exemplified. These can be used only by 1 type or in mixture of 2 or more types.
특히 바람직하게는 아민계 경화제이며, 예컨대, 메타크실렌디아민, 이소포론디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 디아미노디페닐메탄 등의 지방족 폴리아민류, 지환족 폴리아민류, 방향족 폴리아민류, 이들 폴리아민류의 에폭시수지 어덕트물, 폴리아미드아민류, 폴리아미드수지 등을 들 수 있다. 이것들은 1종 만으로, 또는 2종 이상 혼합하여 사용할 수 있다.Especially preferably, it is an amine hardening | curing agent, For example, aliphatic polyamines, such as metha xylene diamine, isophorone diamine, diethylene triamine, triethylene tetratamine, diamino diphenylmethane, alicyclic polyamine, aromatic polyamine, these Epoxy resin adducts of polyamines, polyamide amines, polyamide resins, and the like. These can be used only by 1 type or in mixture of 2 or more types.
상기 에폭시수지(A) 및 경화제(B)의 혼합비율은 양성분의 종류에 따라 적절히 선택할 수 있다. 일반적으로 에폭시수지 100중량부당 경화제 1∼200중량부의 범위에서 선택된다. 경화제(B)로서 바람직한 아민계 경화제를 사용할 경우에는 통상, (B)중의 활성수소당량/(A)중의 에폭시당량의 당량비가 0.5∼1.0의 범위로 되도록 선택하는 것이 적당하다.The mixing ratio of the epoxy resin (A) and the curing agent (B) can be appropriately selected depending on the type of cationic component. Generally, it is selected in the range of 1 to 200 parts by weight of the curing agent per 100 parts by weight of epoxy resin. When using an amine hardening | curing agent suitable as a hardening | curing agent (B), it is usual to select so that the equivalence ratio of the active hydrogen equivalent in (B) / the epoxy equivalent in (A) may be in the range of 0.5-1.0.
본 발명에서 사용되는 방향족성 석유수지(C)로서는 페놀성 수산기를 함유하는 상온에서 고형상의 석유수지로서, 연화점이 50∼150℃, 바람직하게는 80∼110℃의 것을 사용한다.As the aromatic petroleum resin (C) used in the present invention, as a solid petroleum resin at room temperature containing a phenolic hydroxyl group, one having a softening point of 50 to 150 ° C, preferably 80 to 110 ° C is used.
상기 석유수지로서는 에틸렌, 프로필렌 등을 제조하기 위하여 나프타, 부탄 등의 탄화수소를 열분해할 때에 부생하는 분해유중, 주로 비점범위가 140∼220℃의 범위에 있는 성분을 포함하는 분류분을 원료로 한다. 이와 같은 분류분에는 스티렌, α-, 또는 β-메틸스티렌, 비닐톨루엔, 인덴, 메틸인덴 외에 디시클로펜타디엔, 디메틸시클로펜타디엔 등의 불포화성분 및 에틸벤젠, 트리메틸벤젠, 인단, 메틸인단, 나프탈렌 등의 포화성분이 포함된다. 또한 증류조작시에 디시클로펜타디엔, 디메틸시클로펜타디엔 등이 열분해하므로써 생성된 시클로펜타디엔, 메틸시클로펜타디엔 등의 공액 디엔도 포함된다.As the petroleum resin, a fractionated fraction containing a component having a boiling point in the range of 140 to 220 占 폚 is mainly used as a raw material in decomposition oil generated by thermal decomposition of hydrocarbons such as naphtha and butane in order to produce ethylene, propylene, and the like. . Such fractions include styrene, α- or β-methylstyrene, vinyltoluene, indene, methyl indene, unsaturated components such as dicyclopentadiene, dimethylcyclopentadiene, ethylbenzene, trimethylbenzene, indane, methyl indane, Saturated components, such as naphthalene, are contained. Moreover, conjugated dienes, such as cyclopentadiene and methylcyclopentadiene produced by thermal decomposition of dicyclopentadiene, dimethylcyclopentadiene, etc. at the time of distillation operation, are also included.
본 발명에서는 상기 분해유의 증류에 의해 얻어지는 분류분으로서, 인덴류 함유율이 60∼90중량%인 분류분을 원료로 한다. 이 범위를 벗어나는 분류분을 사용하면, 결과적으로 방식 도료 조성물로서의 성능이 저하하므로 바람직하지 않다. 여기서, 인덴류 함유율(중량%)은 (인덴 및 메틸인덴 등의 알킬인덴의 합계량/분해유 분류분중의 전체 불포화성분 함유량)×100 으로 정의된다.In this invention, the fractionation fraction obtained by the distillation of the said decomposition oil is a fractionation fraction whose indene content is 60 to 90 weight% as a raw material. Use of fractions out of this range is undesirable because of the deterioration of the performance as an anticorrosive coating composition. Here, indene content rate (weight%) is defined as (total unsaturated component content in the total amount / decomposition oil fractionation fraction of alkyl indenes, such as indene and methyl indene) x100.
바람직하게는, 시클로펜타디엔, 메틸시클로펜타디엔 등의 공액디엔류 함유율이 5중량% 이하인 분류분을 사용한다. 공액디엔류의 함유율을 5중량% 이하로 하므 로써 방식도료로서의 성능을 더욱 향상시킬 수 있다. 여기서, 공액디엔류 함유율(중량%)은 (공액디엔의 합계량/분해유 분류분중의 전체 불포화성분 함유량)×100 으로 정의된다.Preferably, the fractionation fraction whose conjugated diene content rate, such as cyclopentadiene and methylcyclopentadiene, is 5 weight% or less is used. By adjusting the content of conjugated dienes to 5% by weight or less, the performance as an anticorrosive coating can be further improved. Here, conjugated diene content rate (weight%) is defined as (total unsaturated component content in the total amount / decomposition oil fractionation of conjugated diene) x100.
그리고, 상기 각 성분의 분석은 공지의 가스크로마토그래피법에 의해 용이하게 행할 수 있다.In addition, analysis of each said component can be easily performed by a well-known gas chromatography method.
또, 상기 조성의 분해유 분류분은 열분해로 부생하는 분해유에 대하여 적절히 공지의 증류방법을 조합하여 처리하므로써 용이하게 얻을 수 있다.The cracked oil fractionation fraction having the above composition can be easily obtained by appropriately combining a known distillation method with respect to the cracked oil by-produced by pyrolysis.
본 발명의 원료수지는 상기 분해유 분류분의 100중량부에 페놀류 1.0∼10.0중량부를 공존시켜, 분해유 분류분에 대하여 0.01∼3중량%의 프리델-크라프트 촉매를 사용하여 10∼100℃의 범위에서 중합시키므로써 제조할 수 있다.The raw material resin of the present invention coexists with 1.0 to 10.0 parts by weight of phenols in 100 parts by weight of the cracked oil fraction, and is in the range of 10 to 100 ° C. using a 0.01 to 3% by weight Friedel-Craft catalyst based on the cracked fraction. It can be prepared by polymerization in.
페놀류로서는 페놀외에 크레졸, 크실레놀, 터셔리-부틸페놀, 노닐페놀 등의 알킬기 치환의 페놀을 예시할 수 있다. 이것들은 혼합하여 사용할 수도 있다. 바람직하게는, 페놀이다. 페놀류는 프리델-크라프트 촉매의 1성분으로서 반응계에 존재시키는 것도 가능하지만, 통상은 촉매와는 별개로 소정량의 페놀을 반응계에 공급하는 경우가 많다.As phenols, phenol of alkyl group substitution, such as cresol, xylenol, tert-butylphenol, nonylphenol, can be illustrated besides phenol. These can also be mixed and used. Preferably, it is phenol. Phenols may be present in the reaction system as one component of the Friedel-Crafts catalyst, but usually a predetermined amount of phenol is often supplied to the reaction system independently of the catalyst.
프리델-크라프트 촉매로서는 할로겐화 금속, 바람직하게는 삼플루오라이드 붕소, 또는 그의 페놀, 에틸에테르, 부틸에테르, 부틸알콜, 메틸알콜 등의 산소함유 화합물과의 착체가 사용된다.As the Friedel-Crafts catalyst, a metal halide, preferably boron trifluoride, or a complex with an oxygen-containing compound such as phenol, ethyl ether, butyl ether, butyl alcohol or methyl alcohol is used.
중합시간은 뱃치식인 경우에 0.5∼10시간의 범위에서 선택할 수 있다.The polymerization time can be selected in the range of 0.5 to 10 hours in the case of batch type.
상기 분해유 분류분, 페놀류, 프리델-크라프트 촉매등을 소정량 투입하여 공 지의 방법에 의해 중합하므로써 소정의 연화점을 갖는 수지가 얻어진다. 중합후에는 알칼리 등을 사용하여 적절히 촉매를 비활성화시킨 후, 미반응유나 저중합물을 적절히 증류 등으로 분리, 제거하면 목적하는 수지가 얻어진다.Resin having a predetermined softening point is obtained by adding a predetermined amount of the cracked oil fraction, phenols, Friedel-Craft catalyst and the like and polymerizing it by a known method. After polymerization, the catalyst is deactivated appropriately using an alkali or the like, and then the unreacted oil or the low polymer is separated and removed by distillation or the like as appropriate, thereby obtaining the desired resin.
본 발명의 도료 조성물에 사용되는 석유수지(C)는 석유수지 1분자중에 0.1개 이상, 1.0개 미만의 페놀성 수산기를 함유하는 것이다. 바람직하게는, 0.5∼0.9개이다. 그리고, 중합에 있어서는 각 원료의 충전량, 중합조건 등을 적절히 조정하므로써 페놀성 수산기의 양이 상기 범위에 있는 수지를 얻을 수 있다.The petroleum resin (C) used for the coating composition of this invention contains 0.1 or more and less than 1.0 phenolic hydroxyl group in 1 molecule of petroleum resin. Preferably, it is 0.5-0.9. And in superposition | polymerization, resin in which the quantity of a phenolic hydroxyl group exists in the said range can be obtained by adjusting suitably the filling amount of each raw material, superposition | polymerization conditions, etc ..
본 발명에서 사용되는 상기 석유수지(C)의 1분자중에 페놀성 수산기가 1.0개 이상 존재하면, 방식도료용의 수지로서는 바람직하지 않다. 또, 0.1개 미만에서는에폭시수지와의 상용성이 저하하여 마찬가지로 바람직하지 않다. 그리고, 얻어진 수지중에 존재하는 페놀성 수산기의 양은, 예컨대 I.E. 17, C. Anal. Ed. (1945) p.394에 기재된 방법에 의해 측정할 수 있다.If 1.0 or more phenolic hydroxyl groups exist in 1 molecule of the said petroleum resin (C) used by this invention, it is not preferable as resin for anticorrosive coating. Moreover, when less than 0.1, compatibility with epoxy resin falls and it is likewise unpreferable. And the quantity of the phenolic hydroxyl group which exists in obtained resin is IE 17 , C. Anal. Ed. It can be measured by the method described in (1945) p.394.
또 상기 수지(C)의 연화점은 상기와 같이 50∼150℃, 바람직하게는 80∼110℃의 범위이다. 연화점이 50℃ 미만에서는 방식도막의 내수성이 낮고, 도막표면에 수지성분이 누출하여 점착성이 잔존하는 경우가 있으며, 한편, 150℃를 초과하면 도료점도가 높아져서 작업성이 저하하거나, 도막물성이 저하하므로 바람직하지 않다. 그리고 본 발명에 사용되는 수지(C)의 분자량은 수평균분자량으로서 500∼3000의 범위이다.Moreover, the softening point of the said resin (C) is 50-150 degreeC as mentioned above, Preferably it is the range of 80-110 degreeC. If the softening point is less than 50 ° C, the water resistance of the anticorrosive coating film is low, and a resin component may leak on the surface of the coating film, and adhesiveness may remain. On the other hand, if the coating point exceeds 150 ° C, the coating viscosity becomes high, resulting in poor workability or deterioration in coating properties. Therefore, it is not preferable. And the molecular weight of resin (C) used for this invention is a range of 500-3000 as a number average molecular weight.
본 발명의 조성물을 얻는데는 에폭시수지(A) 100중량부에 대하여, 상기 페놀성 수산기를 함유하는 석유수지(C)를 1∼500중량부, 바람직하게는 10∼300중량부 배합한다. 상기 배합량이 1중량부 미만에서는 얻어진 조성물에 충분한 내수성을 얻을 수 없고, 한편 500중량부를 초과하면 도막이 취약해져서 양호한 물성을 얻을 수 없게 되므로 어느 것이나 바람직하지 않다.To obtain the composition of the present invention, 1 to 500 parts by weight, preferably 10 to 300 parts by weight of the petroleum resin (C) containing the phenolic hydroxyl group is added to 100 parts by weight of the epoxy resin (A). When the said compounding quantity is less than 1 weight part, sufficient water resistance cannot be obtained for the obtained composition, On the other hand, when it exceeds 500 weight part, since a coating film becomes weak and a favorable physical property cannot be obtained, either is not preferable.
본 발명의 방식도료 조성물에는 더욱 가소성을 부여하기 위하여 그외의 액상의 개질제, 예컨대 크실렌수지, 톨루엔수지; 부틸글리시딜에테르 등의 에폭시화합물 등의 반응성 희석제 등을, 경화수지 고형분 100중량부에 대하여 50중량부 이하의 범위에서 첨가하여도 된다. 이것들중에서는 내수성 유지면에서 방향족계의 것이 적합하게 사용된다.The anticorrosive coating composition of the present invention includes other liquid modifiers such as xylene resin and toluene resin in order to impart more plasticity; Reactive diluents, such as an epoxy compound, such as butyl glycidyl ether, may be added in 50 weight part or less with respect to 100 weight part of hardening resin solid content. Of these, aromatics are suitably used in terms of water resistance retention.
본 발명의 조성물에는 더욱 필요에 따라 체질안료, 방청안료, 착색안료 등의 안료류; 반응성 희석제; 유기용제, 침강방지제, 흐름방지제, 습윤제, 반응촉진제, 부착성 부여제, 탈수제 등의 통상의 도료용 첨가제 등을 적절히 배합하여도 좋다.The composition of the present invention may further include pigments such as extender pigments, rust preventive pigments and colored pigments as necessary; Reactive diluents; Ordinary paint additives such as organic solvents, sedimentation inhibitors, flow inhibitors, wetting agents, reaction promoters, adhesion imparting agents, and dehydrating agents may be appropriately blended.
또, 본 발명의 조성물은 에폭시수지를 포함하는 주재와 경화제, 바람직하게는 아민계 경화제로 이루어지는 이액형 도료로서, 통상 아연 프라이머 등의 1차 방청 도막상에 도장된다. 즉, 우선 강판에 샷블라스팅(shot blasting)을 하여 밀 스케일(mill scale)을 제거하고, 에틸실리케이트계 등의 무기아연 프라이머를 도포하고, 그후 본 발명의 도료 조성물의 도포를 행한다.In addition, the composition of the present invention is a two-component coating composed of a main material containing an epoxy resin and a curing agent, preferably an amine curing agent, and is usually coated on primary rust-preventive coating films such as zinc primers. That is, first, shot blasting is performed on the steel sheet to remove the mill scale, and inorganic zinc primers such as ethyl silicate are applied, and then the coating composition of the present invention is applied.
프라이머는 아연실리케이트 등에 한하지 않고, 각종의 프라이머를 사용할 수 있다. 또, 프라이머 없는 강판등이라도 도장이 가능하며, 충분한 방식효과가 얻어진다.The primer is not limited to zinc silicate and the like, and various primers can be used. Moreover, even a steel plate without a primer can be applied, and sufficient anticorrosive effect is obtained.
도장방법으로서는, 에어스프레이, 에어레스 스프레이, 브러쉬도장, 롤러 등 종래 공지의 방법을 채용할 수 있으며, 상기 도료 조성물을 건조 막두께로 150∼500㎛로 되도록 도포할 수 있다.As a coating method, conventionally well-known methods, such as an air spray, an airless spray, a brush coating, and a roller, can be employ | adopted, and the said coating composition can be apply | coated so that it may become 150-500 micrometers in dry film thickness.
발명을 실시하기 위한 최선의 형태Best Mode for Carrying Out the Invention
이하, 실시예를 들어서 본 발명을 더 상세히 설명한다. 그리고 「부」및 「%」는 각각 「중량부」및「중량%」를 나타낸다.Hereinafter, the present invention will be described in more detail with reference to Examples. "Part" and "%" represent "weight part" and "weight%", respectively.
[제조예][Production example]
나프타의 열분해에 의해 얻어지는 분해유로부터 비점범위가 140∼220℃인 분류분을 분류하므로써 전체 불포화성분량 51%, 인덴류 함유율 70%, 공액디엔류 함유율 0.5%로 조정된 분해유 분류분을 얻었다.From the cracked oil obtained by pyrolysis of naphtha, fractionated fractions having a boiling point range of 140 to 220 ° C were fractionated to obtain cracked fraction fractions adjusted to 51% total unsaturated component content, 70% indenes content, and 0.5% conjugated diene content.
다음에, 상기 분해유 분류분 100g에 페놀 5g을 첨가하고, 삼플루오라이드 붕소-페놀착체를 0.5g 가하여, 30℃에서 3시간 중합한 후, 수산화나트륨 수용액으로 촉매를 제거하고, 이어서 수세한 후, 증류에 의해 미반응유 및 저중합물을 제거하여 석유수지(A) 56g을 얻었다.Next, 5 g of phenol was added to 100 g of the fractionated oil fractionated powder, 0.5 g of a trifluoride boron-phenol complex was added and polymerized at 30 ° C. for 3 hours, followed by removing the catalyst with an aqueous sodium hydroxide solution, followed by washing with water. The unreacted oil and the low polymer were removed by distillation to obtain 56 g of petroleum resin (A).
얻어진 수지의 연화점은 103℃이며, 분석한 결과, 페놀성 수산기를 분자 1개당 0.8개 갖는 것을 확인하였다.The softening point of the obtained resin was 103 degreeC, and as a result of analysis, it was confirmed that it has 0.8 phenolic hydroxyl groups per molecule.
[비교제조예][Comparative Manufacturing Example]
상기 제조예와 동일하게 하여, 인덴류 함유율 20%, 공액디엔 함유율 6%의 분해유 분류분을 얻었다.In the same manner as in the above-mentioned production example, cracked oil fractionation powder having an indene content of 20% and a conjugated diene content of 6% was obtained.
이것을 동일하게 중합시키므로써 연화점 85℃, 페놀성 수산기를 분자 1개당 0.8개 갖는 석유수지(B)를 얻었다.By polymerizing this in the same manner, a petroleum resin (B) having a softening point of 85 占 폚 and 0.8 phenolic hydroxyl groups per molecule was obtained.
[실시예1]Example 1
용기에 에폭시수지 100부, 티탄 화이트 30부, 탈크 100부, 제조예에서 얻은 석유수지(A) 100부, 탄화수소계 가소제 20부, 흐름방지제 5부 및 크실렌, MIBK 및 시클로헥산의 등량 혼합용제 150부를 첨가하여 교반기로 혼합교반하여 분산시키므로써 주재로 하였다. 이것에 경화제로서 폴리아미드 수지 80부(고형분 환산)를 첨가하여 혼합교반하여 방식도료 조성물을 얻었다. 조성 및 결과를 표1에 나타낸다.100 parts of epoxy resin, 30 parts of titanium white, 100 parts of talc, 100 parts of petroleum resin (A) obtained in the production example, 20 parts of hydrocarbon-based plasticizer, 5 parts of anti-flow agent and equivalent mixing solvent of xylene, MIBK and cyclohexane 150 Part was added, and the mixture was stirred and mixed with a stirrer to prepare a main material. 80 parts (solid content conversion) of polyamide resin was added to this as mixing agent, and it stirred and mixed, and obtained the anticorrosive coating composition. The compositions and results are shown in Table 1.
[실시예2, 비교예]Example 2, Comparative Example
표1에 나타내는 배합으로 동일하게 조성물을 제조하였다.Compositions were prepared in the same manner as in the formulation shown in Table 1.
비교예에서는 비교제조예의 석유수지(B)를 사용하였다. 결과를 표1에 나타낸다.In the comparative example, the petroleum resin (B) of the comparative manufacturing example was used. The results are shown in Table 1.
표1Table 1
주.(1) 에폭시 당량 475; 상품명 「에폰 #1001」, 유카셸에폭시사제Note (1) epoxy equivalent 475; "Epon # 1001", product made in yucca shell epoxy company
(2) 제조예에서 얻은 석유수지(A) (2) Petroleum resin (A) obtained in the production example
(3) 비교제조예에서 얻은 석유수지(B) (3) Petroleum resin (B) obtained by comparative manufacturing example
(4) 탄화수소계 가소제; 상품명 「하이졸 SAS LH」, 니뽄석유화학(주)제 (4) hydrocarbon plasticizers; "Hyazole SAS LH", Nippon Petrochemical Co., Ltd. make
(5) 지방산유도체; 상품명「ASA T-55-20BX」, 이또제유(주)제 (5) fatty acid derivatives; `` ASA T-55-20BX '', manufactured by Ito Oil Co., Ltd.
(6) 폴리아미드수지 경화제; 상품명 「바사미드 115」, 헹켈백수(주)제; 크실렌, MIBK 및 시클로헥산의 등량 혼합용제의 50% 용액으로 하여 제공하였다. (6) polyamide resin curing agents; Trade name "Basamide 115", Henkel White Water Co., Ltd. product; It was provided as a 50% solution of the same mixed solvent of xylene, MIBK and cyclohexane.
그리고, 방식도료 조성물의 성능시험의 방법은 다음과 같다.And, the method of the performance test of the anticorrosive coating composition is as follows.
(1) 내충격 시험(듀폰식)(1) Impact resistance test (dupont type)
각 시료를 탈지한 연마 연강판(200 ×100 ×0.6mm)에 도포기에 의해 약 250㎛의 건조막두께로 되도록 도장하고, 20℃ ×65% RH의 분위기하에서 7일간 건조시켜 각 시험도판을 만들었다.Each sample was coated on a polished mild steel sheet (200 x 100 x 0.6 mm) degreased so as to have a dry film thickness of about 250 mu m, and dried in an atmosphere of 20 DEG C x 65% RH for 7 days to prepare each test plate. .
상기 도판에 대하여 20℃의 분위기중에서 JIS K5400-1990에 규정된 듀폰식 충격시험을 하였다.The plate was subjected to the DuPont impact test specified in JIS K5400-1990 in an atmosphere at 20 ° C.
(2) 내냉열 반복성 시험(2) Cold and heat repeatability test
탈지한 연마 연강판에 실리케이트 아연 프라이머를 약 25㎛의 건조막두께로 되도록 도장하고, 1일 건조시켰다. 이위에 각 시료를 각각 도포기에 의해 약 250㎛의 건조막 두께로 되도록 도장하고, 20℃ ×65% RH의 분위기하에서 7일간 건조시켜 각 시험편을 얻었다.A silicate zinc primer was coated on the degreased polished mild steel sheet so as to have a dry film thickness of about 25 μm, and dried for 1 day. Each sample was coated on this with an applicator so as to have a dry film thickness of about 250 μm, and dried in an atmosphere of 20 ° C. × 65% RH for 7 days to obtain each test piece.
이들 시험편에 대하여 JIS K5400-1990에 따라 내냉열 반복성 시험을 하였다. These test pieces were subjected to the cold and heat repeatability test according to JIS K5400-1990.
(3) 내해수성 시험(3) seawater resistance test
상기 (2)의 내냉열 반복성 시험에서 만든 것과 동일한 시험편을 50℃의 해수중에 6개월 침지하고, 그후의 도면 상태를 육안으로 평가하였다. 평가의 기준은 이하와 같다.The same test piece as made in the cold-heat repeatability test of (2) above was immersed in 50 ° C seawater for 6 months, and the state of the drawings thereafter was visually evaluated. The criteria of evaluation are as follows.
O : 이상없음O: No abnormality
△: 팽창이 약간 발생△: some expansion occurs
X: 팽창이 현저하게 발생X: Swelling occurs remarkably
본 발명의 방식도료 조성물은 인덴류 함유율을 특정한 페놀성 수산기 함유 석유수지를 사용하고 있으므로, 에폭시수지나 경화제 특히 아민계 경화제와 석유수지와의 상용성이 양호하며, 위생상 문제가 없으며, 방식성, 내수성, 부착성 등이 우수하며, 게다가 밝은 색의 도막을 형성할 수 있어, 선박이나 구조물의 방식도료로서 매우 유용하다.
Since the anticorrosive coating composition of the present invention uses a phenolic hydroxyl group-containing petroleum resin having a specific indene content, it has good compatibility with epoxy resins and curing agents, particularly amine-based curing agents and petroleum resins, and has no hygienic problems. It is excellent in water resistance, adhesion, and the like, and can form a bright colored film, which is very useful as an anticorrosive coating for ships or structures.
Claims (4)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP98-148353 | 1998-05-13 | ||
JP14835398A JP4150104B2 (en) | 1998-05-13 | 1998-05-13 | Anticorrosion paint composition |
PCT/JP1999/002489 WO1999058618A1 (en) | 1998-05-13 | 1999-05-13 | Coating composition for corrosion proofing |
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KR20010014326A KR20010014326A (en) | 2001-02-26 |
KR100577920B1 true KR100577920B1 (en) | 2006-05-09 |
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KR1019997012470A KR100577920B1 (en) | 1998-05-13 | 1999-05-13 | Coating Composition for Corrosion Proofing |
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JP (1) | JP4150104B2 (en) |
KR (1) | KR100577920B1 (en) |
CN (1) | CN1162486C (en) |
FI (1) | FI121995B (en) |
WO (1) | WO1999058618A1 (en) |
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KR101194454B1 (en) * | 2005-03-24 | 2012-10-24 | 도호 가가꾸 고오교 가부시키가이샤 | Epoxy coating composition |
EP1980580A1 (en) | 2006-02-03 | 2008-10-15 | Asahi Kasei Chemicals Corporation | Microcapsule type hardener for epoxy resin, masterbatch type hardener composition for epoxy resin, one-pack type epoxy resin composition, and processed article |
JP5255192B2 (en) * | 2006-08-21 | 2013-08-07 | 中国塗料株式会社 | Epoxy resin composition capable of forming coating film having high elongation rate, anticorrosion coating composition, coating film thereof, base material coated with the coating film, and anticorrosion method for base material |
CN101522739B (en) * | 2006-10-04 | 2012-09-05 | 新日铁化学株式会社 | Epoxy resin, phenol resin, their production methods, epoxy resin composition and cured product |
CN101134867B (en) * | 2007-09-28 | 2012-05-23 | 中山大桥化工有限公司 | Shipping ballast cabin coating composition |
CN101880505B (en) * | 2010-07-06 | 2012-07-18 | 庞贝捷(涂料)昆山有限公司 | Thick film type antirust coating and preparation method thereof |
TWI502016B (en) | 2012-07-31 | 2015-10-01 | Asahi Kasei E Materials Corp | Epoxy resin compositions, epoxy resins and hardened products |
KR101775613B1 (en) | 2014-09-16 | 2017-09-07 | 주식회사 메디바이오랩 | Composition for preventing, alleviating or treating periodontal diseases comprising extract of Garcinia Mangostana or Alpha, Gamma-mangostins |
JP6712402B2 (en) | 2015-11-13 | 2020-06-24 | 味の素株式会社 | Coated particles |
CN106349871A (en) * | 2016-08-26 | 2017-01-25 | 江苏华夏制漆科技有限公司 | Waterborne epoxy quick-drying anti-corrosion coating and preparation method thereof |
TWI723252B (en) | 2017-03-17 | 2021-04-01 | 日商旭化成股份有限公司 | Thermosetting resin composition |
DE112019000385T5 (en) | 2018-01-12 | 2020-09-17 | Ajinomoto Co., Inc. | Coated Particle |
CN111117418A (en) * | 2018-11-01 | 2020-05-08 | 庞贝捷涂料(昆山)有限公司 | Anticorrosive coating composition |
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JPS5952656B2 (en) * | 1977-04-11 | 1984-12-20 | 日石三菱株式会社 | epoxy resin composition |
JPS54131660A (en) * | 1978-04-03 | 1979-10-12 | Mitsui Petrochem Ind Ltd | Epoxy resin composition |
JPH0286644A (en) * | 1988-09-22 | 1990-03-27 | Nippon Steel Chem Co Ltd | Coumarone/indene resin emulsion composition and adhesive |
JP3044567B2 (en) * | 1990-11-06 | 2000-05-22 | 東ソー株式会社 | Hot melt adhesive |
JPH05105858A (en) * | 1991-10-17 | 1993-04-27 | Nippon Steel Chem Co Ltd | Hot-melt self-adhesive composition |
JP3339893B2 (en) * | 1992-12-01 | 2002-10-28 | 新日本石油化学株式会社 | Epoxy resin composition |
JPH09263713A (en) * | 1996-03-28 | 1997-10-07 | Kansai Paint Co Ltd | Anticorrosive coating composition |
JP3783167B2 (en) * | 1996-05-28 | 2006-06-07 | 新日本石油化学株式会社 | Hot melt composition and modified aromatic petroleum resin used therefor |
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1998
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1999
- 1999-05-13 WO PCT/JP1999/002489 patent/WO1999058618A1/en active IP Right Grant
- 1999-05-13 KR KR1019997012470A patent/KR100577920B1/en not_active IP Right Cessation
- 1999-05-13 CN CNB998007374A patent/CN1162486C/en not_active Expired - Lifetime
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KR20010014326A (en) | 2001-02-26 |
CN1162486C (en) | 2004-08-18 |
FI20000039A (en) | 2000-01-10 |
FI121995B (en) | 2011-07-15 |
JPH11323247A (en) | 1999-11-26 |
CN1272125A (en) | 2000-11-01 |
JP4150104B2 (en) | 2008-09-17 |
WO1999058618A1 (en) | 1999-11-18 |
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