WO2025216402A1 - Polyester resin composition, and paint composition comprising polyester resin prepared therefrom - Google Patents
Polyester resin composition, and paint composition comprising polyester resin prepared therefromInfo
- Publication number
- WO2025216402A1 WO2025216402A1 PCT/KR2025/000692 KR2025000692W WO2025216402A1 WO 2025216402 A1 WO2025216402 A1 WO 2025216402A1 KR 2025000692 W KR2025000692 W KR 2025000692W WO 2025216402 A1 WO2025216402 A1 WO 2025216402A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester resin
- bio
- acid
- resin composition
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Definitions
- the present invention relates to an environmentally friendly polyester resin composition and a paint composition comprising a polyester resin produced therefrom.
- PCM Pre-Coated Metal
- paints for PCM must have excellent processability, and depending on the application, additional properties such as excellent hardness, scratch resistance, and weather resistance are required.
- Various PCM paints are used, including acrylic, urethane, epoxy, polyester, silicone, fluorine, and polyvinyl chloride.
- polyester paint compositions due to their excellent processability, are the most commonly used. Research and development are actively being conducted to improve the properties of such polyester paint compositions, and as an example, Korean Patent Publication No.
- 10-2001-0048577 discloses a polyester resin composition obtained by condensing a glycol compound containing bisphenol A, bisphenol F and/or bisphenol S having a hydroxy equivalent of 100 to 400 and an aromatic acid-containing diacid compound, to which ethylene oxide or propylene oxide is added.
- polyester paint compositions are manufactured using resins, monomers, and solvents derived from fossil fuels like petroleum and coal. This inevitably leads to the production of carbon dioxide, a contributor to global warming. Therefore, the development of environmentally friendly polyester paint compositions that can minimize carbon dioxide emissions is urgently needed.
- the present invention provides an environmentally friendly polyester resin composition capable of minimizing carbon dioxide emissions and a paint composition comprising a polyester resin manufactured therefrom.
- the present invention provides an environmentally friendly polyester resin composition capable of minimizing carbon dioxide emissions and a paint composition comprising a polyester resin manufactured therefrom.
- the polyester resin composition of the present invention and the paint composition comprising the polyester resin manufactured therefrom are environmentally friendly and exhibit physical properties equivalent to or higher than those of conventional fossil fuel-based polyester resins and paint compositions comprising the same.
- the polyester resin composition of the present invention and the paint composition comprising the polyester resin manufactured therefrom have a high bio-content and are thus applicable to various industrial fields requiring a high bio-content.
- the “weight average molecular weight” used herein is measured by a conventional method known in the art, and can be measured, for example, by a gel permeation chromatography (GPC) method.
- the “glass transition temperature” is measured by a conventional method known in the art, and can be measured, for example, by a differential scanning calorimetry (DSC) method.
- the functional group such as the “hydroxyl value” is measured by a conventional method known in the art, and can be measured, for example, by a titration method.
- the polyester resin composition of the present invention comprises an acid monomer and an alcohol monomer.
- the acid monomer may be an aliphatic acid, an aromatic acid, or a mixture thereof.
- isophthalic acid, terephthalic acid, adipic acid, trimellitic anhydride, dimer acid, sebacic acid, succinic acid, phthalic anhydride, benzene tricarboxylic acid anhydride, naphthalene tricarboxylic acid anhydride, etc. may be used, and these may be used alone or in combination of two or more.
- the acid monomer may include at least one selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, trimellitic anhydride, and dimer acid. In this case, as the number of ester bonds in the polyester resin increases, the weight average molecular weight of the polyester resin can be further increased, and when applied to a paint, the adhesion, processability, and storability can be further improved.
- the alcohol monomer may be a polyfunctional alcohol, and may be an aliphatic alcohol, an aromatic alcohol, or a mixture thereof.
- ethylene glycol, propylene glycol, 1,2-butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylol propane, glycerol, bisphenol A (BPA), an alkoxylated alcohol, propanediol, isosorbide, etc. may be used, and these may be used alone or in combination of two or more.
- the alcohol monomer may include at least one selected from the group consisting of ethylene glycol, neopentyl glycol, and ethoxylated bisphenol A. In this case, the price competitiveness, reactivity and hardness of the polyester resin can be further improved.
- At least one of the above acid monomers and alcohol monomers is a bio-based monomer.
- the bio-based acid monomer and/or bio-based alcohol monomer is derived from plants such as rapeseed oil, castor oil, and corn oil, and can reduce carbon dioxide emissions, unlike conventional polyester resins manufactured using acid monomers and alcohol monomers manufactured from fossil fuels.
- the bio-based acid monomer may include at least one selected from the group consisting of bio-based dimer acid, bio-based sebacic acid, bio-based succinic acid, and bio-based azelaic acid.
- the bio-based alcohol monomer may include at least one selected from the group consisting of bio-based propanediol, bio-based isosorbide, and bio-based dimer alcohol.
- the above bio-based acid monomer may be included in an amount of 20 to 45 wt%, for example, 25 to 35 wt%, based on the total weight of the polyester resin composition. If the content of the bio-based acid monomer is less than the above-mentioned range, processability may be reduced during paint production, and resin storability may be poor, resulting in cracking. If the content exceeds the above-mentioned range, corrosion resistance may be reduced, tackiness may be strong, curing may be reduced, and paint foaming may be poor.
- the above bio-based alcohol monomer may be included in an amount of 20 to 25 wt% based on the total weight of the polyester resin composition. If the content of the bio-based alcohol monomer is less than the above-mentioned range, processability may be reduced during paint production, resin storability may be poor, resulting in haziness over time, and solvent compatibility may be reduced. If the content exceeds the above-mentioned range, corrosion resistance may be reduced, and curing degree, alkali resistance, and paint defoaming may be poor.
- the above polyester resin composition may further include a solvent. This can enhance the solubility and lower the viscosity of the composition, thereby improving workability.
- a solvent commonly used in the relevant technical field can be used without particular limitation, including solvent naphtha, cyclohexanone, xylene, and the like.
- the polyester resin composition may include 20 to 45 wt% of the acid monomer, 5 to 25 wt% of the alcohol monomer, and 45 to 55 wt% of the solvent, based on the total weight of the polyester resin composition.
- the total content of the bio-based monomer in the polyester resin composition i.e., the bio content of the polyester resin manufactured from the polyester resin composition, may be 20 wt% or more, for example, 30 to 50 wt%, or as another example, 35 to 45 wt%. If the bio content is less than the above-mentioned range, carbon dioxide emissions may increase, which may be unfriendly to the environment, and if it exceeds the above-mentioned range, the strength and hardness of the coating film may decrease, which may deteriorate the physical properties of the coating film.
- the coating composition of the present invention is environmentally friendly and can be applied to various industrial fields requiring a high bio content by using a polyester resin with a high bio content.
- the bio-content can be calculated as the proportion of radioactive carbon (C14) in the total carbon content.
- Biomass materials contain radioactive carbon (C14), a carbon isotope, whereas petrochemical-derived materials do not. Therefore, the bio-content can be calculated by calculating the proportion of C14 in the total carbon content.
- the weight average molecular weight of the polyester resin manufactured from the polyester resin composition may be 3,000 to 10,000 g/mol, for example, 5,500 to 7,500 g/mol. If the weight average molecular weight of the polyester resin is less than the above-mentioned range, the molecular weight may be small, which may deteriorate the basic physical properties of the coating film, such as processability, hardness, corrosion resistance, and adhesion, and if it exceeds the above-mentioned range, the content of the solvent added for viscosity control may increase, making it difficult to form a coating film of a predetermined thickness, and compatibility with other resins or additives may deteriorate.
- the glass transition temperature of the polyester resin manufactured from the polyester resin composition may be 1 to 20°C, for example, 5 to 10°C. If the glass transition temperature of the polyester resin is less than the above-mentioned range, the flexibility of the resin increases, but the glass transition temperature of the coating film may decrease, resulting in deterioration of chemical resistance, corrosion resistance, and hardness. If the glass transition temperature exceeds the above-mentioned range, the flexibility of the resin may decrease, the glass transition temperature of the coating film may increase, resulting in deterioration of processability.
- the hydroxyl value of the polyester resin manufactured from the polyester resin composition may be 15 to 55 KOHmg/g, for example, 25 to 35 KOHmg/g. If the hydroxyl value of the polyester resin is less than the above-mentioned range, the bonding strength may be reduced due to a lack of OH groups in the resin, which may result in reduced water resistance and curing properties. If the hydroxyl value exceeds the above-mentioned range, OH groups may remain in the paint, which may result in excessive bonding within the paint, which may result in reduced processability and moldability.
- the acid value of the polyester resin prepared from the polyester resin composition may be 5 KOHmg/g or less, for example, 1 to 5 KOHmg/g. If the acid value of the polyester resin is less than the above-mentioned range, the reaction time may be prolonged, which may result in a deterioration in the color and appearance of the resin. If the acid value exceeds the above-mentioned range, the basic physical properties of the paint, such as processability, corrosion resistance, and hardness, may be deteriorated due to failure to reach an appropriate molecular weight.
- the viscosity (25°C) of the polyester resin prepared from the polyester resin composition may be 2,000 to 7,000 mPas, for example, 2,500 to 5,500 mPas. If the viscosity of the polyester resin is less than the above-mentioned range, the molecular weight of the resin may decrease, resulting in deterioration in processability, corrosion resistance, hardness, etc., and if it exceeds the above-mentioned range, the storability and compatibility of the resin may decrease.
- the solids content of the polyester resin manufactured from the polyester resin composition may be 40 to 70%, for example, 49 to 51%. If the solids content of the polyester resin is less than the aforementioned range, the resin viscosity may be too low to meet the target viscosity of the paint, and if it exceeds the aforementioned range, the resin viscosity may be too high, resulting in poor workability.
- the paint composition according to the present invention comprises a polyester resin prepared from the aforementioned polyester resin composition.
- the paint composition of the present invention is environmentally friendly due to its high bio-content, and is applicable to various industrial fields requiring a high bio-content.
- the paint composition according to the present invention may further include pigments, solvents, curing accelerators, and additives commonly used in the relevant technical fields, as needed.
- additives usable in the present invention include leveling agents, plasticizers, anti-settling agents, waxes, light stabilizers, gloss regulators, and the like.
- the mixture was cooled to 150 °C or lower, 210 g of bio-based acid monomer (Dimer acid, Cargill's Pripol 1009) was added, and esterification was performed at 250 °C and 200 rpm for 2 hours.
- the acid value was measured to be 20 mgKOH/g or less
- the mixture was cooled to 150°C or less, 20 g of xylene was added, and after refluxing at 230°C and 200 rpm, when the acid value became 5 mgKOH/g or less, the mixture was diluted with a solvent to produce a polyester resin of Synthesis Example 1.
- the physical properties of the produced polyester resin are shown in Table 1.
- Polyester resins of Synthetic Examples 2 to 9 were manufactured in the same manner as Synthetic Example 1, except that the compositions were as shown in Table 1 below.
- Polyester 1 Polyester resin of Synthesis Example 1
- Polyester 2 Polyester resin of Synthesis Example 2
- Polyester 3 Polyester resin of Synthetic Example 3
- Polyester 4 Polyester resin of Synthetic Example 4
- Polyester 5 Polyester resin of Synthetic Example 5
- Polyester 6 Polyester resin of Synthetic Example 6
- Polyester 7 Polyester resin of Synthetic Example 7
- Polyester 8 Polyester resin of synthetic example 8
- Polyester 9 Polyester resin of Synthetic Example 9
- polyester resin Mw 3,300 g/mol, Ohv 61 KOHmg/g, Tg 13 °C, NV 60%, viscosity (25 °C) 600-1,000 cps
- Solvent 1 Dibasic ester (ADD00198)
- Solvent 2 Propylene glycol methyl ether acetate (AAF00305)
- Solvent 3 Solvent naphtha (petroleum), light arom (AAB11161)
- Additive 1 Silicone-based defoaming agent (AEN01377)
- the paint composition of each experimental example was coated on a GI steel plate for PCM (thickness: 5 to 15 ⁇ m) and cured by heating and drying (PMT 232 °C) to prepare a specimen.
- the paint composition of each experimental example was divided into 300 g portions and stirred at 1,500 rpm for 30 seconds. Then, the presence of bubbles was observed and compared relative to each other to evaluate them as excellent ( ⁇ ), good ( ⁇ ), average ( ⁇ ), or poor ( ⁇ ).
- the gloss of each specimen surface was measured at a measurement angle of 60° and evaluated as excellent ( ⁇ ), good ( ⁇ ), average ( ⁇ ), or poor ( ⁇ ) through relative comparison.
- each specimen was tested by bending (0T, 1T, 2T) and clamping it in a vice. Then, the processability was evaluated by checking for cracks in the processed area using a 15x magnifying glass.
- each specimen was bent (0T, 1T, 2T) and fixed in a vice according to ASTM D4145, and the presence of cracks in the processed area was observed using a 15x magnifying glass and evaluated as excellent ( ⁇ ), good ( ⁇ ), average ( ⁇ ), or poor ( ⁇ ) through relative comparison.
- the paint composition of Experimental Example 1-5 using the polyester resin (Synthesis Example 1-5) according to the present invention exhibited excellent physical properties across all measured items.
- it exhibited similar physical properties to the paint composition of Experimental Example 9 using a petrochemical-based polyester resin (Synthesis Example 9).
- the paint composition of Experimental Example 6-8 using a polyester resin (Synthesis Example 6-8) outside the bio-content range according to the present invention exhibited generally inferior physical properties compared to the paint composition of Experimental Example 1-5.
- the present invention provides an environmentally friendly polyester resin composition capable of minimizing carbon dioxide emissions and a paint composition comprising a polyester resin manufactured therefrom.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
본 발명은 친환경적인 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물에 관한 것이다.The present invention relates to an environmentally friendly polyester resin composition and a paint composition comprising a polyester resin produced therefrom.
PCM(Pre-Coated Metal)은 금속에 도료를 도장한 후 가공한 것으로, 가전 제품 및 건재 등의 다양한 용도로 사용되고 있다. 이에, PCM(Pre-Coated Metal)용 도료는 가공성이 우수해야 하며, 용도에 따라, 추가적으로 우수한 경도, 내스크래치성, 내후성 등이 요구된다. PCM 도료로는 아크릴계, 우레탄계, 에폭시계, 폴리에스터계, 실리콘계, 불소계, 폴리염화비닐계 등의 다양한 도료가 사용되나, 가공성이 우수한 폴리에스터계 도료 조성물이 주로 사용되고 있다. 이러한 폴리에스터계 도료 조성물의 물성을 향상시키기 위한 연구 개발이 활발히 이루어지고 있고, 일례로, 대한민국 공개특허 10-2001-0048577은 에틸렌옥사이드 또는 프로필렌옥사이드가 부가되고 하이드록시 당량이 100~400인 비스페놀 에이, 비스페놀 에프 및/또는 비스페놀 에스를 포함하는 글리콜 화합물 및 아로마틱산을 포함하는 이가산 화합물을 축합하여 얻어지는 폴리에스테르 수지 조성물을 개시하고 있다.Pre-Coated Metal (PCM) is metal coated with paint and then processed. It is used in a variety of applications, including home appliances and building materials. Therefore, paints for PCM (Pre-Coated Metal) must have excellent processability, and depending on the application, additional properties such as excellent hardness, scratch resistance, and weather resistance are required. Various PCM paints are used, including acrylic, urethane, epoxy, polyester, silicone, fluorine, and polyvinyl chloride. However, polyester paint compositions, due to their excellent processability, are the most commonly used. Research and development are actively being conducted to improve the properties of such polyester paint compositions, and as an example, Korean Patent Publication No. 10-2001-0048577 discloses a polyester resin composition obtained by condensing a glycol compound containing bisphenol A, bisphenol F and/or bisphenol S having a hydroxy equivalent of 100 to 400 and an aromatic acid-containing diacid compound, to which ethylene oxide or propylene oxide is added.
그러나, 종래의 폴리에스터계 도료 조성물은 석유, 석탄과 같은 화석 연료로부터 제조된 수지, 모노머 및 용제를 사용하여 제조된 것으로, 제조 과정에서 지구 온난화의 원인이 되는 이산화탄소를 발생할 수밖에 없다는 문제가 있다. 이에, 이산화탄소의 배출을 최소화할 수 있는 친환경적인 폴리에스터계 도료 조성물에 대한 개발이 요구된다. However, conventional polyester paint compositions are manufactured using resins, monomers, and solvents derived from fossil fuels like petroleum and coal. This inevitably leads to the production of carbon dioxide, a contributor to global warming. Therefore, the development of environmentally friendly polyester paint compositions that can minimize carbon dioxide emissions is urgently needed.
본 발명은 이산화탄소의 배출을 최소화할 수 있는 친환경적인 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물을 제공한다.The present invention provides an environmentally friendly polyester resin composition capable of minimizing carbon dioxide emissions and a paint composition comprising a polyester resin manufactured therefrom.
본 발명은 산 모노머 및 알코올 모노머를 포함하는 폴리에스터 수지 조성물로서, 상기 산 모노머 및 상기 알코올 모노머 중 1 이상이 바이오 베이스(bio base) 모노머이고, 상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 바이오 함량(bio content)이 20 중량% 이상인 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물을 제공한다.The present invention provides a polyester resin composition comprising an acid monomer and an alcohol monomer, wherein at least one of the acid monomer and the alcohol monomer is a bio-based monomer, and a polyester resin produced from the polyester resin composition has a bio content of 20 wt% or more, and a paint composition comprising a polyester resin produced therefrom.
본 발명은 이산화탄소의 배출을 최소화할 수 있는 친환경적인 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물을 제공한다. 본 발명의 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물은 친환경적인 동시에, 종래 화석 연료 베이스의 폴리에스터 수지 및 이를 포함하는 도료 조성물에 비해 동등 이상의 물성을 나타낸다. 본 발명의 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물은 바이오 함량이 높아, 높은 바이오 함량을 요구하는 다양한 산업 분야에 적용 가능하다.The present invention provides an environmentally friendly polyester resin composition capable of minimizing carbon dioxide emissions and a paint composition comprising a polyester resin manufactured therefrom. The polyester resin composition of the present invention and the paint composition comprising the polyester resin manufactured therefrom are environmentally friendly and exhibit physical properties equivalent to or higher than those of conventional fossil fuel-based polyester resins and paint compositions comprising the same. The polyester resin composition of the present invention and the paint composition comprising the polyester resin manufactured therefrom have a high bio-content and are thus applicable to various industrial fields requiring a high bio-content.
이하, 본 발명에 대하여 상세히 설명한다. 그러나, 하기 내용에 의해서만 한정되는 것은 아니며, 필요에 따라 각 구성 요소가 다양하게 변형되거나 선택적으로 혼용될 수 있다. 따라서, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.The present invention will be described in detail below. However, it is not limited to the following description, and each component may be modified or selectively mixed as needed. Therefore, it should be understood that all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention are included.
본 명세서에서 사용된 “중량평균분자량"은 해당 기술 분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 GPC(gel permeation chromatography) 방법으로 측정할 수 있다. “유리전이온도”는 해당 기술 분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 시차주사열량분석법(differential scanning calorimetry, DSC)으로 측정할 수 있다. “수산기가”와 같은 작용기가는 해당 기술 분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 적정(titration)의 방법으로 측정할 수 있다. The “weight average molecular weight” used herein is measured by a conventional method known in the art, and can be measured, for example, by a gel permeation chromatography (GPC) method. The “glass transition temperature” is measured by a conventional method known in the art, and can be measured, for example, by a differential scanning calorimetry (DSC) method. The functional group such as the “hydroxyl value” is measured by a conventional method known in the art, and can be measured, for example, by a titration method.
<폴리에스터 수지 조성물><Polyester resin composition>
본 발명의 폴리에스터 수지 조성물은 산 모노머 및 알코올 모노머를 포함한다. The polyester resin composition of the present invention comprises an acid monomer and an alcohol monomer.
상기 산 모노머로는 지방족 산, 방향족 산, 또는 이들의 혼합물을 사용할 수 있다. 예를 들어, 이소프탈산(Isophthalic acid), 테레프탈산(terephthalic acid), 아디프산(Adipic acid), 트리멜리트산 무수물(Trimellitic anhydride), 다이머산(Dimer acid), 세바식산(Sebacic acid), 숙신산(succinic acid), 무수프탈산(Phthalic anhydride), 벤젠트리카르복실산 무수물(benzene tricarboxylic acid anhydride), 나프탈렌 트리카르복실산 무수물(naphthalene tricarboxylic acid anhydride) 등을 사용할 수 있고, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 일례로, 상기 산 모노머는 이소프탈산(Isophthalic acid), 테레프탈산(terephthalic acid), 아디프산(Adipic acid), 트리멜리트산 무수물(Trimellitic anhydride) 및 다이머산(Dimer acid)으로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다. 이 경우, 폴리에스터 수지 내 에스터 결합이 많아짐에 따라 폴리에스터 수지의 중량평균분자량을 더욱 높일 수 있고, 도료에 적용 시 부착성, 가공성 및 저장성을 더욱 향상시킬 수 있다. The acid monomer may be an aliphatic acid, an aromatic acid, or a mixture thereof. For example, isophthalic acid, terephthalic acid, adipic acid, trimellitic anhydride, dimer acid, sebacic acid, succinic acid, phthalic anhydride, benzene tricarboxylic acid anhydride, naphthalene tricarboxylic acid anhydride, etc. may be used, and these may be used alone or in combination of two or more. For example, the acid monomer may include at least one selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, trimellitic anhydride, and dimer acid. In this case, as the number of ester bonds in the polyester resin increases, the weight average molecular weight of the polyester resin can be further increased, and when applied to a paint, the adhesion, processability, and storability can be further improved.
상기 알코올 모노머로는 다관능 알코올을 사용할 수 있고, 지방족 알코올, 방향족 알코올, 또는 이들의 혼합물을 사용할 수 있다. 예를 들어, 에틸렌글리콜(Ethylene glycol), 프로필렌글리콜(Propylene glycol), 1,2-부틸렌글리콜(1,2-Butylene glycol), 네오펜틸글리콜(Neopentyl glycol), 1,6-헥산디올(1,6-Hexanediol), 트리메틸올프로판(Trimethylol propane), 글리세롤(Glycerol), 비스페놀 A(BPA), 알콕시화 알코올(alkoxylated alcohol), 프로판디올, 이소솔바이드 등을 사용할 수 있고, 이들을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 일례로, 상기 알코올 모노머는 에틸렌글리콜(Ethylene glycol), 네오펜틸글리콜(Neopentyl glycol) 및 에톡시화 비스페놀 A(Ethoxylated bisphenol A)로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다. 이 경우, 폴리에스터 수지의 가격 경쟁력, 반응성 및 경도를 더욱 향상시킬 수 있다. The alcohol monomer may be a polyfunctional alcohol, and may be an aliphatic alcohol, an aromatic alcohol, or a mixture thereof. For example, ethylene glycol, propylene glycol, 1,2-butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylol propane, glycerol, bisphenol A (BPA), an alkoxylated alcohol, propanediol, isosorbide, etc. may be used, and these may be used alone or in combination of two or more. For example, the alcohol monomer may include at least one selected from the group consisting of ethylene glycol, neopentyl glycol, and ethoxylated bisphenol A. In this case, the price competitiveness, reactivity and hardness of the polyester resin can be further improved.
상기 산 모노머 및 상기 알코올 모노머 중 1 종 이상은 바이오 베이스(bio base) 모노머이다. 바이오 베이스 산 모노머 및/또는 바이오 베이스 알코올 모노머는 유채씨유, 피마자유, 옥수수유 등의 식물에서 유래된 것으로, 화석 연료로부터 제조된 산 모노머 및 알코올 모노머를 사용하여 제조된 종래의 폴리에스터 수지와 달리, 이산화탄소의 배출량을 저감시킬 수 있다. At least one of the above acid monomers and alcohol monomers is a bio-based monomer. The bio-based acid monomer and/or bio-based alcohol monomer is derived from plants such as rapeseed oil, castor oil, and corn oil, and can reduce carbon dioxide emissions, unlike conventional polyester resins manufactured using acid monomers and alcohol monomers manufactured from fossil fuels.
일례로, 상기 바이오 베이스 산 모노머는 바이오 베이스 다이머산(Dimer acid), 바이오 베이스 세바식산(Sebacic acid), 바이오 베이스 숙신산(succinic acid) 및 바이오 베이스 아젤라익산(Azelaic acid)으로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다. 일례로, 상기 바이오 베이스 알코올 모노머는 바이오 베이스 프로판디올, 바이오 베이스 이소솔바이드 및 바이오 베이스 다이머알콜로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다.For example, the bio-based acid monomer may include at least one selected from the group consisting of bio-based dimer acid, bio-based sebacic acid, bio-based succinic acid, and bio-based azelaic acid. For example, the bio-based alcohol monomer may include at least one selected from the group consisting of bio-based propanediol, bio-based isosorbide, and bio-based dimer alcohol.
상기 바이오 베이스 산 모노머는 폴리에스터 수지 조성물 총 중량을 기준으로, 20 내지 45 중량%, 예를 들어 25 내지 35 중량% 포함될 수 있다. 상기 바이오 베이스 산 모노머의 함량이 전술한 범위 미만인 경우 도료 제조 시 가공성이 저하되고, 수지 저장성이 열세해져 티가 발생될 수 있다. 전술한 범위 초과인 경우 내식성이 저하되고, 끈적임(Tacky성)이 강해 경화도가 저하되고, 도료 소포성이 열세해질 수 있다. The above bio-based acid monomer may be included in an amount of 20 to 45 wt%, for example, 25 to 35 wt%, based on the total weight of the polyester resin composition. If the content of the bio-based acid monomer is less than the above-mentioned range, processability may be reduced during paint production, and resin storability may be poor, resulting in cracking. If the content exceeds the above-mentioned range, corrosion resistance may be reduced, tackiness may be strong, curing may be reduced, and paint foaming may be poor.
상기 바이오 베이스 알코올 모노머는 폴리에스터 수지 조성물 총 중량을 기준으로, 20 내지 25 중량% 포함될 수 있다. 상기 바이오 베이스 알코올 모노머의 함량이 전술한 범위 미만인 경우 도료 제조 시 가공성이 저하되고, 수지 저장성이 열세해져 시간 경과에 따라 흐릿함(Hazy)이 발생되며, 용제 상용성이 저하될 수 있다. 전술한 범위 초과인 경우 내식성이 저하되고, 경화도, 내알칼리성 및 도료 소포성이 열세해질 수 있다. The above bio-based alcohol monomer may be included in an amount of 20 to 25 wt% based on the total weight of the polyester resin composition. If the content of the bio-based alcohol monomer is less than the above-mentioned range, processability may be reduced during paint production, resin storability may be poor, resulting in haziness over time, and solvent compatibility may be reduced. If the content exceeds the above-mentioned range, corrosion resistance may be reduced, and curing degree, alkali resistance, and paint defoaming may be poor.
상기 폴리에스터 수지 조성물은 용제를 더 포함할 수 있다. 이 경우, 용해력을 향상시키고, 조성물의 점도를 낮춰 작업성을 향상시킬 수 있다. 상기 용제로는 해당 기술 분야에서 사용되는 통상의 용제를 특별한 제한 없이 사용할 수 있고, 예를 들어 솔벤트 나프타, 사이클로헥사논, 자일렌 등을 사용할 수 있다. The above polyester resin composition may further include a solvent. This can enhance the solubility and lower the viscosity of the composition, thereby improving workability. Any solvent commonly used in the relevant technical field can be used without particular limitation, including solvent naphtha, cyclohexanone, xylene, and the like.
상기 폴리에스터 수지 조성물은 폴리에스터 수지 조성물 총 중량을 기준으로, 상기 산 모노머 20 내지 45 중량%, 상기 알코올 모노머 5 내지 25 중량% 및 상기 용제 45 내지 55 중량%를 포함할 수 있다. The polyester resin composition may include 20 to 45 wt% of the acid monomer, 5 to 25 wt% of the alcohol monomer, and 45 to 55 wt% of the solvent, based on the total weight of the polyester resin composition.
상기 폴리에스터 수지 조성물 내 바이오 베이스 모노머의 총 함량, 즉, 상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 바이오 함량(bio content)은 20 중량% 이상, 예를 들어 30 내지 50 중량%, 다른 예로 35 내지 45 중량%일 수 있다. 바이오 함량이 전술한 범위 미만인 경우 이산화탄소의 배출이 많아져 환경 친화적이지 못할 수 있고, 전술한 범위 초과인 경우 도막의 강도 및 경도가 낮아져 도막 물성이 저하될 수 있다. 본 발명의 도료 조성물은 바이오 함량이 높은 폴리에스터 수지를 사용함으로써, 친환경적이고, 높은 바이오 함량을 요구하는 다양한 산업 분야에 적용 가능하다.The total content of the bio-based monomer in the polyester resin composition, i.e., the bio content of the polyester resin manufactured from the polyester resin composition, may be 20 wt% or more, for example, 30 to 50 wt%, or as another example, 35 to 45 wt%. If the bio content is less than the above-mentioned range, carbon dioxide emissions may increase, which may be unfriendly to the environment, and if it exceeds the above-mentioned range, the strength and hardness of the coating film may decrease, which may deteriorate the physical properties of the coating film. The coating composition of the present invention is environmentally friendly and can be applied to various industrial fields requiring a high bio content by using a polyester resin with a high bio content.
상기 바이오 함량(bio content)는 전체 탄소의 함량 중 방사성 탄소(C14)의 함량으로 계산될 수 있다. 바이오 매스 물질에는 탄소의 동위원소인 방사성 탄소(C14)가 포함되어 있는 반면, 석유 화학 유래 물질에는 C14가 포함되어 있지 않으므로, 전체 탄소 함량 중 C14의 함량을 계산하여 바이오 함량을 계산할 수 있다.The bio-content can be calculated as the proportion of radioactive carbon (C14) in the total carbon content. Biomass materials contain radioactive carbon (C14), a carbon isotope, whereas petrochemical-derived materials do not. Therefore, the bio-content can be calculated by calculating the proportion of C14 in the total carbon content.
상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 중량평균분자량은 3,000 내지 10,000 g/mol, 예를 들어 5,500 내지 7,500 g/mol일 수 있다. 상기 폴리에스터 수지의 중량평균분자량이 전술한 범위 미만인 경우 분자량이 작아 가공성, 경도, 내식성, 부착성 등의 도막의 기본 물성이 저하될 수 있고, 전술한 범위 초과인 경우 점도 조절을 위해 추가되는 용제의 함량이 늘어 소정 두께의 도막을 형성하기 어려워질 수 있고, 타 수지 또는 첨가제와의 상용성이 저하될 수 있다.The weight average molecular weight of the polyester resin manufactured from the polyester resin composition may be 3,000 to 10,000 g/mol, for example, 5,500 to 7,500 g/mol. If the weight average molecular weight of the polyester resin is less than the above-mentioned range, the molecular weight may be small, which may deteriorate the basic physical properties of the coating film, such as processability, hardness, corrosion resistance, and adhesion, and if it exceeds the above-mentioned range, the content of the solvent added for viscosity control may increase, making it difficult to form a coating film of a predetermined thickness, and compatibility with other resins or additives may deteriorate.
상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 유리전이온도는 1 내지 20 ℃, 예를 들어 5 내지 10 ℃일 수 있다. 상기 폴리에스터 수지의 유리전이온도가 전술한 범위 미만인 경우 수지의 유연성이 커지나, 도막의 유리전이온도가 낮아져 내약품성, 내식성 및 경도가 저하될 수 있고, 전술한 범위 초과인 경우 수지의 유연성이 작아지고 도막의 유리전이온도가 높아져 가공성이 저하될 수 있다. The glass transition temperature of the polyester resin manufactured from the polyester resin composition may be 1 to 20°C, for example, 5 to 10°C. If the glass transition temperature of the polyester resin is less than the above-mentioned range, the flexibility of the resin increases, but the glass transition temperature of the coating film may decrease, resulting in deterioration of chemical resistance, corrosion resistance, and hardness. If the glass transition temperature exceeds the above-mentioned range, the flexibility of the resin may decrease, the glass transition temperature of the coating film may increase, resulting in deterioration of processability.
상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 수산기가는 15 내지 55 KOHmg/g, 예를 들어 25 내지 35 KOHmg/g일 수 있다. 상기 폴리에스터 수지의 수산기가가 전술한 범위 미만인 경우 수지 내의 OH기가 부족함에 따라 결합력이 저하되어 내수성 및 경화성이 저하될 수 있고, 전술한 범위 초과인 경우 도료 내에 OH기가 잔존하여 도료 내 과결합이 발생함에 따라 가공성 및 성형성이 저하될 수 있다.The hydroxyl value of the polyester resin manufactured from the polyester resin composition may be 15 to 55 KOHmg/g, for example, 25 to 35 KOHmg/g. If the hydroxyl value of the polyester resin is less than the above-mentioned range, the bonding strength may be reduced due to a lack of OH groups in the resin, which may result in reduced water resistance and curing properties. If the hydroxyl value exceeds the above-mentioned range, OH groups may remain in the paint, which may result in excessive bonding within the paint, which may result in reduced processability and moldability.
상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 산가는 5 KOHmg/g 이하, 예를 들어 1 내지 5 KOHmg/g일 수 있다. 상기 폴리에스터 수지의 산가가 전술한 범위 미만인 경우 반응 시간이 길어져 수지의 컬러와 외관이 저하될 수 있고, 전술한 범위 초과인 경우 적정 분자량에 미치지 못하여 가공성, 내식성, 경도 등의 도료의 기본 물성이 저하될 수 있다.The acid value of the polyester resin prepared from the polyester resin composition may be 5 KOHmg/g or less, for example, 1 to 5 KOHmg/g. If the acid value of the polyester resin is less than the above-mentioned range, the reaction time may be prolonged, which may result in a deterioration in the color and appearance of the resin. If the acid value exceeds the above-mentioned range, the basic physical properties of the paint, such as processability, corrosion resistance, and hardness, may be deteriorated due to failure to reach an appropriate molecular weight.
상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 점도(25 ℃)는 2,000 내지 7,000 mPas, 예를 들어 2,500 내지 5,500 mPas일 수 있다. 상기 폴리에스터 수지의 점도가 전술한 범위 미만인 경우 수지의 분자량이 작아져 가공성, 내식성, 경도 등이 저하될 수 있고, 전술한 범위 초과인 경우 수지 저장성과 상용성이 저하될 수 있다.The viscosity (25°C) of the polyester resin prepared from the polyester resin composition may be 2,000 to 7,000 mPas, for example, 2,500 to 5,500 mPas. If the viscosity of the polyester resin is less than the above-mentioned range, the molecular weight of the resin may decrease, resulting in deterioration in processability, corrosion resistance, hardness, etc., and if it exceeds the above-mentioned range, the storability and compatibility of the resin may decrease.
상기 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지의 고형분 함량은 40 내지 70%, 예를 들어 49 내지 51%일 수 있다. 상기 폴리에스터 수지의 고형분이 전술한 범위 미만인 경우 수지 점도가 너무 낮아 도료의 목표 점도를 맞추지 못할 수 있고, 전술한 범위 초과인 경우 수지 점도가 너무 높아 작업성이 열세해질 수 있다.The solids content of the polyester resin manufactured from the polyester resin composition may be 40 to 70%, for example, 49 to 51%. If the solids content of the polyester resin is less than the aforementioned range, the resin viscosity may be too low to meet the target viscosity of the paint, and if it exceeds the aforementioned range, the resin viscosity may be too high, resulting in poor workability.
<도료 조성물><Paint composition>
본 발명에 따른 도료 조성물은 전술한 폴리에스터 수지 조성물로부터 제조된 폴리에스터 수지를 포함한다. 본 발명의 도료 조성물은 바이오 함량이 높아 친환경적이고, 높은 바이오 함량을 요구하는 다양한 산업 분야에 적용 가능하다.The paint composition according to the present invention comprises a polyester resin prepared from the aforementioned polyester resin composition. The paint composition of the present invention is environmentally friendly due to its high bio-content, and is applicable to various industrial fields requiring a high bio-content.
또한, 본 발명에 따른 도료 조성물은 필요에 따라 안료, 용제, 경화 촉진제 및 해당 기술 분야에서 통상적으로 사용되는 첨가제를 더 포함할 수 있다. 본 발명에서 사용 가능한 첨가제의 비제한적인 예로는 레벨링제, 가소제, 침강 방지제, 왁스, 광안정제, 광택 조절제 등이 있다.Additionally, the paint composition according to the present invention may further include pigments, solvents, curing accelerators, and additives commonly used in the relevant technical fields, as needed. Non-limiting examples of additives usable in the present invention include leveling agents, plasticizers, anti-settling agents, waxes, light stabilizers, gloss regulators, and the like.
이하 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나, 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐, 어떠한 의미로든 본 발명의 범위가 실시예로 한정되는 것은 아니다.The present invention will be described in more detail through the following examples. However, the following examples are intended only to aid understanding of the present invention and are not intended to limit the scope of the present invention in any way.
[합성예 1][Synthesis Example 1]
교반기, 콘덴서, 질소 투입 장치, 온도 콘트롤러 및 온도계를 장착한 유리 플라스크에 에틸렌글리콜 70 g, 네오펜틸글리콜 50.6 g, 에톡시레이티드 비스페놀 에이 33.1 g, 트리메틸올프로판 4.5 g, 테레프탈산 102.1 g, 이소프탈산 100 g, 트리멜리트산 무수물 3 g, 촉매(butylchlorodihydroxytin) 0.1 g을 넣고, 250 ℃에서 200 rpm으로 2 시간 동안 에스테르화 반응을 실시하였다. 산가가 10 mgKOH/g 이하로 측정되었을 시, 150 ℃이하로 냉각하고, 바이오 베이스 산 모노머(Dimer acid, Cargill社 Pripol 1009) 210 g을 넣고, 250 ℃에서 200 rpm으로 2 시간 동안 에스테르화 반응을 실시하였다. 산가가 20 mgKOH/g 이하로 측정되었을 시, 150 ℃ 이하로 냉각하고, 자일렌 20 g을 넣고, 230 ℃에서 200 rpm으로 환류 반응 후, 산가가 5 mgKOH/g 이하가 되었을 때 용제로 희석하여 합성예 1의 폴리에스터 수지를 제조하였다. 제조된 폴리에스터 수지의 물성은 표 1에 나타내었다.In a glass flask equipped with a stirrer, condenser, nitrogen injection device, temperature controller, and thermometer, 70 g of ethylene glycol, 50.6 g of neopentyl glycol, 33.1 g of ethoxylated bisphenol A, 4.5 g of trimethylolpropane, 102.1 g of terephthalic acid, 100 g of isophthalic acid, 3 g of trimellitic anhydride, and 0.1 g of catalyst (butylchlorodihydroxytin) were added, and esterification was performed at 250 °C and 200 rpm for 2 hours. When the acid value was measured to be 10 mgKOH/g or less, the mixture was cooled to 150 °C or lower, 210 g of bio-based acid monomer (Dimer acid, Cargill's Pripol 1009) was added, and esterification was performed at 250 °C and 200 rpm for 2 hours. When the acid value was measured to be 20 mgKOH/g or less, the mixture was cooled to 150°C or less, 20 g of xylene was added, and after refluxing at 230°C and 200 rpm, when the acid value became 5 mgKOH/g or less, the mixture was diluted with a solvent to produce a polyester resin of Synthesis Example 1. The physical properties of the produced polyester resin are shown in Table 1.
[합성예 2-9][Synthesis Example 2-9]
하기 표 1의 조성에 따른 것을 제외하고는 합성예 1과 동일한 방법으로 합성예 2 내지 9의 폴리에스터 수지를 제조하였다. Polyester resins of Synthetic Examples 2 to 9 were manufactured in the same manner as Synthetic Example 1, except that the compositions were as shown in Table 1 below.
[실험예 1-9: 도료 조성물 제조][Experimental Example 1-9: Preparation of Paint Composition]
하기 표 2에 따라, 각 실험예의 도료 조성물을 제조하였다. According to Table 2 below, the paint composition for each experimental example was prepared.
폴리에스터 1: 합성예 1의 폴리에스터 수지Polyester 1: Polyester resin of Synthesis Example 1
폴리에스터 2: 합성예 2의 폴리에스터 수지Polyester 2: Polyester resin of Synthesis Example 2
폴리에스터 3: 합성예 3의 폴리에스터 수지Polyester 3: Polyester resin of Synthetic Example 3
폴리에스터 4: 합성예 4의 폴리에스터 수지Polyester 4: Polyester resin of Synthetic Example 4
폴리에스터 5: 합성예 5의 폴리에스터 수지Polyester 5: Polyester resin of Synthetic Example 5
폴리에스터 6: 합성예 6의 폴리에스터 수지Polyester 6: Polyester resin of Synthetic Example 6
폴리에스터 7: 합성예 7의 폴리에스터 수지Polyester 7: Polyester resin of Synthetic Example 7
폴리에스터 8: 합성예 8의 폴리에스터 수지Polyester 8: Polyester resin of synthetic example 8
폴리에스터 9: 합성예 9의 폴리에스터 수지Polyester 9: Polyester resin of Synthetic Example 9
보조 수지: 폴리에스터 수지(Mw 3,300 g/mol, Ohv 61 KOHmg/g, Tg 13 ℃, NV 60 %, 점도(25 ℃) 600-1,000 cps)Auxiliary resin: polyester resin (Mw 3,300 g/mol, Ohv 61 KOHmg/g, Tg 13 ℃, NV 60%, viscosity (25 ℃) 600-1,000 cps)
멜라민: Methylated melamine resin(ACM00167)Melamine: Methylated melamine resin (ACM00167)
용제 1: Dibasic ester(ADD00198)Solvent 1: Dibasic ester (ADD00198)
용제 2: Propylene glycol methyl ether acetate(AAF00305)Solvent 2: Propylene glycol methyl ether acetate (AAF00305)
용제 3: Solvent naphtha(petroleum), light arom(AAB11161)Solvent 3: Solvent naphtha (petroleum), light arom (AAB11161)
첨가제 1: 실리콘계 소포제(AEN01377)Additive 1: Silicone-based defoaming agent (AEN01377)
첨가제 2: 소광제(Silicon dioxide)Additive 2: Matting agent (Silicon dioxide)
촉매: Sulfonic acidCatalyst: Sulfonic acid
[물성 평가][Physical property evaluation]
각 실험예에 따라 제조된 도료 조성물의 물성을 하기 방법으로 측정한 후, 그 결과를 하기 표 3에 나타내었다.The properties of the paint composition manufactured according to each experimental example were measured using the following method, and the results are shown in Table 3 below.
시편 제조Sample manufacturing
PCM용 GI 강판 위에 각 실험예의 도료 조성물을 코팅하고(두께: 5~15 ㎛), 가열 건조(PMT 232 ℃)하여 경화시켜 시편을 제조하였다.The paint composition of each experimental example was coated on a GI steel plate for PCM (thickness: 5 to 15 ㎛) and cured by heating and drying (PMT 232 ℃) to prepare a specimen.
WET 외관WET exterior
각 시편에 부풀음, 박리, 표면 갈라짐, 핀홀, 기포, 이물 등의 결함이 없는지를 육안으로 관찰하여, 하기 기준에 따라 외관을 평가하였다.Each specimen was visually observed for defects such as swelling, peeling, surface cracks, pinholes, bubbles, and foreign matter, and the appearance was evaluated according to the following criteria.
[평가 기준][metewand]
우수(◎): 결함(표면 갈라짐, 기포 등) 미발생Excellent (◎): No defects (surface cracks, bubbles, etc.)
불량(Х): 결함(표면 갈라짐, 기포 등) 발생Defective (X): Occurrence of defects (surface cracks, bubbles, etc.)
소포성Vesicular
각 실험예의 도료 조성물을 300 g 소분하여 1,500 rpm으로 30초 교반한 후, 기포 발생 여부를 관찰하고 상대 비교하여 우수(◎), 양호(○), 보통(△), 불량(Х)으로 평가하였다.The paint composition of each experimental example was divided into 300 g portions and stirred at 1,500 rpm for 30 seconds. Then, the presence of bubbles was observed and compared relative to each other to evaluate them as excellent (◎), good (○), average (△), or poor (Х).
광택gloss
글로스 미터(gloss meter)를 이용하여, 측정 각도 60 ° 에서 각 시편 표면의 광택을 측정하고 상대 비교하여 우수(◎), 양호(○), 보통(△), 불량(Х)으로 평가하였다. Using a gloss meter, the gloss of each specimen surface was measured at a measurement angle of 60° and evaluated as excellent (◎), good (○), average (△), or poor (Х) through relative comparison.
가공성Processability
ASTM D4145에 따라, 각 시편을 굽혀(0T,1T,2T) 바이스(VICE)에 물려 시험한 후, 가공 부위의 크랙(CRACK) 발생 여부를 15배 확대경을 이용하여 확인하여 가공성을 평가하였다.According to ASTM D4145, each specimen was tested by bending (0T, 1T, 2T) and clamping it in a vice. Then, the processability was evaluated by checking for cracks in the processed area using a 15x magnifying glass.
[평가 기준][metewand]
매우 우수: 0T NO CRACKVery good: 0T NO CRACK
우수: 0T 점 CRACKExcellent: 0T points CRACK
보통: 0T CRACKNormal: 0T CRACK
미세 열세: 1T 점 CRACKMicro-disadvantage: 1T point CRACK
불량: 1T CRACKDefect: 1T CRACK
경화도(MEK Rubbing)Hardening (MEK Rubbing)
거즈(GUAZE)에 용제(MEK)를 적신 후, 각 시편의 표면을 1 kg 하중으로 문지른 후, 표면 상태를 상대 비교하여 우수(◎), 양호(○), 보통(△), 불량(Х)으로 평가하였다.After wetting the gauze with the solvent (MEK), the surface of each specimen was rubbed with a 1 kg load, and the surface condition was compared relative to each other and evaluated as excellent (◎), good (○), average (△), or poor (Х).
내한 백화Korean department store
각 시편을 0 ℃에서 1 시간 보관한 후, ASTM D4145에 따라, 각 시편을 굽혀(0T,1T,2T) 바이스(VICE)에 고정한 후, 가공 부위의 크랙(CRACK) 발생 여부를 15배 확대경을 이용하여 관찰하고 상대 비교하여 우수(◎), 양호(○), 보통(△), 불량(Х)으로 평가하였다. After storing each specimen at 0℃ for 1 hour, each specimen was bent (0T, 1T, 2T) and fixed in a vice according to ASTM D4145, and the presence of cracks in the processed area was observed using a 15x magnifying glass and evaluated as excellent (◎), good (○), average (△), or poor (Х) through relative comparison.
내약품성Chemical resistance
각 시편을 5% NaOH 및 5% CH3COOH에 24 시간 침지 후, 도막의 외관을 육안으로 관찰하였으며, ASTM D714-87 기준에 따라 평가하였다.After immersing each specimen in 5% NaOH and 5% CH 3 COOH for 24 hours, the appearance of the coating was visually observed and evaluated according to the ASTM D714-87 standard.
상기 표 2의 결과로부터 확인되는 바와 같이, 본 발명에 따른 폴리에스터 수지(합성예 1-5)를 사용한 실험예 1-5의 도료 조성물의 경우, 측정 항목 전반적으로 우수한 물성을 나타내었다. 특히, 친환경적인 바이오 베이스의 폴리에스터 수지를 사용하였음에도 불구하고, 석유 화학 베이스의 폴리에스터 수지(합성예 9)를 사용한 실험예 9의 도료 조성물과 유사한 수준의 물성을 나타내었다. 반면, 본 발명에 따른 바이오 함량 범위를 벗어나는 폴리에스터 수지(합성예 6-8)를 사용한 실험예 6-8의 도료 조성물의 경우, 실험예 1-5의 도료 조성물에 비해 전반적으로 물성이 열세하게 나타났다.As can be seen from the results in Table 2 above, the paint composition of Experimental Example 1-5 using the polyester resin (Synthesis Example 1-5) according to the present invention exhibited excellent physical properties across all measured items. In particular, despite the use of an eco-friendly bio-based polyester resin, it exhibited similar physical properties to the paint composition of Experimental Example 9 using a petrochemical-based polyester resin (Synthesis Example 9). On the other hand, the paint composition of Experimental Example 6-8 using a polyester resin (Synthesis Example 6-8) outside the bio-content range according to the present invention exhibited generally inferior physical properties compared to the paint composition of Experimental Example 1-5.
본 발명은 이산화탄소의 배출을 최소화할 수 있는 친환경적인 폴리에스터 수지 조성물 및 이로부터 제조된 폴리에스터 수지를 포함하는 도료 조성물을 제공한다.The present invention provides an environmentally friendly polyester resin composition capable of minimizing carbon dioxide emissions and a paint composition comprising a polyester resin manufactured therefrom.
Claims (9)
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| KR10-2024-0047969 | 2024-04-09 | ||
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101736189B1 (en) * | 2016-05-30 | 2017-05-30 | 주식회사 삼양사 | Polyester resin comprisng biomass-derived oligomer and method for preparing the same, and powder coating composition comprising the resin |
| CN111592803A (en) * | 2020-06-08 | 2020-08-28 | 亚士漆(上海)有限公司 | Bio-based water-based paint and preparation method and application thereof |
| KR102382596B1 (en) * | 2021-10-14 | 2022-04-04 | 주영산업 주식회사 | Eco-friendly polyurea paint composition using biomass-derived material and manufacturing method thereof |
| KR20220080439A (en) * | 2020-12-07 | 2022-06-14 | 주식회사 삼양사 | Polyol composition obtained by addition reaction of lactone-based compound to anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition, polyseter resin prepared by using the polyol composition and method for preparing the same, and powder coating composition comprising the resin |
| US20230348663A1 (en) * | 2021-03-22 | 2023-11-02 | Mitsubishi Chemical Corporation | Polyester resin and method of producing same, and paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101736189B1 (en) * | 2016-05-30 | 2017-05-30 | 주식회사 삼양사 | Polyester resin comprisng biomass-derived oligomer and method for preparing the same, and powder coating composition comprising the resin |
| CN111592803A (en) * | 2020-06-08 | 2020-08-28 | 亚士漆(上海)有限公司 | Bio-based water-based paint and preparation method and application thereof |
| KR20220080439A (en) * | 2020-12-07 | 2022-06-14 | 주식회사 삼양사 | Polyol composition obtained by addition reaction of lactone-based compound to anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition, polyseter resin prepared by using the polyol composition and method for preparing the same, and powder coating composition comprising the resin |
| US20230348663A1 (en) * | 2021-03-22 | 2023-11-02 | Mitsubishi Chemical Corporation | Polyester resin and method of producing same, and paint |
| KR102382596B1 (en) * | 2021-10-14 | 2022-04-04 | 주영산업 주식회사 | Eco-friendly polyurea paint composition using biomass-derived material and manufacturing method thereof |
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