KR100411620B1 - Fluoro-coating composition for pvc frame - Google Patents
Fluoro-coating composition for pvc frame Download PDFInfo
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- KR100411620B1 KR100411620B1 KR1019950066596A KR19950066596A KR100411620B1 KR 100411620 B1 KR100411620 B1 KR 100411620B1 KR 1019950066596 A KR1019950066596 A KR 1019950066596A KR 19950066596 A KR19950066596 A KR 19950066596A KR 100411620 B1 KR100411620 B1 KR 100411620B1
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- 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
Abstract
Description
본 발명은 PVC 프레임용 불소도료 조성물에 관한 것으로서, 더욱 상세하게는 도장되지 아니한 단순백색으로서 내오염성이 불량한 PVC 창틀과 같은 프레임에 도포하기 위해 용제형 불소수지를 주성분으로 하고 안료, 용제, 경화촉매, 가교제 등의 첨가제와 실란 및 아연화합물을 첨가하여 만든 불소도료 수지조성물을 구성하므로써 이를 건축외장용 PVC 프레임에 코팅시키는 경우 도장특성이 우수하고 도막물성이 장기간 유지되어 내후성 및 내오염성이 크게 향상되며, PVC 프레임의 열적변화를 차단시킬 수 있는 물성 유지가 가능한 개선된 PVC 프레임용 불소도료 수지조성물에 관한 것이다.The present invention relates to a fluorine coating composition for a PVC frame, and more particularly, a simple white, unpainted, which is mainly composed of a solvent-type fluorine resin to be applied to a frame such as a PVC window frame having poor stain resistance, and includes a pigment, a solvent and a curing catalyst. By constituting fluorine paint resin composition made by adding additives such as, crosslinking agent, silane and zinc compound, when coating it on PVC frame for building exterior, the coating property is excellent and the coating property is maintained for a long time, which greatly improves weather resistance and pollution resistance. An improved fluorine coating resin composition for PVC frames capable of maintaining physical properties that can prevent thermal changes of PVC frames.
일반적으로 건축외장재로 널리 이용되고 있는 PVC(폴리비닐클로라이드) 프레임(frame)은 대개 창틀에 많이 적용되고 있으나 내후성 및 내구성이 많이 떨어져 이에 대한 보완이 요구된다.In general, PVC (polyvinyl chloride) frame, which is widely used as a building exterior material is commonly applied to the window frame, but the weather resistance and durability is much lower, and it is required to compensate for it.
PVC 창틀의 주원료인 PVC의 구조는 아래와 같으며, 이는 열이나, 광의 에너지에 의해 탈 HCl이 되어 발색단인 폴리에 구조(착색원인) 또는 주쇄의 절단, 가교 등을 일으켜 물성변화를 일으킨다.The structure of PVC, which is the main raw material of PVC window frames, is as follows, which becomes deHCl due to heat or energy of light, causing changes in physical properties by cutting (crosslinking) of the chromophore (caused in color) or the main chain.
이들의 분해과정을 살펴보면Looking at their decomposition process
즉 PVC의 분해는 폴리머 분자내의 분자내의 취약부분 다시 말해 말단 이중결합, 촉매 결합부, 분지점에서 열 또는 광 등에 의해 탈 HCl이 되는데 이것은 아릴 공명에 의한 소위 지퍼(Zipper) 반응에 의해 이중결합이 연속된 폴리엔 구조를 형성한다.In other words, the decomposition of PVC becomes de-HCl due to the weak part of the molecule in the polymer molecule, that is, the terminal double bond, the catalytic bond, and the heat or light at the branching point, which is caused by the so-called zipper reaction by aryl resonance. To form a continuous polyene structure.
이때 분해요인은 열, 자외선광, 수분, 산소 등이다.The decomposition factors are heat, ultraviolet light, moisture, oxygen and the like.
특히 PVC내에 있는 C-Cl 결합은 지구상에 존재하는 소량의 자외선에 의해서도 그 결합이 파괴되므로, PVC 창틀의 구조적 내구성은 약하다고 할 수밖에 없다.In particular, C-Cl bonds in PVC are broken even by a small amount of ultraviolet light present on the earth, so the structural durability of the PVC window frame is weak.
이러한 특성 때문에 빛 또는 열에 대한 내구성의 약점을 막기 위해 지당 또는 PVC 안정제 등을 투입하는 방법을 기존에는 사용하고 있으나, 이들의 효과는 일시적인 효과이외는 기대하기가 어려웠다.Because of this property, to prevent the weakness of the durability against light or heat, conventional methods of injecting the land sugar or PVC stabilizer, etc. have been used in the past, but its effect was difficult to expect other than the temporary effect.
따라서 차후 아파트 베란다용 등의 외장재로서의 PVC 창틀의 수요를 대비하여 볼 때 PVC의 내후성의 보완은 필수적인 사항으로 판단된다.Therefore, in order to meet the demand for PVC window frames as exterior materials for apartment verandas, it is necessary to supplement the weathering resistance of PVC.
PVC 창틀의 구조적인 내후성 결함을 보완하는 방안으로는 현재 라미네이트 필름을 소재에 부착하는 방법, 아크릴 수지를 이용(CO-EXTRUSION)하는 방법, 도료를 도장하는 방법 등이 검토되고 있으나, 소비자의 욕구를 다양하게 만족할 수 있는 칼라 다양화, 가격에 따른 다양한 제품선정, 고내후성 등을 감안할 때 도료를 도장하는 방법이 가장 유리하다.In order to compensate for the structural weather resistance defects of PVC window frames, a method of attaching a laminate film to a material, a method of using an acrylic resin (CO-EXTRUSION), and a method of painting a paint are currently being considered. Considering the diversified color variety, selection of various products according to price, and high weather resistance, the method of coating the paint is most advantageous.
한편, 현재 기존 샤시 시장 대부분을 점유하고 있는 알루미늄 샤시는 그 동안의 알루미늄 가격의 상승으로 PVC 창틀에 비하여 가격경쟁력을 상실하고 있으나, PVC 창틀의 내구력, 내후성이 알루미늄 샤시를 대치할 만큼의 수준에 있지 못하여 대체사용이 늦어지고 있다.Meanwhile, aluminum chassis, which currently occupies most of the existing chassis market, is losing price competitiveness compared to PVC window frames due to the rise in aluminum prices.However, the durability and weather resistance of PVC window frames are not sufficient to replace aluminum chassis. Alternative use is being delayed.
이를 극복하기 위해서는 기존 알루미늄 샤시가 차지하고 있는 시장을 대치할 수 있는 우수한 내구력의 PVC 창틀을 개발할 필요가 있으며, 또한 소비자의 다양한 욕구를 만족시킬 수 있는 여러 종의 색상과 우수한 외관을 가진 PVC 창틀의 개발이 절실한 실정이다.To overcome this problem, it is necessary to develop a durable PVC window frame that can replace the market occupied by the existing aluminum chassis, and also develop a PVC window frame with various colors and excellent appearance to satisfy various needs of consumers. This is an urgent situation.
종래에 PVC프레임용 불소도료 조성물로서 클로로트리플루오로에틸렌(CTFE)을 주쇄로 하는 불소수지를 사용하고 여기에 안료와 용제, 경화촉매, 가교제, 희석제 및 UV 흡수제를 첨가하여 제조한 것이 알려져 있다.Conventionally, it is known to use a fluorine resin containing chlorotrifluoroethylene (CTFE) as a main chain as a fluorine coating composition for PVC frames, and to which a pigment, a solvent, a curing catalyst, a crosslinking agent, a diluent and a UV absorber are added thereto.
그러나, 이러한 종래의 불소도료 조성물은 카르복실값이 없는 수지를 사용하여 내구성은 우수한 특성을 나타내었으나 안료를 감싸주는 웨팅성(wetting property)이 약하여 안료분산용으로 적합하지 않은 문제가 있었다. 또한, 이러한 종래의 도료조성물은 일반적으로 PVC 소재와의 부착력이 약하여 도장성이 떨어지기 때문에 2∼4회 반복하여 도포해주어야만 어느 정도 도포효과를 얻을 수 있어서 사용상 개선의 여지도 많았다.However, such a conventional fluorine coating composition exhibits excellent durability using a resin having no carboxyl value, but has a problem in that it is not suitable for pigment dispersion due to weak wetting property surrounding the pigment. In addition, such a conventional paint composition generally has a weak adhesion to the PVC material and the paintability is inferior, so if applied repeatedly 2-4 times to obtain a certain coating effect was much room for improvement in use.
따라서, 본 발명은 종래 PVC 프레임에 적용되었던 내후성 및 내오염성 부여 방법에서 나타나는 문제점을 개선하고 PVC 프레임의 적용성을 증진시키기 위하여, PVC 프레임의 코팅용 도료로서 카르복실값을 갖는 용제형 불소수지에 여러 첨가제와 특히 실란 화합물 및 아연화합물을 첨가한 조성물을 제조하므로써 PVC 프레임에 도포 적용시 부착력과 안료 분산성 및 보호기능이 우수하여 기존의 내후성 및 내오염성은 물론 외관 향상 및 도포특성이 크게 개선된 PVC 프레임용 불소도료조성물을 제공하는데 그 목적이 있다.Therefore, the present invention is to improve the problems in the weathering and fouling imparting method applied to the conventional PVC frame and to improve the applicability of the PVC frame, to a solvent-type fluorine resin having a carboxyl value as a coating material for coating the PVC frame. By producing various additives, especially silane compound and zinc compound, it has excellent adhesion and pigment dispersibility and protection when applied to PVC frame, which greatly improves weather resistance and stain resistance as well as appearance and coating properties. The purpose is to provide a fluorine coating composition for PVC frames.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 용제형 불소수지인 클로로트리플루오로에틸렌 수지를 기본 성분으로 하고 여기서 안료, 용제, 경화촉매, 가교제, 희석제 및 UV 흡수제가 함유되어 있는 PVC 프레임용 불소도료조성물에 있어서, 상기 클로로트리플루오로에틸렌 수지로 카르복실값이 3∼6인 것을 전체 도료조성에 대하여 20∼40 중량%로 함유하고, 상기 공지의 첨가제 이외에 실란화합물 0.01∼0.1 중량%와 아연 화합물 0.01∼0.1 중량%가 첨가 혼합되어 있는 것을 그 특징으로 한다.The present invention is a fluorotrifluoroethylene composition for PVC frame containing chlorotrifluoroethylene resin, which is a solvent-type fluororesin as a basic component, and containing a pigment, a solvent, a curing catalyst, a crosslinking agent, a diluent, and a UV absorber. 20 to 40 wt% of the ethylene value of 3 to 6 based on the total coating composition of the low ethylene resin, 0.01 to 0.1 wt% of the silane compound and 0.01 to 0.1 wt% of the zinc compound in addition to the known additives It is characterized by that.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 종래의 PVC 프레임용 불소도료 조성물에 있어서, 종래에 용제형 불소수지로 사용되었던 카르복실값이 없는 클로로트리플루오로(CTFE)를 주쇄로 하는 수지를 카르복실값이 3∼6개인 것으로 대체하여 사용함과 동시에 새로운 첨가제로서 실란 화합물 및 아연화합물을 추가로 소량 첨가하여서 안료 분산성이나 도포 특성 등 제반 물성을 크게 개선시킨 것이다. 본 발명에 따른 불소도료 조성물은 카르복실값이 3∼6인 CTFE를 주쇄로 하는 수지 20∼40 중량%, 공지의 세라믹안료 15∼30 중량%, 용제로서 셀로솔브 아세테이트, 크실렌 및 메틸이소부틸케톤이 혼합된 혼합용매 5∼40 중량%, 공지의 경화촉매 0.01∼0.1 중량%, 가교제 2∼40 중량%, 통상의 희석제 15∼45 중량%, 그리고 UV 흡수제 0.1∼5 중량%로 이루어질 수 있다.The present invention is a fluorocarbon resin composition having a carboxyl value of 3 to 6 as a main chain of a fluorotrifluoro (CTFE) having no carboxyl value, which is conventionally used as a solvent-type fluorine resin, in the conventional PVC frame fluorine coating composition. In addition to the addition of a small amount of the silane compound and zinc compound as a new additive as a new additive, the physical properties such as pigment dispersibility and coating properties are greatly improved. The fluorine coating composition according to the present invention is 20 to 40% by weight of resin having a CTFE having a carboxyl value of 3 to 6 as a main chain, 15 to 30% by weight of a known ceramic pigment, and cellosolve acetate, xylene and methyl isobutyl ketone as solvents. 5 to 40% by weight of this mixed mixed solvent, 0.01 to 0.1% by weight of a known curing catalyst, 2 to 40% by weight of a crosslinking agent, 15 to 45% by weight of a conventional diluent, and 0.1 to 5% by weight of a UV absorber.
본 발명에서, 주성분으로 사용되는 용제형 불소수지인 CTFE를 주쇄로 하는 수지의 경우 카르복실값이 3 보다 적으면 저장성이 저하되고 안료에 대한 웨팅성이 저하되어 바람직하지 못하고 6 보다 크게 되면 분자량이 작아져서 내구성이 약해진다.In the present invention, in the case of resin having a main chain of CTFE, a solvent-type fluorine resin used as a main component, when the carboxyl value is less than 3, the storage property is lowered, the wettability to the pigment is lowered, which is undesirable, and when the molecular weight is greater than 6, It becomes small and the durability becomes weak.
본 발명에서 사용된 CTFE의 경우 CTFE 골격을 주쇄로 하여 주쇄의 말단 또는 측쇄에 비닐에테르(VE), 비닐에스테르(VES) 또는 이들이 혼재된 상태로 도입된 용제형 불소수지로서 불소함량이 고형분 기준으로 20∼30 중량%인 것을 사용한다.The CTFE used in the present invention is a solvent-type fluorine resin introduced in a state in which a vinyl ether (VE), a vinyl ester (VES) or a mixture thereof is present at the end or side chain of the main chain with the CTFE skeleton as the main chain, and the fluorine content is based on the solid content. 20-30 weight% is used.
이와 같은 본 발명에 따른 CTFE 수지는 카르복실값이 있는 것이기 때문에 안료분산성과 소재와의 부착력을 향상시켜주고 또 내구성도 증대시켜 주는 효과가 있어서 도포특성을 크게 향상시켜준다.Since the CTFE resin according to the present invention has a carboxyl value, it has an effect of improving the pigment dispersibility and adhesion to the material and also increasing the durability, thereby greatly improving the coating properties.
본 발명에서의 CTFE 수지에 카르복실값을 상승시켜 주기 위해서는 비닐 에테르 또는 비닐에스테르를 CTFE에 혼합시켜주게 되면 통상의 방법으로 반응시켜서 카르복실값을 상승시킬 수 있다.In order to increase the carboxyl value in the CTFE resin in the present invention, when the vinyl ether or vinyl ester is mixed with the CTFE, the carboxyl value can be increased by reacting in a conventional manner.
본 발명에서 사용되는 세라믹 안료는 색상을 부여해주면서 내열성, 내자외선성 및 내약품성에 기여하여 제품의 내구력을 높게 유지해 주는 것인바, 예컨대 TiO2계 안료를 사용할 수 있다. 그 사용량이 과다하면 도막형성이 어려워 도막 물성이 저하되고 너무 적으면 색상부여효과가 떨어져 외관이 좋지 못하고 내구력을 저하시킬 수 있다.The ceramic pigments used in the present invention contribute to heat resistance, UV resistance and chemical resistance while imparting color to maintain high durability of the product. For example, a TiO 2 pigment may be used. If the amount is excessively used, the coating film formation is difficult, and the coating film properties are lowered. If the amount is too small, the color imparting effect is lowered, which may result in poor appearance and lower durability.
본 발명에서 사용되는 용제는 전체 배합량에 대하여 셀로솔브 아세테이트가 1∼10 중량%, 크실렌이 5∼20 중량%, 메틸이소부틸케톤이 3∼15 중량%로 혼합된 혼합용제를 사용하는 바, 셀로솔브 아세테이트는 레벨특성을 유지하기 위해 사용되고 크실렌은 도료 도포작업자가 도료를 사용할 수 있는 시간인 포트라이프성을 확보해 주기 위해 사용되며, 메틸이소부틸케톤은 내쌔깅성(anti-sagging property)을 부여해주기 위해 사용되는 것으로 이들 혼합용매가 과량 사용되면 전체적인 물성에서 부착력 저하나 내구력 저하의 문제가 있고 너무 소량 사용되면 상기한 각 특성을 기대하기 어렵다.The solvent used in the present invention uses a mixed solvent in which 1-10% by weight of cellosolve acetate, 5-20% by weight of xylene, and 3-15% by weight of methyl isobutyl ketone are used. Sorbate acetate is used to maintain level properties and xylene is used to ensure port life, which is the time the painter can use the paint. Methyl isobutyl ketone provides anti-sagging properties. When used in excess of these mixed solvents, there is a problem of deterioration of adhesion or durability in the overall physical properties, and when used in a small amount, it is difficult to expect each of the above characteristics.
본 발명에서 사용되는 경화촉매는 도막건조 및 경화시간 단축의 목적으로 사용되는 것으로 통상의 디부틸틴 디라우레이트 등을 소량으로 사용한다.The curing catalyst used in the present invention is used for the purpose of drying the coating film and shortening the curing time, and a small amount of ordinary dibutyltin dilaurate is used.
가교제는 역시 통상의 것으로서 예컨대 헥사메틸렌 디이소시아네이트 등을사용할 수 있으며, 그 사용량이 5 중량% 보다 적으면 가교불량으로 도막물성이 크게 저하되어 내구력이 보장되지 않게 되고, 20 중량%보다 많으면 도막에 튐(brittle) 현상이 발생되어 바람직하지 못하다.As the crosslinking agent, a hexamethylene diisocyanate or the like may also be used. For example, when the amount of the crosslinking agent is less than 5 wt%, the coating properties are greatly reduced due to crosslinking defects, and durability is not guaranteed. It is undesirable to have a brittle phenomenon.
또한, 희석제는 도막의 두께를 유지시켜주기 위해 사용되는 것으로 예컨대 메틸아세테이트 또는 메틸이소부틸케톤 등이 사용될 수 있으며, UV 흡수제로는 예컨대 벤조-트리아졸계의 UV 흡수제가 사용될 수 있는바, 0.1 중량%보다 적은 량으로 사용하면 내후성이 다소 저하되고 5 중량% 보다 과량 사용되면 다른 물성에 악영향을 미친다.In addition, the diluent is used to maintain the thickness of the coating film, such as methyl acetate or methyl isobutyl ketone may be used, such as UV absorbers, for example, benzo-triazole-based UV absorbers can be used, 0.1% by weight When used in a smaller amount, the weather resistance is slightly lowered, and when used in excess of 5% by weight, adversely affect other physical properties.
본 발명에 따르면 상기의 첨가제 이외에 실란 화합물을 사용하는 바, 예컨대 에폭시드 실란이 사용될 수 있다. 실란 화합물은 PVC 소재와의 부착력을 향상시켜 주므로써 아연 화합물과 함께 사용되어 종래의 수회코팅을 단 한번의 코팅이 가능하도록 하는데 결정적으로 기여한다. 만일 실란 화합물이 0.01 중량% 보다 적게 사용되는 경우 부착령이 저하되고 내수성이 떨어지며, 0.1 중량% 보다 과량 사용되면 도료의 겔화 현상이 야기되어 저장성이 불량하게 되는 문제가 있다.According to the invention a silane compound is used in addition to the above additives, for example epoxide silane can be used. The silane compound is used in conjunction with the zinc compound by improving adhesion to the PVC material, thereby contributing decisively to making a conventional single coating coating possible. If the silane compound is used less than 0.01% by weight, the adhesion order is lowered and the water resistance is lowered. If the silane compound is used in excess of 0.1% by weight, the gelling phenomenon of the paint is caused, resulting in poor storage.
특히, 실란 화합물은 아연 화합물과 함께 PVC 소재의 하이드록시기와 반응하여 도막 특성을 크게 향상시켜준다는 점이 매우 특이하다.In particular, the silane compound reacts with the hydroxyl group of the PVC material together with the zinc compound to significantly improve the coating properties.
아연화합물로는 예컨대 아연-옥토에이트를 사용하는 바, 과량 사용되면 도막의 경화가 고르게 일어나지 않고, 너무 소량 사용되면 상기 각 특성을 기대할 수 없는 문제가 있다.As a zinc compound, for example, zinc-octoate is used. When the zinc compound is used in an excessive amount, curing of the coating film does not occur evenly, and when too small, the above characteristics cannot be expected.
본 발명에 따르면 상기와 같은 카르복시값이 3∼6인 CTFE를 주쇄로 하는 수지를 용제와 함께 밀 베이스(Mill base)로 혼합하고 500∼1000 rpm으로 교반한 다음 세라믹 안료를 첨가한 다음 다시 500∼1000 rpm으로 교반하여 혼합시키고 나서, 세이크(shake)형 분산기로 다시 1∼3 시간 교반시킨 다음 입도가 20 ㎛ 이하로 유지되면 그 이외의 모든 첨가제를 교반하에 투입하여 도료 수지조성물을 제조한다.According to the present invention, a resin having a CTFE having a carboxyl value of 3 to 6 as a main chain is mixed with a solvent to a mill base, stirred at 500 to 1000 rpm, and then a ceramic pigment is added again to 500 to After stirring and mixing at 1000 rpm, the mixture was stirred for 1 to 3 hours again with a shake-type disperser, and when the particle size was maintained at 20 μm or less, all other additives were added under stirring to prepare a coating resin composition.
상술한 바와 같이, 본 발명에 따라 제조된 불소 도료 조성물은 PVC 프레임에 적용시키는 경우 종래의 것에 비하여 내구성 등 제반 물성이 전혀 뒤지지 않으면서 PVC 수지와의 부착력 등 도장특성과 내수성이 향상되고 안료 분산성이 우수하여 외관도 미려한 도포가 가능한 효과가 있는 것이다.As described above, the fluorine coating composition prepared according to the present invention improves coating properties and water resistance, such as adhesion to PVC resin, and pigment dispersibility, without any inferior physical properties such as durability when applied to a PVC frame. It is excellent in this, and the appearance is also beautiful and the effect which can be applied is possible.
이하, 본 발명을 실시예에 의거 상세히 설명하겠는 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.
실시예Example
용제형 불소수지로서 클로로트리플루오로(CTFE) 골격을 주쇄로 하고 주쇄의 말단 또는 측쇄에 비닐에테르(VE)가 결합되어 있는 CTFE/VE형 수지(Lumiflon 400, 일본 아사히 글라스 사, 고형분 30 중량%, 카르복실값 6) 20 g에 셀로솔브 아세테이트 3 g, 메틸이소부틸케톤 5.22 g, 크실렌 7 g을 투입한 후 일반 교반용 믹서로 800 rpm으로 10분간 교반한다.CTFE / VE resin (Lumiflon 400, Asahi Glass, Japan, Solid content 30% by weight, with chlorotrifluoro (CTFE) skeleton as main chain and vinyl ether (VE) bonded to terminal or side chain of main chain as solvent type fluorocarbon resin) , 3 g of cellosolve acetate, 5.22 g of methyl isobutyl ketone, and 7 g of xylene were added to 20 g of carboxyl value 6), followed by stirring for 10 minutes at 800 rpm with a general stirring mixer.
이 교반된 용액에 TiO2 25 g, 흄 실리카 0.3 g을 넣고 800 rpm으로 다시 10분간 교반한 다음, 이 도료를 유리비드를 이용하여 도료의 입자경이 10 ㎛ 이하가 되도록 교반한다.25 g of TiO2 and 0.3 g of fume silica were added to the stirred solution, and the mixture was stirred at 800 rpm for 10 minutes. Then, the paint was stirred using glass beads so that the particle size of the coating was 10 µm or less.
분산된 도료에 분자량이 10,000 이상인 불소수지로서 카르복실값이 없는CTFE/VE형 수지(Lumiflon 200, 일본 아사히 글라스 사, 고형분 60 중량%)를 30 g 투입하고, 디부틸틴 디라우레이트 0.02 g, 자이렌 9 g, 벤조-트리아졸계의 UV 흡수제(Tinuvin 384, 시바가이기 사)를 0.4 g 넣은 후에 800 rpm으로 10분간 교반한다.30 g of CTFE / VE resin having no carboxyl value (Lumiflon 200, Asahi Glass, Japan, 60 wt% solids) was added to the dispersed paint as a fluorine resin having a molecular weight of 10,000 or more, 0.02 g of dibutyltin dilaurate, 9 g of styrene and 0.4 g of a benzo-triazole-based UV absorber (Tinuvin 384, Shivagaigi Co., Ltd.) were added thereto, followed by stirring at 800 rpm for 10 minutes.
그 후 에폭시형 실록산(A-184, 다우코닝사 제품)을 0.03 g 및 Zn-옥토아세테이트 0.03 g을 투입하고 1500 rpm으로 45분간 교반하여서 제 1조성물을 제조한다.Thereafter, 0.03 g of Zn-octoacetate and 0.03 g of epoxy siloxane (A-184, available from Dow Corning) were added thereto, followed by stirring at 1500 rpm for 45 minutes to prepare a first composition.
이와 별도로 가교제로서 헥사메틸렌 디이소시아네이트형 수지(NPI사, coronate HX) 33 g에 셀로솔브 아세테이트와 부틸 아세테이트를 50/50으로 혼합한 혼합용매를 투입하여 800 rpm에서 10분간 교반하여서 제 2조성물로서 경화용 수지를 제조한다.Separately, 33 g of hexamethylene diisocyanate resin (NPI, coronate HX) as a crosslinking agent was added to a mixed solvent of 50/50 of cellosolve acetate and butyl acetate, and stirred at 800 rpm for 10 minutes to cure as a second composition. Prepare a resin for use.
이렇게 얻어진 상기 제 1 조성물과 제 2 조성물을 85 : 15의 중량비로 혼합시켜서 목적하는 불소도료 조성물을 제조한다.The first composition and the second composition thus obtained are mixed at a weight ratio of 85:15 to prepare a desired fluorine coating composition.
비교예 1Comparative Example 1
상기 실시예에서 초기단계에 첨가한 카르복실값 6인 CTFE/VE형 수지(Lumiflon 400) 대신에 카르복실값이 없는 CTFE/VE형 수지(Lumiflon 200)를 같은 량으로 첨가하고 그 이외의 공정은 실시예와 동일하게 실시하였다.Instead of CTFE / VE type resin (Lumiflon 400) having a carboxyl value of 6 added in the initial step in the above embodiment, CTFE / VE type resin (Lumiflon 200) having no carboxyl value was added in the same amount, and the other steps were performed. It carried out similarly to the Example.
비교예 2Comparative Example 2
상기 실시예와 동일하게 실시하되 에폭시형 실록산을 첨가하지 않았다.It carried out similarly to the said Example, but did not add the epoxy siloxane.
시험예Test Example
상기 실시예와 비교예 1∼2에서 제조된 조성물에 대하여 다음 도장 조건으로 처리 후 외관, 부착성, 촉진내후성, 내습성, 내산성, 내 알카리성을 시험하고 그결과는 다음 표에 나타내었다.The compositions prepared in Examples and Comparative Examples 1 and 2 were tested under the following coating conditions, and then tested for appearance, adhesion, accelerated weather resistance, moisture resistance, acid resistance, and alkali resistance, and the results are shown in the following table.
[도장조건][Painting conditions]
·희석 : 셀로솔브아세테이트(1308)/에틸아세테이트(1302) 혼합용제를 15∼20% 사용하고 점도를 18∼20 SEC로 조정함Dilution: Use 15-20% of the cellosolve acetate (1308) / ethyl acetate (1302) mixed solvent and adjust the viscosity to 18-20 sec.
·스프레이 : 5∼6 psi로 IWATA 061 GUN을 사용함.Spray: IWATA 061 GUN at 5 to 6 psi.
·DFT : 25∼30 UDFT: 25-30 U
·외관 : 교정시력 0.8 이상으로 목시거리 250∼300 mm 거리에서 외관 확인Appearance: Appearance check at visual distance 250 ~ 300 mm with correction vision 0.8
[시험방법][Test Methods]
·부착성 : 면도칼을 이용하여 시험편 표면까지 닿도록 1 mm 간격의 눈금 100개를 만들고 그 위에 셀로판 접착 테이프를 충분히 압착하여 90° 방향으로 당겨 도막박리 상태 검사Adhesion: Make 100 scales with a 1 mm interval to reach the surface of the specimen by using a razor, and sufficiently press the cellophane adhesive tape on it and pull it in the direction of 90 ° to inspect the peeling of the film.
·촉진내후성 : W-O-M 2000시간 폭로, Q.U.V 2000시간 폭로Promoting weather resistance: W-O-M 2000 hours exposed, Q.U.V 2000 hours exposed
·내습성 : 40 ℃ 상대습도 90 % 이상에서 240시간 시험편을 침적시킨 후 꺼내어 실온 1시간 방치 후 표면상태 검사 및 밀착성 시험Moisture resistance: After depositing test specimens for 240 hours at 90 ° C or higher relative humidity of 40 ℃, remove them, and leave them for 1 hour at room temperature.
·내산성 : 0.1 N H2SO45 mL 적하(SPOT법), 25℃×48시간 방치 후 물로 씻어내고, 1시간 방치 후 도막표면 검사Acid resistance: 5 mL of 0.1 NH 2 SO 4 is added dropwise (SPOT method), washed with water after standing at 25 ° C for 48 hours, and inspected after coating for 1 hour.
·내알카리성 : 0.1 N NaOH 5 mL(SPOT법), 25℃×48시간 방치 후 물로 씻어내고, 1시간 방치 후 도막표면 검사Alkali resistance: 0.1 N NaOH 5 mL (SPOT method), left at 25 ° C for 48 hours, washed with water and left for 1 hour to inspect the coating film
[표][table]
Claims (2)
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| KR1019950066596A KR100411620B1 (en) | 1995-12-29 | 1995-12-29 | Fluoro-coating composition for pvc frame |
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| KR100584155B1 (en) * | 1997-12-31 | 2006-08-03 | 주식회사 케이씨씨 | Non-polluting fluorine coating composition |
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| KR100484291B1 (en) * | 1996-12-30 | 2006-01-12 | 고려화학 주식회사 | Durable and non-polluting, natural dry fluorine membrane composition |
| KR100740327B1 (en) * | 2001-12-29 | 2007-07-18 | 주식회사 케이씨씨 | Fluorine resine composition |
| KR100463049B1 (en) * | 2002-05-11 | 2004-12-23 | 최경복 | Painting method of pvc fittings |
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| JPH06172451A (en) * | 1992-12-08 | 1994-06-21 | Central Glass Co Ltd | Coating resin |
| KR950008515A (en) * | 1993-09-02 | 1995-04-17 | 귄터 슈마허, 클라우스 대너 | Pyrido [1,2,3-d, e] [1,3,4] benzoxadiazine derivatives |
| JPH07188604A (en) * | 1993-12-28 | 1995-07-25 | Central Glass Co Ltd | Fluororesin coating composition |
| KR960022907A (en) * | 1994-12-30 | 1996-07-18 | 김충세 | UV Curable Coating Composition |
-
1995
- 1995-12-29 KR KR1019950066596A patent/KR100411620B1/en not_active IP Right Cessation
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900014543A (en) * | 1989-03-02 | 1990-10-24 | 다나까 마스오 | Fluorine-based resin composition, curable composition and coating composition |
| JPH0625589A (en) * | 1990-12-21 | 1994-02-01 | Elf Atochem Sa | Coating and varnish composition based on crosslinkable fluorocopolymer |
| JPH05117577A (en) * | 1991-10-31 | 1993-05-14 | Dainippon Ink & Chem Inc | Resin composition for coating material |
| JPH05320563A (en) * | 1992-05-28 | 1993-12-03 | Daikin Ind Ltd | Paint composition |
| JPH06122730A (en) * | 1992-10-12 | 1994-05-06 | Toagosei Chem Ind Co Ltd | Fluorocopolymer and coating composition based on the same |
| JPH06172451A (en) * | 1992-12-08 | 1994-06-21 | Central Glass Co Ltd | Coating resin |
| KR950008515A (en) * | 1993-09-02 | 1995-04-17 | 귄터 슈마허, 클라우스 대너 | Pyrido [1,2,3-d, e] [1,3,4] benzoxadiazine derivatives |
| JPH07188604A (en) * | 1993-12-28 | 1995-07-25 | Central Glass Co Ltd | Fluororesin coating composition |
| KR960022907A (en) * | 1994-12-30 | 1996-07-18 | 김충세 | UV Curable Coating Composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100584155B1 (en) * | 1997-12-31 | 2006-08-03 | 주식회사 케이씨씨 | Non-polluting fluorine coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970042882A (en) | 1997-07-26 |
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