KR20200043679A - Composition for restoring discolored anti-fouling paint - Google Patents
Composition for restoring discolored anti-fouling paint Download PDFInfo
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
Description
본 발명은 방오도료 복원용 조성물에 관한 것으로서, 보다 구체적으로는 선박 수선부에 해양생물 부착 방지를 위해 시공되는 방오도료의 변색 복원을 도모하기 위한 방오도료의 표면변색 복원용 조성물에 관한 것이다.The present invention relates to a composition for restoring antifouling paints, and more particularly, to a composition for restoring surface discoloration of antifouling paints to promote discoloration restoration of antifouling paints constructed to prevent marine organisms from attaching to a ship's repair part.
일반적으로 선박 수선부에 시공되는 방오도료는 해수에 연속적으로 침지되어 있을 때 그 기작이 발현되어 방오 성능을 발휘한다. In general, the antifouling paint applied to the ship's repair section exhibits its anti-fouling performance when the mechanism is expressed when it is continuously immersed in seawater.
그러나 SPC(self-polishing copolymer) 타입의 방오도료는 해수에 연속적으로 침지되지 못하고 일정기간 대기에 노출될 경우 변색(예, whitening)이 발생되는데, 이는 방오도료 최외각에 존재하는 리치층(leached layer)에 Na, Ca, K 등의 이온이 흡착되는 현상, 방오제로 배합되는 아산화동(Cu2O)이 염화물, 탄산가스 또는 산소와 반응하여 탄산염(carbonate)화 되는 현상 그리고 자외선에 의한 수지의 노화가 복합적으로 작용하여 발생되는 것으로 알려져 있다.However, the self-polishing copolymer (SPC) type antifouling paint is not continuously immersed in seawater and discoloration (e.g., whitening) occurs when exposed to the air for a certain period of time, which is the leached layer at the outermost part of the antifouling paint. ) Adsorption of ions such as Na, Ca, K, copper oxide (Cu 2 O), which is formulated as an antifouling agent, reacts with chloride, carbon dioxide or oxygen to carbonate, and aging of the resin by ultraviolet rays It is known that is caused by a complex action.
이러한 변색은 방오도료의 성능과는 무관한 단순 미관상의 문제이지만 선박 주문주의 클레임으로 인해 진수상태에서 재도장을 해야 하므로 추가비용 발생 및 환경문제를 야기시킨다.Although this discoloration is a simple aesthetic problem irrelevant to the performance of the antifouling paint, it must be repainted in the launching state due to the claims of the ship orderer, causing additional cost and environmental problems.
방오도료의 변색 대책과 관련되어 참조할 수 있는 선행기술문헌으로 한국 등록특허공보 제1879458호, 한국 공개특허공보 제2013-0018945호 등이 있다.Prior art documents that can be referred to in relation to anti-discoloration measures of antifouling paints include Korean Patent Publication No. 1879458, Korean Patent Publication No. 2013-0018945.
전자는 A) 카르복실산기를 포함하는 단량체와 알킬기를 포함하는 단량체의 라디칼 반응에 의해 제조된 아크릴 수지, 또는 알코올기를 포함하는 단량체 및 산기를 포함하는 단량체의 축합반응에 의해 제조된 폴리에스테르 수지; B) 2가 금속; 및 C) 카르복실산기와 아민기를 포함한다. 이에, 방오도료의 내변색성 및 내크랙성을 향상하는 효과를 기대한다.The former is A) an acrylic resin prepared by radical reaction of a monomer containing a carboxylic acid group and a monomer containing an alkyl group, or a polyester resin produced by a condensation reaction of a monomer containing an alcohol group and a monomer containing an acid group; B) divalent metals; And C) carboxylic acid groups and amine groups. Accordingly, the effect of improving the discoloration resistance and crack resistance of the antifouling paint is expected.
후자는 고형분의 산가가 50~200 ㎎KOH/g이고, 고형분의 수산기가가 100 ㎎KOH/g 이하이며, 25℃에 있어서의 점도가 500 mPaㆍs 이하인 폴리에스테르 수지를 함유하는 제1 성분과, 산화아연을 함유하는 페이스트인 제2 성분의 2액으로 형성된다. 이에, 자외선이나 수분 등에 의한 변색, 크랙을 방지하는 동시에 기계적 강도가 우수한 방오도막을 기대한다.The latter is a first component containing a polyester resin having an acid value of 50 to 200 mgKOH / g of solid content, a hydroxyl value of solid content of 100 mgKOH / g or less, and a viscosity at 25 ° C of 500 mPa · s or less. , It is formed of two liquids of the second component, a paste containing zinc oxide. Accordingly, anti-fouling coatings having excellent mechanical strength while preventing discoloration and cracking due to ultraviolet rays or moisture are expected.
그러나, 상기한 선행문헌에 의하더라도 선박 건조 과정에서 해수에 침지되지 않은 상태라면 변색을 방지하기 미흡하다.However, even according to the above-mentioned prior literature, it is insufficient to prevent discoloration if it is not immersed in seawater during the shipbuilding process.
상기와 같은 종래의 문제점들을 개선하기 위한 본 발명의 목적은, 선박 건조시 방오도료의 성능에 영향이 없으면서 해양 환경오염을 유발하지 않는 친환경 성분의 수용액으로 방오도료의 변색 복원을 도모하기 위한 방오도료의 표면변색 복원용 조성물을 제공하는 데 있다.An object of the present invention for improving the conventional problems as described above, an anti-fouling paint for promoting discoloration restoration of the anti-fouling paint as an aqueous solution of an environmentally friendly component that does not cause marine environmental pollution without affecting the performance of the anti-fouling paint during shipbuilding It is to provide a composition for restoring the surface discoloration.
상기 목적을 달성하기 위하여, 본 발명은 선박용 방오도료의 표면변색을 복원하기 위한 조성물에 있어서: 상기 방오도료의 수지내 -COOR 작용기의 가수분해를 촉진시키는 수용성 기재에 물과 보조재를 혼합하여 생성되는 것을 특징으로 한다.In order to achieve the above object, the present invention is a composition for restoring the surface discoloration of a marine antifouling paint: It is produced by mixing water and an auxiliary material on a water-soluble substrate that promotes hydrolysis of a -COOR functional group in the resin of the antifouling paint. It is characterized by.
본 발명의 세부 구성으로서, 상기 수용성 기재는 구연산(citric acid)과 에탄올(ethanol)을 혼합하여 생성되는 것을 특징으로 한다.As a detailed configuration of the present invention, the water-soluble substrate is characterized by being produced by mixing citric acid and ethanol.
본 발명의 세부 구성으로서, 상기 보조재는 아크릴수지 에멀젼에 EVA 에멀젼을 혼합한 수용성 피막보호물질을 사용하는 것을 특징으로 한다.As a detailed configuration of the present invention, the auxiliary material is characterized in that a water-soluble film-protecting material in which an EVA emulsion is mixed with an acrylic resin emulsion is used.
본 발명의 세부 구성으로서, 상기 구연산 5~15%, 상기 에탄올 10~20%, 상기 물 60~80%, 상기 보조재 0~5%를 혼합하는 것을 특징으로 한다.As a detailed configuration of the present invention, 5 to 15% of the citric acid, 10 to 20% of the ethanol, 60 to 80% of the water, and 0 to 5% of the auxiliary material are mixed.
본 발명의 세부 구성으로서, 상기 구연산과 상기 에탄올은 방오도료의 표면변색 정도 및 상태에 대응하여 함량을 증감하는 것을 특징으로 한다.As a detailed configuration of the present invention, the citric acid and the ethanol is characterized by increasing or decreasing the content in response to the degree and state of the surface discoloration of the antifouling paint.
이상과 같이 본 발명에 의하면, 건조중인 선박에 대하여 소정의 수용액 상태로 방오도료의 변색 복원을 처리하는 과정에서 방오도료의 성능에 영향이 없으면서 해양 환경오염을 유발하지 않는 친환경성을 갖추는 효과가 있다.According to the present invention as described above, in the process of discoloration restoration of the antifouling paint in a predetermined aqueous solution condition for a ship under construction, there is no effect on the performance of the antifouling paint, and it has an effect of having eco-friendliness that does not cause marine environmental pollution. .
도 1은 본 발명에 따른 조성물을 적용하기 전후의 방오도료 상태를 나타내는 참고 자료1 is a reference material showing the state of the antifouling paint before and after applying the composition according to the present invention
이하, 첨부된 도면에 의거하여 본 발명의 실시예를 상세하게 설명하면 다음과 같다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명은 선박용 방오도료의 표면변색을 복원하기 위한 조성물에 관하여 제안한다. 도 1에 나타내는 방오도료(10)는 유기주석(organo tin) 또는 폴리우레탄(polyurethane)을 매트릭스로 하는 SPC(self-polishing copolymer) 타입을 대상으로 하지만 반드시 이에 국한되는 것은 아니다. 표면변색은 해수에 연속적으로 침지되지 못하고 일정기간 대기에 노출되는 경우 발생한다.The present invention proposes a composition for restoring the surface discoloration of the ship's antifouling paint. The
본 발명은 선박의 건조나 수리 과정에서 방오도료의 표면변색에 의한 재시공을 방지함을 요체로 한다.The present invention is to prevent the re-construction due to the surface discoloration of the antifouling paint during the construction or repair process of the ship.
본 발명에 따르면 상기 방오도료의 수지내 -COOR 작용기의 가수분해를 촉진시키는 수용성 기재에 물과 보조재를 혼합하여 생성되는 것을 특징으로 한다. 수용성 기재는 방오도료의 성능에 영향을 주지 않으면서 해양 환경오염을 유발하지 않는 친환경 성분으로 구성하는 것이 좋다. 방오도료의 -COOR 작용기의 가수분해를 촉진하고 Na, Ca, K 등의 이온을 포착할 수 있는 수용액을 기재로 사용하는 것이 선호된다. 물은 수용성 기재의 농도를 조절하기 위한 성분이고, 보조재는 방오도료의 표면변색 복원을 조력하는 성분이다.According to the present invention, it is characterized in that it is produced by mixing water and an auxiliary material in a water-soluble substrate that promotes the hydrolysis of the -COOR functional group in the resin of the antifouling coating. The water-soluble base material is preferably composed of environmentally friendly ingredients that do not cause marine environmental pollution without affecting the performance of the antifouling paint. It is preferred to use an aqueous solution capable of promoting hydrolysis of the -COOR functional group of the antifouling coating and capturing ions such as Na, Ca, and K as a substrate. Water is a component for controlling the concentration of the water-soluble substrate, and the auxiliary material is a component that assists in restoring surface discoloration of the antifouling paint.
본 발명의 세부 구성으로서, 상기 수용성 기재는 구연산(citric acid)과 에탄올(ethanol)을 혼합하여 생성되는 것을 특징으로 한다. 구연산은 방오도료의 성능에 영향을 주지 않는 친환경 성분으로서 염기의 완만한 중화작용과 색소 안정화로 변질을 방지한다. 저점성과 저비점의 에탄올은 구연산의 분산을 유도하면서 친환경적으로 방오도료의 보존성을 높인다.As a detailed configuration of the present invention, the water-soluble substrate is characterized by being produced by mixing citric acid and ethanol. Citric acid is an eco-friendly ingredient that does not affect the performance of antifouling paints and prevents deterioration by slow neutralization of bases and stabilization of pigments. Low-viscosity and low-boiling ethanol induces the dispersion of citric acid while enhancing the preservation of anti-fouling paints in an environmentally friendly manner.
본 발명의 세부 구성으로서, 상기 보조재는 아크릴수지 에멀젼에 EVA 에멀젼을 혼합한 수용성 피막보호물질을 사용하는 것을 특징으로 한다. 수용성 피막보호물질은 수용성 기재의 작용을 조력하여 적어도 일시적으로 표면변색 방지를 유지한다. 이외에 보조재로 대전방지제, 계면활성제, 자외선안정제, 촉매 등을 선택적으로 미량 포함할 수 있다.As a detailed configuration of the present invention, the auxiliary material is characterized in that a water-soluble film-protecting material in which an EVA emulsion is mixed with an acrylic resin emulsion is used. The water-soluble film-protecting material assists the action of the water-soluble base material to at least temporarily prevent surface discoloration. In addition, as an auxiliary material, an antistatic agent, a surfactant, a UV stabilizer, and a catalyst may be selectively included in a trace amount.
본 발명의 세부 구성으로서, 상기 구연산 5~15%, 상기 에탄올 10~20%, 상기 물 60~80%, 상기 보조재 0~5%를 혼합하는 것을 특징으로 한다. 방오도료의 물성에 따라 구연산 및 에탄올의 함량비에 다소의 변동이 있으나 적정 범위를 유지하는 것이 좋다. 구연산 및 에탄올 함량이 적정 범위에 미달하면 방오도료의 표면변색이 유발되고 적정 범위를 초과하여도 기능성에 유의적 변화가 발견되지 않는다.As a detailed configuration of the present invention, 5 to 15% of the citric acid, 10 to 20% of the ethanol, 60 to 80% of the water, and 0 to 5% of the auxiliary material are mixed. Depending on the properties of the antifouling paint, there are some variations in the content ratio of citric acid and ethanol, but it is good to maintain the proper range. If the citric acid and ethanol content is less than the appropriate range, surface discoloration of the antifouling paint is induced, and no significant change in functionality is found even if it exceeds the appropriate range.
본 발명의 세부 구성으로서, 상기 구연산과 상기 에탄올은 방오도료의 표면변색 정도 및 상태에 대응하여 함량을 증감하는 것을 특징으로 한다. 방오도료의 표면변색 정도 및 상태가 심한 경우 구연산과 에탄올의 함량은 적정 범위의 상한치에 근접하도록 설정한다. 구연산과 에탄올의 함량 증가는 반대로 물의 함량 감소를 수반한다.As a detailed configuration of the present invention, the citric acid and the ethanol is characterized by increasing or decreasing the content in response to the degree and state of the surface discoloration of the antifouling paint. When the degree of surface discoloration and the condition of the antifouling paint are severe, the contents of citric acid and ethanol are set close to the upper limit of the appropriate range. Increasing the content of citric acid and ethanol, on the contrary, involves reducing the water content.
도 1을 참조하면, 선박의 선저 영역에 도포된 방오도료(10)가 일정기간 대기에 노출되는 상태를 예시한다. SPC(self-polishing copolymer) 타입 도료의 특성상 변색을 방지하기 곤란하다. 도 1의 좌측은 방오도료(10)가 표면변색을 유발한 상태를 나타내고, 도 1의 우측은 본 발명의 조성물을 도포하여 방오도로(10)의 표면변색을 제거한 상태를 나타낸다. 본 발명의 조성물은 친환경 수용액을 기반으로 하므로 사용환경이 제한적이지 않아 유연한 시공이 가능하다.Referring to FIG. 1, an example of a state in which the
본 발명은 기재된 실시예에 한정되는 것이 아니고, 본 발명의 사상 및 범위를 벗어나지 않고 다양하게 수정 및 변형할 수 있음이 이 기술의 분야에서 통상의 지식을 가진 자에게 자명하다. 따라서 그러한 변형예 또는 수정예들은 본 발명의 특허청구범위에 속한다 해야 할 것이다.It is obvious to those skilled in the art that the present invention is not limited to the described embodiments, and can be variously modified and modified without departing from the spirit and scope of the present invention. Therefore, such modifications or modifications will have to belong to the claims of the present invention.
10: 방오도료10: antifouling paint
Claims (5)
상기 방오도료의 수지내 -COOR 작용기의 가수분해를 촉진시키는 수용성 기재에 물과 보조재를 혼합하여 생성되는 것을 특징으로 하는 방오도료의 표면변색 복원용 조성물.In the composition for restoring the surface discoloration of marine antifouling paint:
A composition for restoring surface discoloration of an antifouling paint, characterized in that it is produced by mixing water and an auxiliary material in a water-soluble substrate that promotes hydrolysis of a -COOR functional group in the resin of the antifouling paint.
상기 수용성 기재는 구연산(citric acid)과 에탄올(ethanol)을 혼합하여 생성되는 것을 특징으로 하는 방오도료의 표면변색 복원용 조성물.The method according to claim 1,
The water-soluble substrate is a composition for restoring surface discoloration of an antifouling coating, characterized in that it is produced by mixing citric acid and ethanol.
상기 보조재는 아크릴수지 에멀젼에 EVA 에멀젼을 혼합한 수용성 피막보호물질을 사용하는 것을 특징으로 하는 방오도료의 표면변색 복원용 조성물.The method according to claim 1,
The auxiliary material is a composition for restoring surface discoloration of an antifouling coating, characterized in that a water-soluble film-protecting material obtained by mixing an EVA emulsion with an acrylic resin emulsion is used.
상기 구연산 5~15%, 상기 에탄올 10~20%, 상기 물 60~80%, 상기 보조재 0~5%를 혼합하는 것을 특징으로 하는 방오도료의 표면변색 복원용 조성물.The method according to claim 1,
The composition for restoring surface discoloration of an antifouling coating, characterized in that the mixture of 5 to 15% citric acid, 10 to 20% of ethanol, 60 to 80% of water, and 0 to 5% of the auxiliary material.
상기 구연산과 상기 에탄올은 방오도료의 표면변색 정도 및 상태에 대응하여 함량을 증감하는 것을 특징으로 하는 방오도료의 표면변색 복원용 조성물.The method according to claim 4,
The citric acid and the ethanol is a composition for restoring the surface discoloration of the antifouling paint, characterized in that the content increases or decreases in response to the degree and state of the surface discoloration of the antifouling paint.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130018945A (en) | 2010-06-23 | 2013-02-25 | 주고꾸 도료 가부시키가이샤 | Stain-proof coating composition, stain-proof coating film, and method for prevention of staining of base material |
| KR101879458B1 (en) | 2012-01-26 | 2018-07-17 | 주식회사 케이씨씨 | Resin for antifouling patint having excellent discoloration-resistance and crack-resistance and antifouling paint composition comprising the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130018945A (en) | 2010-06-23 | 2013-02-25 | 주고꾸 도료 가부시키가이샤 | Stain-proof coating composition, stain-proof coating film, and method for prevention of staining of base material |
| KR101879458B1 (en) | 2012-01-26 | 2018-07-17 | 주식회사 케이씨씨 | Resin for antifouling patint having excellent discoloration-resistance and crack-resistance and antifouling paint composition comprising the same |
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