WO2021137537A1 - Epoxy resin, epoxy paint composition containing same, coating film formed by epoxy paint composition, and substrate with coating film adhered thereto - Google Patents
Epoxy resin, epoxy paint composition containing same, coating film formed by epoxy paint composition, and substrate with coating film adhered thereto Download PDFInfo
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- WO2021137537A1 WO2021137537A1 PCT/KR2020/019125 KR2020019125W WO2021137537A1 WO 2021137537 A1 WO2021137537 A1 WO 2021137537A1 KR 2020019125 W KR2020019125 W KR 2020019125W WO 2021137537 A1 WO2021137537 A1 WO 2021137537A1
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- 0 CC(C)(CC(*)COC(CCC=C1)=C1OC(C)(C)C1OC1)OC(CCCC1)C1OCC1CC1 Chemical compound CC(C)(CC(*)COC(CCC=C1)=C1OC(C)(C)C1OC1)OC(CCCC1)C1OCC1CC1 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Definitions
- the present invention relates to an epoxy resin, an epoxy coating composition comprising the same, a coating film formed by the epoxy coating composition, and a substrate to which the coating film is attached.
- Epoxy resins generally have high corrosion resistance and high chemical resistance, so they are the most widely used resins for ship paints, heavy-duty anticorrosive paints, and overall industries.
- liquid BPA epoxy resin is produced through polycondensation reaction of epichlorohydrin with bisphenol A, and it is widely used.
- ECH Ephloro Hydrine
- the coating film produced after the curing reaction with the epoxy curing agent is brittle because it is manufactured as a paint, causing cracks in the coating film due to external impact. cause major flaws in
- the liquid product is transferred to a semi-solid and solid phase due to the increase in viscosity due to the increase in molecular weight, so a larger amount of an organic solvent, which is a volatile organic compound, must be used.
- polyamide or polyamide used as a curing agent for epoxy resin according to the increase in molecular weight Compatibility with phenalkamine and the like is problematic, and in this case, problems such as poor curing and poor adhesion of the coating film are caused.
- VOCs volatile organic compounds
- Patent Document 1 Korean Patent No. 10-1264516
- the technical problem to be solved by the present invention is to provide a low-viscosity epoxy resin capable of producing a solvent-free paint and an epoxy paint composition including the same.
- n is an integer of 0 to 4.
- n is an integer of 0 to 4.
- Another aspect of the present invention relates to an epoxy paint composition
- n is an integer of 0 to 4.
- n is an integer of 0 to 4.
- Another aspect of the present invention relates to a coating film formed of the epoxy coating composition.
- Another aspect of the present invention relates to a substrate with a coating film including the coating film and the substrate.
- the epoxy resin according to the present invention can be used as a paint without mixing of a solvent and/or a diluent based on a low viscosity, and the drying speed is significantly improved compared to the existing coating film in film forming using the epoxy paint composition containing the epoxy resin, , it is possible to manufacture a coating film having an equivalent or higher level of overall physical properties.
- epoxy resin paints have excellent physical properties such as adhesion, heat resistance, water resistance, chemical resistance, and mechanical strength, and are widely used as paints for ships, heavy-duty anticorrosives, and constructions.
- Bisphenol A type epoxy resin which is a typical epoxy resin, must be designed using a solvent and/or diluent because of its high viscosity.
- the present invention provides an epoxy paint composition comprising an epoxy resin in a low-viscosity form.
- n is an integer of 0 to 4.
- n is an integer of 0 to 4.
- the catechol-type epoxy resin has a low-viscosity property, unlike the conventional high-viscosity bisphenol A-type epoxy resin, so that the amount of solvent and/or diluent is significantly reduced or not used, so a low-solvent-type or solvent-free coating composition with little VOC emission. can be manufactured.
- a catechol-type epoxy resin in which other functional groups, including an alkyl group, are not substituted in the benzene ring of the above formula a coating film having physical properties equivalent to or higher than that of the conventional level can be implemented as a whole, and in particular, the drying rate can be improved. have.
- a coating film formed using an epoxy paint composition containing an epoxy resin that satisfies the mol % condition of the repeating unit satisfies the mol % condition in the measurement of mechanical strength such as impact resistance. It was confirmed that it has excellent mechanical strength compared to the epoxy resin not used.
- the epoxy paint composition including the epoxy resin satisfying the above conditions has the advantage of controlling the drying rate of the coating film as well as the improved drying rate described above.
- the viscosity of the epoxy resin may be 2000 cps or less at 25 °C, for example, 200 to 2000 cps or 200 to 1800 cps.
- the viscosity of the epoxy resin may be 200 to 1600 cps, 200 to 1000 cps, or 200 to 800 cps at 25°C.
- the viscosity of the epoxy resin exceeds 2000 cps, it may be difficult to form a uniform coating film due to a decrease in applicability in a solvent-free coating material.
- the epoxy equivalent of the epoxy resin may be 120 to 185 g / eq.
- the equivalent weight of the epoxy resin may be 140 to 183 g / eq.
- Another aspect of the present invention provides an epoxy paint composition
- n is an integer of 0 to 4.
- a phosphorus epoxy paint composition is provided.
- n is an integer of 0 to 4.
- n is an integer of 0 to 4.
- the viscosity of the epoxy resin may be 2000 cps or less at 25 ° C.
- the epoxy equivalent of the epoxy resin may be 120 to 185 g / eq.
- the epoxy equivalent of the epoxy resin may be 140 to 183 g / eq.
- the description of the epoxy paint composition is the same as described above in the epoxy resin part, so it will be omitted.
- the epoxy paint composition may include a main part and a curing agent part including the epoxy resin.
- the main part may include 5 to 50 parts by weight of the epoxy resin and 50 to 95 parts by weight of the pigment based on 100 parts by weight of the main part.
- the main part may include 15 to 30 parts by weight of the epoxy resin and 70 to 85 parts by weight of the pigment based on 100 parts by weight of the main part, for example, 20 to 30 parts by weight of the epoxy resin and the pigment. 70 to 80 parts by weight may be included.
- the pigment may be an extender pigment or a color pigment, and the aforementioned pigments may be used alone or in combination of two or more.
- the extender pigment fills the pores in the coating film, complements hardness and chemical properties, and controls gloss.
- extender pigments known in the art may be used without limitation, and examples thereof include silica, barite (natural barium sulfate), blancfix (synthetic barium sulfate), talc, calcium carbonate, calcium carbonate, and the like.
- the above-mentioned components may be used alone or in combination of two or more.
- the color pigment is included for the purpose of expressing a desired color (colored) in the paint by mixing with the epoxy resin.
- color pigment organic pigments, inorganic pigments, metallic pigments, aluminum-pastes, pearls, etc. commonly used in the art may be used without limitation, and these may be used alone or in combination of two or more.
- one or a mixture of two or more selected from the group consisting of titanium dioxide, bismuth vanadate, cyanine green, carbon black, iron oxide, iron oxide sulfur, navy blue, and cyanine blue may be used.
- the curing agent may include a curing agent and a curing accelerator.
- a curing agent used in a subject including an epoxy resin it may include a conventional curing agent known in the art without being particularly limited.
- it may include an amine-based curing agent or a polyamide-based curing agent.
- the curing agent part may include an amine-based curing agent.
- amine-based curing agent a conventional resin for an amine-based curing agent known in the art may be used without limitation.
- a conventional resin for an amine-based curing agent known in the art may be used without limitation.
- the content of the amine-based curing agent is not particularly limited, and may be, for example, 30 to 60% by weight based on the total weight of the curing agent part.
- the content of the aliphatic amine resin may be 20 to 40% by weight based on the total weight of the curing agent part, and the content of the aromatic amine resin may be 10 to 20% by weight based on the total weight of the curing agent part.
- the content of the amine-based curing agent is less than the above range, the appearance of the coating film after curing may be poor, and a problem of lowering the hardness may occur. If the content of the amine-based curing agent is less than the above range, workability is deteriorated and drying time is delayed. can occur
- the curing accelerator is a material that promotes the reaction between the epoxy resin and the amine-based curing agent, and any conventional material known in the art may be used without limitation.
- Non-limiting examples of the curing accelerator that can be used may be at least one selected from the group consisting of tridimethylamino methylphenol, triphenyl phosphite, and amino ethylpiperazine.
- the content of the curing accelerator is not particularly limited, and may be, for example, 10 to 30% by weight based on the total weight of the curing agent part. If the content of the curing accelerator is out of the range, physical properties such as chemical resistance and water resistance of the coating film may deteriorate, and the appearance of the coating film may deteriorate.
- the epoxy paint composition may include conventional additives known in the art within a range that does not impair the inherent properties of the composition as additives.
- Non-limiting examples of additives that can be used include a dispersant, an antifoaming agent, a defoaming agent, a leveling agent, a weathering additive, a desiccant, an appearance control agent, an anti-settling agent, a coupling agent, or a mixture of two or more thereof.
- two or more additives selected from the group consisting of an anti-settling agent, a dispersing agent, an antifoaming agent, a defoaming agent, and a leveling agent may be mixed.
- the content of the additive may be appropriately adjusted within a content range known in the art, and for example, may be 1 to 8% by weight based on the total weight of the main part.
- the anti-settling agent serves to prevent sedimentation of materials to form a coating film with a uniform property, and conventional ones known in the art may be used without limitation.
- a clay-type anti-settling agent and the like there is a clay-type anti-settling agent and the like.
- the content of the anti-settling agent is not particularly limited, and may be, for example, 0.1 to 0.7 wt%. When the content of the anti-settling agent is less than 0.1 wt %, the leveling of the coating film is very good, but the storability of the paint is poor, and when it exceeds 0.7 wt %, the storage stability of the paint is excellent, but the leveling of the coating film may be poor.
- An antifoaming agent and a defoaming agent can be mixed together to remove air bubbles from the surface of the coating film and allow the bubbles in the coating film to rise to the surface quickly. If the bubbles inside do not rise and remain in the coating film, poor adhesion to the material and/or deterioration of physical properties may result. Even if the bubbles inside rise, the flowability of the coating film decreases when the coating film is cured to some extent. As a result, bubble marks may remain on the surface of the coating film. In addition, when various color pigments are used, color separation occurs due to different fluidity for each pigment, so that the color before and after curing is different, or the appearance is poor because the color is different for each painted part.
- the main part includes one or more additives such as the above-described dispersing agent, defoaming agent, defoaming agent, and leveling agent, it is possible to improve the occurrence of coating film defects such as defoaming defects, cratering, and color separation.
- additives such as the above-described dispersing agent, defoaming agent, defoaming agent, and leveling agent
- the dispersant serves to disperse each material constituting the composition and prevent re-agglomeration by maintaining a distance to express uniform physical properties of the coating film.
- a conventional dispersant known in the art may be used, for example, a high molecular weight block copolymer type dispersant.
- the antifoaming agent is a mixture of a lipophilic agent and polysiloxane, and serves to enhance the appearance of the coating film by suppressing air bubbles generated during coating.
- Conventional antifoaming agents known in the art may be used without limitation.
- an antifoaming agent of the polysiloxane type can be used.
- the defoaming agent serves to prevent and remove bubbles during coating and improve the manufacturing process.
- a non-silicone-based polymer-type defoaming agent may be used.
- the leveling agent is to improve the appearance characteristics of the coating film while enhancing adhesion in the composition by leveling the composition so that the composition is coated evenly and smoothly.
- a conventional leveling agent known in the art may be used without limitation, and for example, an acrylic-based, silicone-based, polyester-based, or amine-based leveling agent may be used.
- Another aspect of the present invention relates to a coating film formed of the epoxy coating composition, and a substrate with a coating film comprising the coating film and the substrate formed of the epoxy coating composition.
- the coating film is formed using the above-described epoxy coating composition, and the substrate with the coating film is a laminate including the coating film and an object (substrate) to be coated.
- the thickness of the coating film may vary depending on the use of the coating film, but is not particularly limited, and may be, for example, 50 to 500 ⁇ m, or 100 to 300 ⁇ m.
- degassing was performed at a temperature of 150 ° C. less than 10 torr, and the epoxy equivalent of the final resin was 142 g/eq, 226 ppm chlorine, 85% yield, and 220 cps viscosity.
- the reaction was carried out in the same manner as in Example 1, except that 2.5 g (0.5 wt%) of benzyl trimethyl ammonium chloride (BTMAC) was added instead of 48 g (0.599 mol) of 50% caustic soda.
- the final resin had an epoxy equivalent of 193 g/eq, a chlorine content of 177 ppm, and a viscosity of 2403 cps.
- cresol red indicator 3 drops were added, and titration was performed with a 0.1 NaOH (methanol) solution at the point where the color changed from pink to yellow and became purple as the endpoint. At the same time, a blank test was performed.
- a sample was collected in a 200 ml Erlenmeyer flask and calibrated to 0.1 mg. After dissolving by adding 25 ml of 1,4-dioxane, 25 ml of a 0.1 N KOH (methanol) solution was added, and a glass cooling tube was attached, followed by reaction in a water bath at 70° C. for 30 minutes. After cooling to room temperature, the glass cooling tube was washed with 5-10 ml of methanol and added to the flask.
- the solution in the Erlenmeyer flask was transferred to a 200 ml beaker, the Erlenmeyer flask was washed 2-3 times with 80% acetone again, and the washing solution was added to the beaker, and the total amount was 100 ml. 3 ml of acetic acid was added and titrated with 0.01 N AgNO 3 aqueous solution. Measurements were performed at two points simultaneously, and if the difference between the measurements was within 0.003%, the average value was recorded to the third decimal place. At the same time, a blank test was conducted.
- Chlorine content (%) ⁇ [(V-B) x 0.01 x 35.5 x F] / (1,000 x W) ⁇ x 100
- Liquid paints were prepared using the resins of Examples and Comparative Examples, and a coating film was formed.
- the paint performance evaluation method is described below.
- the force required for the dolly to fall was measured using a portable adhesion test device.
- the 30° mirror glossiness of the paint film was measured with a reflectometer.
- Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 drying speed ⁇ ⁇ ⁇ ⁇ film formation impossible X film formation impossible adhesion ⁇ ⁇ ⁇ ⁇ ⁇ Flexibility ⁇ ⁇ ⁇ X ⁇ impact resistance ⁇ ⁇ ⁇ X ⁇ chemical resistance solvent resistance ⁇ ⁇ ⁇ ⁇ ⁇ acid/base ⁇ ⁇ ⁇ X ⁇ surface gloss ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
- Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Drying speed (min) 173 207 235 291 film formation impossible 359 film formation impossible Adhesion (MPa) 7.5 7.6 7.3 5.6 5.3 Flexibility (mm) 6.9 6.7 6.7 5.8 6.3 surface gloss 30.9 31.1 28.9 20.5 19.8
- the epoxy resins of Examples 1 to 3 can form a coating film without solvent mixing and can be used as a solvent-free paint, and overall physical properties such as adhesion, bending resistance, impact resistance, chemical resistance, and surface gloss are compared. It was superior to the coating film using the solvent-type bisphenol-A type epoxy resin as well as the resin of Example 1, and it was confirmed that the drying rate was also greatly shortened.
- the epoxy resin according to the present invention can be used as a paint without mixing a solvent and/or a diluent based on a low viscosity, and the drying rate is significantly higher than that of the existing coating film in film forming using the epoxy paint composition containing the epoxy resin. It is improved, and it is possible to manufacture a coating film having an equivalent or higher level of overall physical properties.
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Abstract
The present invention relates to an epoxy resin, an epoxy paint composition containing same, a coating film formed by said epoxy paint composition, and a substrate with said coating film adhered thereto. The epoxy resin according to the present invention can be used as a paint without adding a solvent and/or a thinner due to having a low viscosity, and the epoxy paint composition containing the epoxy resin can be used to produce a coating film with significantly improved drying speed and equal or better overall physical properties compared to conventional coating films.
Description
본 발명은 에폭시 수지, 이를 포함하는 에폭시 도료 조성물, 상기 에폭시 도료 조성물에 의해 형성된 도막 및 상기 도막 부착 기재에 관한 것이다.The present invention relates to an epoxy resin, an epoxy coating composition comprising the same, a coating film formed by the epoxy coating composition, and a substrate to which the coating film is attached.
에폭시 수지는 일반적으로 고 내식성, 고 내화학성의 특성을 갖고 있어 선박 도료, 중방식 도료 및 산업 전반에 가장 광범위하게 사용되는 수지이다. Epoxy resins generally have high corrosion resistance and high chemical resistance, so they are the most widely used resins for ship paints, heavy-duty anticorrosive paints, and overall industries.
일반적으로 비스페놀 A에 에피클로로하이드린의 중 축합 반응을 통하여 액상 BPA 에폭시 수지를 제조하여 많이 사용되며, 비스페놀 A와 ECH(Ephichloro Hydrine)의 몰비를 조절하여 분자량 및 에폭시 당량에 따른 제품의 용도에 맞게 사용된다. Generally, liquid BPA epoxy resin is produced through polycondensation reaction of epichlorohydrin with bisphenol A, and it is widely used. By adjusting the molar ratio of bisphenol A and ECH (Ephichloro Hydrine), it is suitable for the purpose of the product according to the molecular weight and epoxy equivalent. used
하지만 일반적인 에폭시 수지의 경우 점도가 상온 25 ℃에서 13,000 cps로 선박 도료 및 중방식 도료 제조 시에 다량의 자이렌 및 알코올류 등의 휘발성 유기 용제가 사용되며, 이로 기인하여 대기 환경오염 및 작업자 인체에 유해한 결과를 초래한다. However, in the case of general epoxy resin, a large amount of volatile organic solvents such as xylene and alcohol are used when manufacturing marine paints and heavy anticorrosive paints with a viscosity of 13,000 cps at room temperature of 25 ℃, which causes air pollution and human body. lead to harmful consequences;
또한 이러한 액상 에폭시 수지의 경우 도료로 제조되어 에폭시 경화제와 경화 반응 후 생성된 도막이 취성을 가져 외부의 충격에 의해 도막의 균열을 야기하며 외부 환경에 피 도착물이 도출되어 선박 및 철 구조물 등에 부식 등의 큰 결함을 야기한다. 이러한 문제를 해결하기 위해서는 비스페놀 A의 추가 중합 반응을 통해 분자량 및 에폭시 당량을 상승시킨 제품을 사용 해야만 한다.In addition, in the case of such a liquid epoxy resin, the coating film produced after the curing reaction with the epoxy curing agent is brittle because it is manufactured as a paint, causing cracks in the coating film due to external impact. cause major flaws in In order to solve this problem, it is necessary to use a product whose molecular weight and epoxy equivalent have been increased through an additional polymerization reaction of bisphenol A.
그러나 이러한 경우 분자량 상승에 따른 점도 상승으로 액상 제품이 반 고상 및 고상으로 전이되어 더 많은 량의 휘발성 유기 화합물인 유기 용제가 사용되어야 하며, 더욱이 분자량 상승에 따른 에폭시 수지의 경화제로 사용되는 폴리 아마이드 또는 펜알카민 등과의 상용성이 문제가 야기되며 이런 경우 도막의 경화 불량 및 부착력 불량 등의 문제를 초래하게 된다. However, in this case, the liquid product is transferred to a semi-solid and solid phase due to the increase in viscosity due to the increase in molecular weight, so a larger amount of an organic solvent, which is a volatile organic compound, must be used. Moreover, polyamide or polyamide used as a curing agent for epoxy resin according to the increase in molecular weight Compatibility with phenalkamine and the like is problematic, and in this case, problems such as poor curing and poor adhesion of the coating film are caused.
또한 최근 휘발성 유기 화합물(volatile organic compounds; VOC)사용 규제에 따른 휘발성 유기 용제의 사용량이 규제되고 있는 실정이어서 이러한 문제를 해결할 수 있는 도료용 수지의 연구가 시급한 실정이다.In addition, the use of volatile organic solvents is regulated according to the recent regulations on the use of volatile organic compounds (VOCs), so there is an urgent need to research resins for paints that can solve this problem.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 1) 한국등록특허 제10-1264516호(Patent Document 1) Korean Patent No. 10-1264516
따라서, 본 발명이 해결하고자 하는 기술적 과제는 무용제형 도료의 제조가 가능한 저점도형 에폭시 수지 및 이를 포함하는 에폭시 도료 조성물을 제공하는 것이다.Accordingly, the technical problem to be solved by the present invention is to provide a low-viscosity epoxy resin capable of producing a solvent-free paint and an epoxy paint composition including the same.
또한, 상기 에폭시 도료 조성물로 형성된 도막 및 상기 도막과 기재를 포함하는 도막 부착 기재를 제공하는 것이다.In addition, it is to provide a coating film formed of the epoxy coating composition, and a substrate with a coating film comprising the coating film and the substrate.
본 발명의 일 측면은 하기 화학식 1로 표시되고, 하기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 에폭시 수지에 관한 것이다.One aspect of the present invention relates to an epoxy resin represented by the following Chemical Formula 1, and containing 50 mol% or more of a compound having n=0 in the following Chemical Formula 1.
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
본 발명의 다른 측면은 하기 화학식 1로 표시되고, 하기 화학식 1에서 n=0인 화합물, n=1인 화합물 및 n=2인 화합물의 혼합물을 포함하는 에폭시 수지에 관한 것이다.Another aspect of the present invention is It relates to an epoxy resin comprising a mixture of a compound represented by the following formula (1), and a compound having n=0, a compound having n=1, and a compound having n=2 in the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
본 발명의 또 다른 측면은 하기 화학식 1로 표시되는 에폭시 수지를 포함하고, 상기 에폭시 수지는 하기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 것인 에폭시 도료 조성물에 관한 것이다.Another aspect of the present invention relates to an epoxy paint composition comprising an epoxy resin represented by the following formula (1), wherein the epoxy resin comprises 50 mol% or more of a compound having n = 0 in the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
본 발명의 또 다른 측면은 하기 화학식 1로 표시되는 에폭시 수지를 포함하고, 상기 에폭시 수지는 하기 화학식 1에서 n=0인 화합물, n=1인 화합물 및 n=2인 화합물의 혼합물을 포함하는 것인 에폭시 도료 조성물에 관한 것이다.Another aspect of the present invention includes an epoxy resin represented by the following formula (1), wherein the epoxy resin includes a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1) It relates to a phosphorus epoxy paint composition.
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
본 발명의 또 다른 측면은 상기 에폭시 도료 조성물로 형성된 도막에 관한 것이다.Another aspect of the present invention relates to a coating film formed of the epoxy coating composition.
본 발명의 또 다른 측면은 상기 도막과 기재를 포함하는 도막 부착 기재에 관한 것이다.Another aspect of the present invention relates to a substrate with a coating film including the coating film and the substrate.
본 발명에 따른 에폭시 수지는 낮은 점도를 바탕으로 용제 및/또는 희석제의 배합 없이 도료로 사용될 수 있으며, 상기 에폭시 수지를 포함하는 에폭시 도료 조성물을 이용한 제막에서 기존 도막과 비교하여 건조 속도가 현저히 개선되며, 전반적인 물성이 동등 이상 수준을 갖는 도막을 제조할 수 있다. The epoxy resin according to the present invention can be used as a paint without mixing of a solvent and/or a diluent based on a low viscosity, and the drying speed is significantly improved compared to the existing coating film in film forming using the epoxy paint composition containing the epoxy resin, , it is possible to manufacture a coating film having an equivalent or higher level of overall physical properties.
[규칙 제91조에 의한 정정 25.02.2021]
도면의 간단한 설명 [Correction by Rule 91 25.02.2021]
Brief description of the drawing
도면의 간단한 설명 [Correction by Rule 91 25.02.2021]
Brief description of the drawing
[규칙 제91조에 의한 정정 25.02.2021]
도 1은 실시예 1에서 얻은 에폭시 수지의 GPC 분석 결과 그래프이다[Correction by Rule 91 25.02.2021]
1 is a graph of the results of GPC analysis of the epoxy resin obtained in Example 1.
도 1은 실시예 1에서 얻은 에폭시 수지의 GPC 분석 결과 그래프이다[Correction by Rule 91 25.02.2021]
1 is a graph of the results of GPC analysis of the epoxy resin obtained in Example 1.
[규칙 제91조에 의한 정정 25.02.2021]
[Correction by Rule 91 25.02.2021]
[Correction by Rule 91 25.02.2021]
[규칙 제91조에 의한 정정 25.02.2021]
이하에서, 본 발명의 여러 측면 및 다양한 구현예에 대해 더욱 구체적으로 설명한다.[Correction by Rule 91 25.02.2021]
Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.
이하에서, 본 발명의 여러 측면 및 다양한 구현예에 대해 더욱 구체적으로 설명한다.[Correction by Rule 91 25.02.2021]
Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.
본 발명에서 사용한 용어는 단지 특정 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 발명에서, '포함하다'또는 '가지다'등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present invention, terms such as 'comprise' or 'have' are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.
종래 에폭시 수지 도료는 접착력, 내열성, 내수성, 내약품성, 기계적 강도 등의 물성이 우수하여 선박, 중방식용, 건축용 도료로 널리 사용되고 있다. 대표적인 에폭시 수지인 비스페놀A 형 에폭시 수지는 높은 점도 때문에 반드시 용제 및/또는 희석제를 사용하여 도료 배합을 설계하여야 한다.Conventional epoxy resin paints have excellent physical properties such as adhesion, heat resistance, water resistance, chemical resistance, and mechanical strength, and are widely used as paints for ships, heavy-duty anticorrosives, and constructions. Bisphenol A type epoxy resin, which is a typical epoxy resin, must be designed using a solvent and/or diluent because of its high viscosity.
한편, 비스페놀A 형 에폭시 수지를 이용한 도료의 배합에 사용되는 용제와 희석제는 본질적으로 VOC 방출을 수반하나, 최근 휘발성 유기화합물(VOC) 관련 규제가 강화되고 있는 추세이다. 도료 업체 또한 VOC 저감을 위해 현재 적용 중인 용제형 도료에서 용제를 사용하지 않는 무용제형 도료 및 하이 솔리드형(높은 고형분) 도료 개발에 집중하고 있으며, 저점도형의 주제 또는 VOC 방출량이 적은 희석제 개발에 힘쓰고 있는 상황이다.On the other hand, solvents and diluents used in the formulation of paints using bisphenol A-type epoxy resins intrinsically accompany VOC emission, but regulations related to volatile organic compounds (VOCs) are being strengthened in recent years. Paint companies are also concentrating on the development of solvent-free paints and high-solids (high solids) paints that do not use solvents from currently applied solvent paints to reduce VOCs, and are focusing on developing low-viscosity subjects or diluents with low VOC emissions. writing situation.
이에 본 발명은 저점도 형태의 에폭시 수지를 포함하는 에폭시 도료 조성물을 제공한다.Accordingly, the present invention provides an epoxy paint composition comprising an epoxy resin in a low-viscosity form.
구체적으로, 본 발명의 일 측면은 하기 화학식 1로 표시되고, 하기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 에폭시 수지를 제공한다.Specifically, one aspect of the present invention provides an epoxy resin comprising 50 mol% or more of a compound represented by the following formula (1), wherein n = 0 in the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
본 발명의 다른 측면은 하기 화학식 1로 표시되고, 하기 화학식 1에서 n=0인 화합물, n=1인 화합물 및 n=2인 화합물의 혼합물을 포함하는 에폭시 수지를 제공한다.Another aspect of the present invention is It is represented by the following Chemical Formula 1, and provides an epoxy resin comprising a mixture of a compound having n=0, a compound having n=1, and a compound having n=2 in the following Chemical Formula 1.
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
상기 카테콜형 에폭시 수지는 종래의 고점도 비스페놀 A형 에폭시 수지와는 달리 저점도 특성을 가져 용제 및/또는 희석제의 사용량을 현저하게 줄이거나 사용하지 않아 VOC 방출량이 거의 없는 저용제형 또는 무용제형 도료 조성물을 제조할 수 있다. 또한, 상기 화학식의 벤젠 고리에 알킬기를 비롯한 여타 작용기가 치환되지 않은 카테콜형 에폭시 수지를 포함함으로써, 전반적으로 종래 수준과 동등 이상 수준의 물성을 갖는 도막을 구현할 수 있으며, 특히 건조 속도가 개선될 수 있다.The catechol-type epoxy resin has a low-viscosity property, unlike the conventional high-viscosity bisphenol A-type epoxy resin, so that the amount of solvent and/or diluent is significantly reduced or not used, so a low-solvent-type or solvent-free coating composition with little VOC emission. can be manufactured. In addition, by including a catechol-type epoxy resin in which other functional groups, including an alkyl group, are not substituted in the benzene ring of the above formula, a coating film having physical properties equivalent to or higher than that of the conventional level can be implemented as a whole, and in particular, the drying rate can be improved. have.
일 구현예에 따르면, 상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 것일 수 있다. 예를 들어, 상기 에폭시 수지는 화학식 1에서 n=0인 화합물을 55 몰% 이상, 60 몰%이상, 또는 65 몰%이상 포함할 수 있다.According to one embodiment, the epoxy resin may include 50 mol% or more of the compound having n=0 in Formula 1 above. For example, the epoxy resin may include 55 mol% or more, 60 mol% or more, or 65 mol% or more of the compound having n=0 in Formula 1.
상기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 조건을 만족하는 에폭시 수지를 포함하는 에폭시 도료 조성물은 용제 또는 희석제를 전혀 포함하지 않고도 도막 형성이 가능한 이점을 갖는다.The epoxy paint composition including an epoxy resin that satisfies the condition of including 50 mol% or more of the compound of n=0 in Formula 1 has the advantage of being able to form a coating film without including any solvent or diluent.
다른 구현예에 따르면, 상기 에폭시 수지는 상기 화학식 1에서 n=0 내지 1인 화합물을 90 몰% 이상 포함하는 것일 수 있다. 후술하는 실시예에서 확인할 수 있는 바와 같이, 상기 반복단위의 몰% 조건을 만족하는 에폭시 수지를 포함하는 에폭시 도료 조성물을 이용하여 형성한 도막은 내충격성 등의 기계적 강도 측정에서 상기 몰% 조건을 만족하지 않는 에폭시 수지에 비하여 우수한 기계적 강도를 가지는 것을 확인할 수 있었다. According to another embodiment, the epoxy resin may include 90 mol% or more of the compound having n=0 to 1 in Formula 1 above. As can be seen in Examples to be described later, a coating film formed using an epoxy paint composition containing an epoxy resin that satisfies the mol % condition of the repeating unit satisfies the mol % condition in the measurement of mechanical strength such as impact resistance. It was confirmed that it has excellent mechanical strength compared to the epoxy resin not used.
일 구현예에 따르면, 상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 내지 90 몰%, n=1인 화합물을 5 내지 40 몰% 및 n=2 이상인 화합물을 1 내지 11 몰% 포함하는 것일 수 있다. 예를 들어, n=0인 화합물을 60 내지 88 몰%, n=1인 화합물을 8 내지 30 몰% 및 n=2 이상인 화합물을 3 내지 10 몰% 포함하는 것일 수 있다. 상기 조건을 만족하는 에폭시 수지를 포함하는 에폭시 도료 조성물은 상술한 건조속도가 개선된 특성뿐만 아니라, 도막의 건조 속도도 제어할 수 있는 이점이 있다. 또한, 접착력, 굴곡접착력이 우수하며, 동시에 내용제성, 내산성, 내염기성을 포함하는 내화학성, 표면 광택도 등의 전반적인 물성이 향상된 도막을 형성할 수 있음을 확인하였다.According to one embodiment, the epoxy resin contains 50 to 90 mol% of the compound having n=0 in Formula 1, 5 to 40 mol% of the compound having n=1, and 1 to 11 mol% of the compound having n=2 or more may be doing For example, it may include 60 to 88 mol% of the compound having n=0, 8 to 30 mol% of the compound having n=1, and 3 to 10 mol% of the compound having n=2 or more. The epoxy paint composition including the epoxy resin satisfying the above conditions has the advantage of controlling the drying rate of the coating film as well as the improved drying rate described above. In addition, it was confirmed that it was possible to form a coating film having excellent adhesion and flexural adhesion, and at the same time improving overall physical properties such as solvent resistance, acid resistance, chemical resistance including basic resistance, and surface glossiness.
일 구현예에 따르면, 상기 에폭시 수지의 점도는 25 ℃에서 점도는 2000 cps 이하일 수 있으며, 예를 들어 200 내지 2000 cps 또는 200 내지 1800 cps일 수 있다. 상기 점도 범위를 만족하는 경우 작업성이 우수하여 상기 에폭시 수지를 포함하는 도료에 양호한 건조속도, 접착력, 내굴곡성, 내충격성, 내화학성 및 표면 광택도가 부여될 수 있다. 또한, 에폭시 수지를 포함하는 도료의 건조 속도 및 표면 광택도를 더욱 향상시키기 위하여 상기 에폭시 수지의 점도가 25 ℃에서 200 내지 1600 cps, 200 내지 1000 cps, 또는 200 내지 800 cps일 수 있다. 한편, 상기 에폭시 수지의 점도가 2000 cps를 초과하는 경우 무용제형 도료에서 도포성 저하로 인하여 균일한 도막의 형성이 어려울 수 있다.According to one embodiment, the viscosity of the epoxy resin may be 2000 cps or less at 25 °C, for example, 200 to 2000 cps or 200 to 1800 cps. When the above viscosity range is satisfied, workability is excellent, and good drying speed, adhesion, bending resistance, impact resistance, chemical resistance, and surface glossiness can be imparted to the paint containing the epoxy resin. In addition, in order to further improve the drying rate and surface glossiness of the paint containing the epoxy resin, the viscosity of the epoxy resin may be 200 to 1600 cps, 200 to 1000 cps, or 200 to 800 cps at 25°C. On the other hand, when the viscosity of the epoxy resin exceeds 2000 cps, it may be difficult to form a uniform coating film due to a decrease in applicability in a solvent-free coating material.
상기 에폭시 수지의 에폭시 당량은 120 내지 185 g/eq일 수 있다. 예를 들어, 상기 에폭시 수지의 당량은 140 내지 183 g/eq일 수 있다. 상기 에폭시 수지의 에폭시 당량이 상기 범위를 만족하는 경우에 수지의 점도를 낮출 수 있는 효과가 있다.The epoxy equivalent of the epoxy resin may be 120 to 185 g / eq. For example, the equivalent weight of the epoxy resin may be 140 to 183 g / eq. When the epoxy equivalent of the epoxy resin satisfies the above range, there is an effect of lowering the viscosity of the resin.
본 발명의 또 다른 측면은 하기 화학식 1로 표시되는 에폭시 수지를 포함하고, 상기 에폭시 수지는 하기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 것인 에폭시 도료 조성물을 제공한다.Another aspect of the present invention provides an epoxy paint composition comprising an epoxy resin represented by the following formula (1), wherein the epoxy resin comprises 50 mol% or more of a compound having n = 0 in the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
본 발명의 또 다른 측면은 하기 화학식 1로 표시되는 에폭시 수지를 포함하고, 상기 에폭시 수지는 하기 화학식 1에서 n=0인 화합물, n=1인 화합물 및 n=2인 화합물의 혼합물을 포함하는 것인 에폭시 도료 조성물을 제공한다.Another aspect of the present invention includes an epoxy resin represented by the following formula (1), wherein the epoxy resin includes a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1) A phosphorus epoxy paint composition is provided.
[화학식 1][Formula 1]
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함할 수 있다. The epoxy resin may include 50 mol% or more of the compound having n=0 in Formula 1 above.
상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
상기 에폭시 수지는 상기 화학식 1에서 n=0 내지 1인 화합물을 90 몰% 이상 포함할 수 있다.The epoxy resin may include 90 mol% or more of the compound having n=0 to 1 in Formula 1 above.
상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 내지 90 몰%, n=1인 화합물을 5 내지 40 몰% 및 n=2 이상인 화합물을 1 내지 11 몰% 포함하는 것일 수 있으며, 예를 들어 n=0인 화합물을 60 내지 88 몰%, n=1인 화합물을 8 내지 30 몰% 및 n=2 이상인 화합물을 3 내지 10 몰% 포함하는 것일 수 있다.The epoxy resin may include 50 to 90 mol% of a compound having n=0 in Formula 1, 5 to 40 mol% of a compound having n=1, and 1 to 11 mol% of a compound having n=2 or more, for example, For example, it may include 60 to 88 mol% of the compound having n=0, 8 to 30 mol% of the compound having n=1, and 3 to 10 mol% of the compound having n=2 or more.
상기 에폭시 수지의 점도는 25 ℃에서 점도는 2000 cps 이하일 수 있으며, 예를 들어 200 내지 2000 cps, 200 내지 1800 cps, 200 내지 1600 cps 200 내지 1000 cps, 또는 200 내지 800 cps일 수 있다. The viscosity of the epoxy resin may be 2000 cps or less at 25 ° C. For example, 200 to 2000 cps, 200 to 1800 cps, 200 to 1600 cps 200 to 1000 cps, or 200 to 800 cps.
상기 에폭시 수지의 에폭시 당량은 120 내지 185 g/eq일 수 있다. 예를, 들어, 상기 에폭시 수지의 에폭시 당량은 140 내지 183 g/eq일 수 있다. The epoxy equivalent of the epoxy resin may be 120 to 185 g / eq. For example, the epoxy equivalent of the epoxy resin may be 140 to 183 g / eq.
상기 에폭시 도료 조성물에 관한 설명은 에폭시 수지 부분에서 상술한 바와 동일하므로 생략하기로 한다.The description of the epoxy paint composition is the same as described above in the epoxy resin part, so it will be omitted.
일 구현예에 따르면, 상기 에폭시 도료 조성물은 상기 에폭시 수지를 포함하는 주제부 및 경화제부를 포함할 수 있다. According to one embodiment, the epoxy paint composition may include a main part and a curing agent part including the epoxy resin.
일 구현예에 따르면, 상기 주제부는 상기 주제부 100 중량부를 기준으로 상기 에폭시 수지를 5 내지 50 중량부 및 안료 50 내지 95 중량부 포함할 수 있다. According to one embodiment, the main part may include 5 to 50 parts by weight of the epoxy resin and 50 to 95 parts by weight of the pigment based on 100 parts by weight of the main part.
다른 구현예에 따르면, 상기 주제부는 상기 주제부 100 중량부를 기준으로 상기 에폭시 수지 15 내지 30 중량부 및 안료 70 내지 85 중량부를 포함할 수 있으며, 예를 들어 상기 에폭시 수지 20 내지 30 중량부 및 안료 70 내지 80 중량부 포함할 수 있다.According to another embodiment, the main part may include 15 to 30 parts by weight of the epoxy resin and 70 to 85 parts by weight of the pigment based on 100 parts by weight of the main part, for example, 20 to 30 parts by weight of the epoxy resin and the pigment. 70 to 80 parts by weight may be included.
상기 안료는 체질안료 또는 색상안료일 수 있으며, 전술한 안료를 단독 사용하거나 또는 2종 이상 혼용할 수 있다.The pigment may be an extender pigment or a color pigment, and the aforementioned pigments may be used alone or in combination of two or more.
상기 체질안료는 도막 내의 기공을 충전시키고, 경도 및 약품성 등을 보완하고 광택을 조절하는 역할을 한다. The extender pigment fills the pores in the coating film, complements hardness and chemical properties, and controls gloss.
상기 체질안료는 당 분야에 알려진 통상적인 체질안료를 제한 없이 사용할 수 있으며, 일례로 실리카, 바라이트(천연바륨설페이트), 블랑픽스(합성바륨설페이트), 탈크, 칼슘 카보네이트, 탄산칼슘 등이 있다. 전술한 성분을 단독 사용하거나 또는 2종 이상 혼용할 수 있다.As the extender, conventional extender pigments known in the art may be used without limitation, and examples thereof include silica, barite (natural barium sulfate), blancfix (synthetic barium sulfate), talc, calcium carbonate, calcium carbonate, and the like. The above-mentioned components may be used alone or in combination of two or more.
상기 색상안료는 에폭시 수지와 혼합하여 도료에 원하는 색상(유색)을 발현하는 목적으로 포함된다. The color pigment is included for the purpose of expressing a desired color (colored) in the paint by mixing with the epoxy resin.
상기 색상안료는 당 분야에서 통상적으로 사용되는 유기 안료, 무기 안료, 메탈릭 안료, 알루미늄-페이스트(Alpaste), 펄(pearl) 등을 제한 없이 사용할 수 있으며, 이들을 단독 또는 2종 이상 혼용할 수 있다. 예를 들어, 티타늄 디옥사이드, 비스무스 바나데이트, 시아닌 그린, 카본 블랙, 산화철적, 산화철황, 네이비 블루, 시아닌 블루로 이루어진 군에서 선택되는 1종 또는 2종 이상의 혼합물을 사용할 수 있다.As the color pigment, organic pigments, inorganic pigments, metallic pigments, aluminum-pastes, pearls, etc. commonly used in the art may be used without limitation, and these may be used alone or in combination of two or more. For example, one or a mixture of two or more selected from the group consisting of titanium dioxide, bismuth vanadate, cyanine green, carbon black, iron oxide, iron oxide sulfur, navy blue, and cyanine blue may be used.
상기 경화제부에는 경화제 및 경화촉진제 등을 포함할 수 있다. 에폭시 수지를 포함하는 주제에 사용되는 경화제라면 당 업계에 알려진 통상적인 경화제를 특별히 제한되지 않고 포함할 수 있으며. 예를 들어 아민계 경화제 또는 폴리아미드계 경화제를 포함할 수 있다. 일 구현예에 따르면, 경화제부에는 아민계 경화제가 포함될 수 있다.The curing agent may include a curing agent and a curing accelerator. As long as it is a curing agent used in a subject including an epoxy resin, it may include a conventional curing agent known in the art without being particularly limited. For example, it may include an amine-based curing agent or a polyamide-based curing agent. According to one embodiment, the curing agent part may include an amine-based curing agent.
상기 아민계 경화제로는 당 분야에 알려진 통상적인 아민계 경화제용 수지를 제한 없이 사용할 수 있다. 일례로 지방족 아민 수지(aliphatic amine base), 방향족 아민 수지(aromatic amine base) 또는 이들의 혼합 형태 등이 있다.As the amine-based curing agent, a conventional resin for an amine-based curing agent known in the art may be used without limitation. For example, there is an aliphatic amine base, an aromatic amine base, or a mixture thereof.
상기 아민계 경화제의 함량은 특별히 제한되지 않으며, 일례로 당해 경화제부의 총 중량을 기준으로 하여 30 내지 60 중량%일 수 있다. 예를 들어, 상기 지방족 아민 수지의 함량은 당해 경화제부의 총 중량을 기준으로 하여 20 내지 40 중량%일 수 있으며, 상기 방향족 아민 수지의 함량은 당해 경화제부의 총 중량을 기준으로 하여 10 내지 20 중량%일 수 있다. 상기 아민계 경화제의 함량이 전술한 범위보다 작을 경우 경화 후 도막 외관이 불량하고, 경도가 저하되는 문제가 발생할 수 있으며, 전술한 범위를 초과할 경우 작업성이 저하되고 건조시간이 늦어지는 문제가 발생할 수 있다.The content of the amine-based curing agent is not particularly limited, and may be, for example, 30 to 60% by weight based on the total weight of the curing agent part. For example, the content of the aliphatic amine resin may be 20 to 40% by weight based on the total weight of the curing agent part, and the content of the aromatic amine resin may be 10 to 20% by weight based on the total weight of the curing agent part. can be If the content of the amine-based curing agent is less than the above range, the appearance of the coating film after curing may be poor, and a problem of lowering the hardness may occur. If the content of the amine-based curing agent is less than the above range, workability is deteriorated and drying time is delayed. can occur
상기 경화촉진제는 에폭시 수지와 아민계 경화제와의 반응을 촉진하는 물질로서, 당 분야에 알려진 통상적인 물질을 제한 없이 사용할 수 있다.The curing accelerator is a material that promotes the reaction between the epoxy resin and the amine-based curing agent, and any conventional material known in the art may be used without limitation.
사용 가능한 경화촉진제의 비제한적인 예로는, 트리디메틸아미노 메틸페놀, 트리페닐 포스파이트 및 아미노 에틸피페라진으로 구성된 군에서 선택되는 1종 이상일 수 있다.Non-limiting examples of the curing accelerator that can be used may be at least one selected from the group consisting of tridimethylamino methylphenol, triphenyl phosphite, and amino ethylpiperazine.
상기 경화촉진제의 함량은 특별히 제한되지 않으며, 일례로 당해 경화제부의 총 중량을 기준으로 하여 10 내지 30 중량%일 수 있다. 상기 경화촉진제의 함량 범위를 벗어날 경우 도막의 내약품성, 내수성 등의 물성이 저하되며, 도막 외관이 불량해질 수 있다.The content of the curing accelerator is not particularly limited, and may be, for example, 10 to 30% by weight based on the total weight of the curing agent part. If the content of the curing accelerator is out of the range, physical properties such as chemical resistance and water resistance of the coating film may deteriorate, and the appearance of the coating film may deteriorate.
상기 에폭시 도료 조성물은 첨가제로 조성물의 고유 특성을 해하지 않는 범위 내에서, 당 업계에 알려진 통상적인 첨가제를 포함할 수 있다. The epoxy paint composition may include conventional additives known in the art within a range that does not impair the inherent properties of the composition as additives.
사용 가능한 첨가제의 비제한적인 예로는 분산제, 소포제, 탈포제, 레벨링제, 내후성 첨가제, 건조제, 외관 조절제, 침강방지제, 커플링제 또는 이들의 2종 이상 혼합물 등이 있다. 예를 들어, 침강방지제, 분산제, 소포제, 탈포제 및 레벨링제로 구성된 군에서 선택되는 2종 이상의 첨가제를 혼용할 수 있다. 본 발명에서, 상기 첨가제의 함량은 당 분야에 공지된 함량 범위 내에서 적절히 조절할 수 있으며, 일례로 상기 주제부의 총 중량을 기준으로 하여 1 내지 8 중량%일 수 있다.Non-limiting examples of additives that can be used include a dispersant, an antifoaming agent, a defoaming agent, a leveling agent, a weathering additive, a desiccant, an appearance control agent, an anti-settling agent, a coupling agent, or a mixture of two or more thereof. For example, two or more additives selected from the group consisting of an anti-settling agent, a dispersing agent, an antifoaming agent, a defoaming agent, and a leveling agent may be mixed. In the present invention, the content of the additive may be appropriately adjusted within a content range known in the art, and for example, may be 1 to 8% by weight based on the total weight of the main part.
상기 침강방지제는 재료들의 침강을 막아 도막이 균일한 성상으로 형성하도록 하는 역할을 하는 것으로서, 당 분야에 알려진 통상적인 것을 제한 없이 사용할 수 있다. 일례로 클레이(clay) 타입의 침강방지제 등이 있다. 상기 침강방지제의 함량은 특별히 제한되지 않으며, 예를 들어 0.1 내지 0.7 중량%일 수 있다. 이러한 침강방지제의 함량이 0.1 중량% 미만일 경우 도막의 레벨링은 매우 우수하지만 도료의 저장성이 불량해지며, 0.7 중량%를 초과할 경우 도료의 저장 안정성은 우수하지만 도막의 레벨링이 불량해질 수 있다.The anti-settling agent serves to prevent sedimentation of materials to form a coating film with a uniform property, and conventional ones known in the art may be used without limitation. For example, there is a clay-type anti-settling agent and the like. The content of the anti-settling agent is not particularly limited, and may be, for example, 0.1 to 0.7 wt%. When the content of the anti-settling agent is less than 0.1 wt %, the leveling of the coating film is very good, but the storability of the paint is poor, and when it exceeds 0.7 wt %, the storage stability of the paint is excellent, but the leveling of the coating film may be poor.
도막 표면의 기포 제거와 함께 도막 내의 기포가 빨리 표면으로 떠오를 수 있도록 소포제와 탈포제를 혼용할 수 있다. 내부의 기포가 떠오르지 못하여 도막 내에 잔존할 경우 소재와의 부착 불량 및/또는 물리적 물성 저하가 초래될 수 있으며, 설령 내부의 기포가 떠오르더라도 도막의 경화가 어느 정도 진행된 상태에서는 도막의 흐름성이 떨어짐에 따라 기포 자국이 도막 표면에 남을 수 있다. 또한, 여러 가지 색상안료가 사용된 경우, 안료마다 유동성이 달라 색 분리가 발생하여 경화 전과 후의 색상이 달라지거나, 도장 부위별로 색상이 달라 외관이 불량하게 될 수 있다. 주제부가 전술한 분산제, 소포제, 탈포제, 레벨링제 등 1종 이상의 첨가제를 포함할 경우, 소포성 불량, 크레터링 발생, 색분리 등의 도막 결함 발생을 개선할 수 있다.An antifoaming agent and a defoaming agent can be mixed together to remove air bubbles from the surface of the coating film and allow the bubbles in the coating film to rise to the surface quickly. If the bubbles inside do not rise and remain in the coating film, poor adhesion to the material and/or deterioration of physical properties may result. Even if the bubbles inside rise, the flowability of the coating film decreases when the coating film is cured to some extent. As a result, bubble marks may remain on the surface of the coating film. In addition, when various color pigments are used, color separation occurs due to different fluidity for each pigment, so that the color before and after curing is different, or the appearance is poor because the color is different for each painted part. When the main part includes one or more additives such as the above-described dispersing agent, defoaming agent, defoaming agent, and leveling agent, it is possible to improve the occurrence of coating film defects such as defoaming defects, cratering, and color separation.
상기 분산제는 조성물을 구성하는 각 재료들을 분산시키고 거리 유지를 통해 재응집을 막아 도막의 균일한 물성을 발현하도록 하는 역할을 한다. 상기 분산제로는 당 분야에 알려진 통상적인 것을 사용할 수 있으며, 예를 들어 고분자량의 블록 공중합체 타입의 분산제 등이 있다.The dispersant serves to disperse each material constituting the composition and prevent re-agglomeration by maintaining a distance to express uniform physical properties of the coating film. As the dispersant, a conventional dispersant known in the art may be used, for example, a high molecular weight block copolymer type dispersant.
상기 소포제는 친유체와 폴리실록산의 혼합물로서 도장시 발생되는 기포를 억제함으로써 도막의 외관을 높여주는 역할을 하는 것으로서, 당 분야에 알려진 통상적인 소포제를 제한 없이 사용할 수 있다. 예를 들어, 폴리실록산 타입의 소포제를 사용할 수 있다.The antifoaming agent is a mixture of a lipophilic agent and polysiloxane, and serves to enhance the appearance of the coating film by suppressing air bubbles generated during coating. Conventional antifoaming agents known in the art may be used without limitation. For example, an antifoaming agent of the polysiloxane type can be used.
상기 탈포제는 도장시 기포 발생을 방지 및 제거하고, 제조 공정을 개선시키는 역할을 하는 것으로서, 예를 들어 비실리콘계 폴리머 타입의 탈포제를 사용할 수 있다.The defoaming agent serves to prevent and remove bubbles during coating and improve the manufacturing process. For example, a non-silicone-based polymer-type defoaming agent may be used.
상기 레벨링제는 상기 조성물이 평탄하고 매끄럽게 코팅되도록 레벨링함으로써, 조성물 내의 접착력을 증진시키면서 도막의 외관 특성을 향상시키기 위한 것이다. 상기 레벨링제로는 당 분야에 알려진 통상적인 것을 제한 없이 사용할 수 있으며, 예를 들어 아크릴계, 실리콘계, 폴리에스테르계, 아민계 레벨링제 등이 있다.The leveling agent is to improve the appearance characteristics of the coating film while enhancing adhesion in the composition by leveling the composition so that the composition is coated evenly and smoothly. As the leveling agent, a conventional leveling agent known in the art may be used without limitation, and for example, an acrylic-based, silicone-based, polyester-based, or amine-based leveling agent may be used.
본 발명의 또 다른 측면은 상기 에폭시 도료 조성물로 형성된 도막 및 상기 에폭시 도료 조성물로 형성된 도막과 기재를 포함하는 도막 부착 기재에 관한 것이다. 상기 도막은 상술한 에폭시 도료 조성물을 사용하여 형성되고, 상기 도막 부착 기재는 상기 도막과 피도물(기재)를 포함하는 적층체이다.Another aspect of the present invention relates to a coating film formed of the epoxy coating composition, and a substrate with a coating film comprising the coating film and the substrate formed of the epoxy coating composition. The coating film is formed using the above-described epoxy coating composition, and the substrate with the coating film is a laminate including the coating film and an object (substrate) to be coated.
상기 도막의 두께는 도막의 용도에 따라 달라질 수 있으나, 특별히 한정되지 않으며, 예를 들어 50 내지 500 μm, 또는 100 내지 300 μm일 수 있다.The thickness of the coating film may vary depending on the use of the coating film, but is not particularly limited, and may be, for example, 50 to 500 μm, or 100 to 300 μm.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어 자명할 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art to which the present invention pertains that the scope of the present invention is not limited by these examples.
실시예 1. 에폭시 수지의 제조Example 1. Preparation of epoxy resin
교반기, 콘데서, 온도계를 구비한 4구 플라스크에, 카테콜 500 g(4.541 몰), 에피클로로히드린 3571 g(38.601 몰)을 넣고 65 ℃까지 승온한 후, 50% 가성소다 48 g(0.599 몰) 30 분 동안 균일 적하한 후 3 시간 동안 반응시켰다. 온도를 62 ℃로 냉각한 후 50% 가성소다 613 g(7.666 몰)을 2 시간 30 분 동안 균일 적하하며, 진공도 130~170 torr 조건으로 물을 제거하였다. 이후 미반응 에피클로로히드린을 제거하기 위해 온도를 150 ℃ 10 torr 미만 조건으로 탈기를 진행하였다. In a four-neck flask equipped with a stirrer, condenser, and thermometer, 500 g (4.541 mol) of catechol and 3571 g (38.601 mol) of epichlorohydrin were put, and the temperature was raised to 65 ° C., and then 48 g (0.599 mol) of 50% caustic soda. ) was uniformly dripped for 30 minutes and then reacted for 3 hours. After cooling the temperature to 62 °C, 613 g (7.666 mol) of 50% caustic soda was uniformly added dropwise for 2 hours and 30 minutes, and water was removed under a vacuum degree of 130 to 170 torr. Thereafter, in order to remove unreacted epichlorohydrin, degassing was performed at a temperature of 150° C. less than 10 torr.
발생한 NaCl염을 제거하기 위해 MIBK 1513 g, 물 1215 g 투입하여 수세를 진행하였다. 이때 에폭시 당량은 143 g/eq 염소분은 1940 ppm이었다.In order to remove the generated NaCl salt, 1513 g of MIBK and 1215 g of water were added and washed with water. At this time, the epoxy equivalent was 143 g/eq chlorine content was 1940 ppm.
추가 폐환반응을 위해 가성소다 6.6 g, 물 9.9 g을 넣고 85 ℃에서 1 시간 30 분 동안 반응시켰다. For further ring closure reaction, 6.6 g of caustic soda and 9.9 g of water were added and reacted at 85° C. for 1 hour and 30 minutes.
반응종료 후 물을 832 g을 넣고 30 분 교반한 후 정치하여 수분리를 진행하였다. 3 회 반복하여 수세를 진행하여, 마지막 수세 중 물층의 pH를 측정하여 5.0~7.5 수준으로 인산을 이용하여 중화하여 수분리를 실시하였다. After completion of the reaction, 832 g of water was added, stirred for 30 minutes, and then left standing to proceed with water separation. Water washing was repeated three times, and the pH of the water layer was measured during the last washing, and neutralized with phosphoric acid to a level of 5.0 to 7.5, followed by water separation.
용제 제거를 위해 온도 150 ℃ 10 torr 미만 조건으로 탈기를 실시하였으며, 최종 수지의의 에폭시 당량은 142 g/eq, 염소분 226 ppm, 수율 85%, 점도 220 cps였다.To remove the solvent, degassing was performed at a temperature of 150 ° C. less than 10 torr, and the epoxy equivalent of the final resin was 142 g/eq, 226 ppm chlorine, 85% yield, and 220 cps viscosity.
[화학식 1][Formula 1]
[규칙 제91조에 의한 정정 25.02.2021]
이때 수지는 상기 화학식 1로 표시되며, n=0인 화합물 87 몰%, n=1인 화합물이 9 몰%, n=2 이상인 화합물이 4 몰%임을 도 1에서 제공된 GPC 분석을 통하여 확인하였다.[Correction by Rule 91 25.02.2021]
At this time, the resin is represented byChemical Formula 1, and it was confirmed through GPC analysis provided in FIG. 1 that 87 mol% of the compound with n=0, 9 mol% of the compound with n=1, and 4 mol% of the compound with n=2 or more.
이때 수지는 상기 화학식 1로 표시되며, n=0인 화합물 87 몰%, n=1인 화합물이 9 몰%, n=2 이상인 화합물이 4 몰%임을 도 1에서 제공된 GPC 분석을 통하여 확인하였다.[Correction by Rule 91 25.02.2021]
At this time, the resin is represented by
[규칙 제91조에 의한 정정 25.02.2021]
[삭제][Correction by Rule 91 25.02.2021]
[delete]
[삭제][Correction by Rule 91 25.02.2021]
[delete]
GPC 분석 결과(Retention Time)GPC analysis result (Retention Time)
36.648 min: n=0 화합물, 34.608 min: 부산물, 33.417 min: n=1 화합물, 31.692 min : n=2 이상 화합물36.648 min: n=0 compound, 34.608 min: by-product, 33.417 min: n=1 compound, 31.692 min: n=2 or more compounds
실시예 2. 에폭시 수지의 제조Example 2. Preparation of Epoxy Resin
에피클로로히드린 2435 g(26.340 몰), 초기 50% 가성소다를 25 g(0.318 몰), 58 g(0.727 몰) 2회 분할하여 균일 적하한 후 4 시간 동안 반응시키고, 이후 투입하는 50% 가성소다 218 g(2.725 몰), 428 g(5.359 몰)을 2회 분할하여 각각 40 분, 75 분 균일 적하한 후 1 시간 동안 반응을 진행한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다. 최종 수지의 에폭시 당량은 166 g/eq, 염소분 184 ppm, 점도 787 cps였다. 이때 수지는 상기 화학식 1로 표시되며, n=0인 화합물 76 몰%, n=1인 화합물 15 몰%, n=2 이상인 화합물 9 몰%을 포함하였다.2435 g (26.340 mol) of epichlorohydrin, 25 g (0.318 mol) of initial 50% caustic soda, and 58 g (0.727 mol) of caustic soda were divided into two portions and uniformly dripped, reacted for 4 hours, and then added 50% caustic 218 g (2.725 mol) of soda and 428 g (5.359 mol) of soda were divided into two portions and uniformly dripped for 40 minutes and 75 minutes, respectively, and then the reaction was carried out in the same manner as in Example 1, except that the reaction was carried out for 1 hour. The final resin had an epoxy equivalent of 166 g/eq, a chlorine content of 184 ppm, and a viscosity of 787 cps. At this time, the resin is represented by Formula 1, and contains 76 mol% of a compound of n=0, 15 mol% of a compound of n=1, and 9 mol% of a compound of n=2 or more.
실시예 3. 에폭시 수지의 제조Example 3. Preparation of Epoxy Resin
에피클로로히드린 1932 g(20.890 몰), 초기 50% 가성소다를 25 g(0.318 몰), 58 g(0.727 몰) 2회 분할하여 균일 적하한 후 각각 2 시간 동안 반응시키고, 이후 투입하는 50% 가성소다 182 g(2.275 몰), 465 g(5.812 몰)을 2회 분할하여 각각 60분, 180분 균일 적하한 후 1 시간 동안 반응을 진행한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다. 최종 수지의 에폭시 당량은 181 g/eq, 염소분 560 ppm, 점도 1640 cps였다. 이때 수지는 상기 화학식 1로 표시되며, n=0인 화합물 58 몰%, n=1인 화합물 32 몰%, n=2 이상인 화합물 10 몰%을 포함하였다. 1932 g (20.890 mol) of epichlorohydrin, 25 g (0.318 mol) and 58 g (0.727 mol) of 50% caustic soda in the initial stage were divided into two portions and uniformly dripped, reacted for 2 hours each, and then added 50% Caustic soda 182 g (2.275 mol) and 465 g (5.812 mol) were divided into two portions and uniformly dripped for 60 minutes and 180 minutes, respectively, and the reaction was carried out in the same manner as in Example 1, except that the reaction was carried out for 1 hour. . The final resin had an epoxy equivalent of 181 g/eq, a chlorine content of 560 ppm, and a viscosity of 1640 cps. In this case, the resin is represented by Formula 1, and contains 58 mol% of a compound having n=0, 32 mol% of a compound having n=1, and 10 mol% of a compound having n=2 or more.
비교예 1. 에폭시 수지의 제조Comparative Example 1. Preparation of epoxy resin
50% 가성소다 48 g(0.599 몰)을 대신하여 BTMAC(benzyl trimethyl ammonium chloride) 2.5 g(0.5 wt%)을 투입하여 반응을 수행한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다. 최종 수지의 에폭시 당량은 193 g/eq, 염소분 177 ppm, 점도 2403 cps였다. 이때 수지는 상기 화학식 1로 표시되며, n=0인 화합물 47 몰%, n=1인 화합물 42 몰%, n=2 이상인 화합물 11 몰%을 포함하였다.The reaction was carried out in the same manner as in Example 1, except that 2.5 g (0.5 wt%) of benzyl trimethyl ammonium chloride (BTMAC) was added instead of 48 g (0.599 mol) of 50% caustic soda. The final resin had an epoxy equivalent of 193 g/eq, a chlorine content of 177 ppm, and a viscosity of 2403 cps. In this case, the resin is represented by Formula 1, and contains 47 mol% of a compound of n=0, 42 mol% of a compound of n=1, and 11 mol% of a compound of n=2 or more.
비교예 2. 에폭시 수지의 제조Comparative Example 2. Preparation of epoxy resin
용제 이소프로필 알코올(isopropyl alcohol) 1132 g, 물 300 g을 추가하여 반응을 수행한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다. 최종 수지의 에폭시 당량은 279 g/eq, 염소분 122 ppm, 점도 11270 cps였다. 이때 수지는 상기 화학식 1로 표시되며, n=0인 화합물 14 몰%, n=1인 화합물 33 몰%, n=2 이상인 화합물 53 몰%을 포함하였다.1132 g of isopropyl alcohol and 300 g of water were added and the reaction was performed in the same manner as in Example 1 above. The epoxy equivalent of the final resin was 279 g/eq, chlorine content 122 ppm, and viscosity 11270 cps. At this time, the resin is represented by Formula 1, and contains 14 mol% of a compound of n=0, 33 mol% of a compound of n=1, and 53 mol% of a compound of n=2 or more.
비교예 3. 비스페놀-A형 에폭시 수지(EEW 188 g/eq) 상용 제품(용제 사용)Comparative Example 3. Bisphenol-A type epoxy resin (EEW 188 g/eq) commercial product (using solvent)
상용 비스페놀A 에폭시 KE-8128(코오롱인더스트리 제조, EEW 188 g/eq) 112.5 g에 자일렌 50 g, MIBK 22.5 g으로 60 ℃에서 완전히 용해하여 고형분 60% 비스페놀-A 에폭시 용액을 제조하였다. Commercially available bisphenol A epoxy KE-8128 (manufactured by Kolon Industries, EEW 188 g/eq) was completely dissolved in 112.5 g of xylene 50 g and MIBK 22.5 g at 60° C. to prepare a bisphenol-A epoxy solution having a solid content of 60%.
비교예 4. 비스페놀-A형 에폭시(EEW 188 g/eq) 상용 제품(용제 미사용)Comparative Example 4. Bisphenol-A type epoxy (EEW 188 g/eq) commercial product (without solvent)
상용 비스페놀A 에폭시 KE-8128(코오롱인더스트리 제조, EEW 188 g/eq) 112.5 g을 용제를 투입하지 않고 고형분 100% 비스페놀-A형 에폭시 수지를 이용하였다.112.5 g of commercial bisphenol A epoxy KE-8128 (manufactured by Kolon Industries, EEW 188 g/eq) was used without adding a solvent, and 100% solid content bisphenol-A type epoxy resin was used.
아래는 상기 실시예 및 비교예의 에폭시 당량 및 염소분 분석방법이다.Below are the epoxy equivalent and chlorine content analysis methods of the Examples and Comparative Examples.
에폭시 당량 분석 방법Epoxy Equivalent Analysis Method
시료 적당량은 공전 삼각플라스크에 채취하고 1,4-다이옥세인 10 ml를 가하여 완전히 용해하였다. 용해 후 0.2 N HCl(다이옥세인) 25 ml를 정확히 가했다. An appropriate amount of the sample was collected in a static Erlenmeyer flask and completely dissolved by adding 10 ml of 1,4-dioxane. After dissolution, exactly 25 ml of 0.2 N HCl (dioxane) was added.
뚜껑을 닫고 플라스크와의 경계에 다이옥세인 한 두방울을 떨어뜨려 닫은 후 30 분 간 실온에서 반응시켰다. 반응 후 약 10 ml 2-메톡시에탄올로 플라스크 및 마개를 씻어 플라스크에 포함시켰다. Close the lid and drop one or two drops of dioxane on the boundary with the flask, and then react at room temperature for 30 minutes. After the reaction, the flask and stopper were washed with about 10 ml 2-methoxyethanol and included in the flask.
크레졸 레드 지시약을 3 방울 가하고 0.1 NaOH(메탄올) 용액으로 핑크색에서 황색으로 변하고 자색이 된 지점을 종점으로 하여 적정했다. 동시에 공시험(blank test)을 실시하였다.3 drops of cresol red indicator were added, and titration was performed with a 0.1 NaOH (methanol) solution at the point where the color changed from pink to yellow and became purple as the endpoint. At the same time, a blank test was performed.
*계산 방법*Calculation method
당량(g/eq)= 10,000 x W/(B-A) x FEquivalent (g/eq) = 10,000 x W/(B-A) x F
B: 공시험 적정시 0.1 N NaOH(메탄올) 소비량(ml)B: 0.1 N NaOH (methanol) consumption during blank titration (ml)
A: 샘플 적정시 0.1 N NaOH(메탄올) 소비량(ml)A: 0.1 N NaOH (methanol) consumption (ml) for sample titration
F: 0.1 N NaOH(메탄올) FactorF: 0.1 N NaOH (methanol) Factor
W: 샘플량(g)W: Sample amount (g)
가수분해성 염소분(Hy-Cl) 분석 방법Analysis of hydrolyzable chlorine (Hy-Cl)
200 ml 삼각플라스크에 시료를 채취하여 0.1 mg까지 정평하였다. 1,4-다이옥세인 25 ml를 가하여 용해한 후 0.1 N KOH(메탄올)용액 25 ml를 가하고 유리냉각관을 부착하여 70 ℃ 수조(water bath)에서 30 분간 반응하였다. 실온까지 냉각 후 유리냉각관을 5-10 ml의 메탄올로 세정하여 플라스크에 더했다. 삼각플라스크 내 용액을 200 ml 비이커에 옮기고 다시 80% 아세톤으로 삼각플라스크를 2-3 회 세정하여 세정액을 비이커에 가하고 전량을 100 ml로 하였다. 아세트산 3 ml를 가하고 0.01 N AgNO3 수용액으로 적정했다. 측정은 2 점을 동시에 수행하고 측정치의 차이가 0.003% 이내의 경우 그 평균치를 소수점 셋째자리까지 기록했다. 동시에 공시험을 실시하였다.A sample was collected in a 200 ml Erlenmeyer flask and calibrated to 0.1 mg. After dissolving by adding 25 ml of 1,4-dioxane, 25 ml of a 0.1 N KOH (methanol) solution was added, and a glass cooling tube was attached, followed by reaction in a water bath at 70° C. for 30 minutes. After cooling to room temperature, the glass cooling tube was washed with 5-10 ml of methanol and added to the flask. The solution in the Erlenmeyer flask was transferred to a 200 ml beaker, the Erlenmeyer flask was washed 2-3 times with 80% acetone again, and the washing solution was added to the beaker, and the total amount was 100 ml. 3 ml of acetic acid was added and titrated with 0.01 N AgNO 3 aqueous solution. Measurements were performed at two points simultaneously, and if the difference between the measurements was within 0.003%, the average value was recorded to the third decimal place. At the same time, a blank test was conducted.
*계산 방법*Calculation method
염소분(%) = {[(V-B) x 0.01 x 35.5 x F] / (1,000 x W)} x 100 Chlorine content (%) = {[(V-B) x 0.01 x 35.5 x F] / (1,000 x W)} x 100
V: 샘플 적정시 0.01 N AgNO3 소비량(ml)V: 0.01 N AgNO 3 consumption during sample titration (ml)
B: 공시험 적정시 0.01 N AgNO3 소비량(ml)B: 0.01 N AgNO 3 consumption (ml) during blank titration
F: 0.01N AgNO3 FactorF: 0.01N AgNO 3 Factor
W: 샘플량(g) W: Sample amount (g)
실험예 1. 도료 성능 평가Experimental Example 1. Evaluation of paint performance
도막 형성film formation
상기 실시예 및 비교예의 수지를 이용하여 액상 도료를 제조하였고, 도막을 형성하였다.Liquid paints were prepared using the resins of Examples and Comparative Examples, and a coating film was formed.
원형 플라스틱 용기에 상기 실시예 및 비교예에 따라 제조한 수지 144 g(27.54%)을 투입하고, 습윤제(wetting agent) 2 g(0.38 g)과 소야 레시틴(Soya lecithin) 5 g(0.96%)을 투입하고 교반하면서, 벤톤(bentone) 10 g(1.91%)을 조금씩 투입하였다. 이어서, TiO2, 탈크(Talc), 산화철흑(iron oxide black)를 각각 80 g(15.29%), 280 g(53.54%), 2 g(0.38%)을 투입한 뒤 1000 rpm의 속도로 15 분간 교반하였다.144 g (27.54%) of the resin prepared according to the above Examples and Comparative Examples was put into a circular plastic container, and 2 g (0.38 g) of a wetting agent and 5 g (0.96%) of Soya lecithin were added. While adding and stirring, 10 g (1.91%) of bentone was added little by little. Then, TiO 2 , talc (Talc), iron oxide black (iron oxide black) 80 g (15.29%), 280 g (53.54%), 2 g (0.38%) was added, respectively, after 15 minutes at a speed of 1000 rpm stirred.
교반한 혼합물에 글라스 비드(glass bead)를 종이컵 기준으로 1.5 컵 투입하였다. 쉐이커(shaker)를 이용하여 분산시키고, 20 분마다 입도를 측정하여 입도가 40 μm 이하가 되었을 때, 분산을 종결하였다. 글라스 비드를 걸러내어 주제 제조를 완료하였다.1.5 cups of glass beads were added to the stirred mixture based on a paper cup. It was dispersed using a shaker, and the particle size was measured every 20 minutes. When the particle size became 40 μm or less, the dispersion was terminated. The glass beads were filtered to complete the preparation of the subject matter.
펜알카민(phenalkamine)류의 경화제인 LITE 2002(AHEW = 104 g/eq)와 상기 제조한 주제를 에폭시와 활성수소 당량비 1:1로 혼합하여 유리 시편과 철 시편에 각각 75 μm, 120 μm 두께로 도포한 후 실온에서 완전 건조하여 도막을 형성하였다.By mixing LITE 2002 (AHEW = 104 g/eq), a phenalkamine-type curing agent, and the above-prepared main agent at an equivalent ratio of epoxy and active hydrogen of 1:1, the glass and iron samples were applied to a thickness of 75 μm and 120 μm, respectively. After coating, it was completely dried at room temperature to form a coating film.
아래에 도료 성능 평가 방법을 기재하였다.The paint performance evaluation method is described below.
(1) 건조속도: ASTM D5895(1) Drying rate: ASTM D5895
건조속도 자동 측정 장비를 이용하여 시간이 경과함에 따라 도장면에 기록된 모양을 보고 판단하였다.It was judged by looking at the shape recorded on the painted surface over time using an automatic drying speed measuring device.
(2) 접착력: ASTM D4541(Dolly test)(2) Adhesion: ASTM D4541 (Dolly test)
도막 표면에 Dolly를 부착한 후, Dolly가 떨어지기 위해 필요한 힘을 휴대용 접착력 테스트 기기를 이용하여 측정하였다.After attaching the dolly to the surface of the coating film, the force required for the dolly to fall was measured using a portable adhesion test device.
(3) 굴곡접착력(내굴곡성): ASTM E643(Erichen Cupping test)(3) Flexural adhesion (flex resistance): ASTM E643 (Erichen Cupping test)
도막에 압입(눌러서 밀어넣는 것)에 의한 점진적인 변형을 가했을 때, 균열 발생 저항성이나 금속 소지로부터의 박리 저항성을 평가하였다.When a gradual deformation by press-fitting (pressing in) was applied to the coating film, the crack generation resistance and peeling resistance from the metal substrate were evaluated.
(4) 내충격성: ASTM D2794(4) Impact resistance: ASTM D2794
Dupont식 충격 시험기를 이용하여 1 kg의 하중을 가진 추로 45 cm의 높이로 낙하하여, 코팅막이 박리되지 않으면 양호, 코팅막이 박리되면 불량으로 평가하였다.Using a Dupont-type impact tester, it was dropped to a height of 45 cm with a weight of 1 kg and evaluated as good if the coating film was not peeled off, and bad if the coating film was peeled off.
(5) 내용제성 및 내산/내염기성(5) Solvent resistance and acid/base resistance
각각의 도막에 자일렌, 5% 황산 수용액, 5% 가성소다를 떨어뜨려 상온에서 72 시간 방치한 후, 도막의 손상 정도를 육안으로 판정하였다.After dropping xylene, 5% sulfuric acid aqueous solution, and 5% caustic soda on each coating film and leaving it at room temperature for 72 hours, the degree of damage to the coating film was visually determined.
(6) 표면 광택도(6) surface glossiness
도료 도막의 30ㅀ경면 광택도를 반사계로 측정하였다.The 30° mirror glossiness of the paint film was measured with a reflectometer.
상기의 방법으로 상술한 바와 같이 제조된 도막의 물성을 다음과 같이 측정하였으며, 그 결과를 하기 표 1에 나타내었으며, 물성의 구체적인 수치는 하기 표 2에 나타내었다.The physical properties of the coating film prepared as described above by the above method were measured as follows, and the results are shown in Table 1 below, and specific values of the physical properties are shown in Table 2 below.
실시예 1Example 1 | 실시예 2Example 2 | 실시예 3Example 3 | 비교예 1Comparative Example 1 | 비교예 2Comparative Example 2 | 비교예 3Comparative Example 3 | 비교예 4Comparative Example 4 | ||
건조속도drying speed | ◎◎ | ◎◎ | ○○ | △△ |
도막 형성 불가film formation impossible |
XX |
도막 형성 불가film formation impossible |
|
접착력adhesion | ◎◎ | ◎◎ | ◎◎ | △△ | △△ | |||
내굴곡성Flexibility | ○○ | ○○ | ○○ | XX | △△ | |||
내충격성impact resistance | ○○ | ○○ | ○○ | XX | △△ | |||
내화학성chemical resistance | 내용제성solvent resistance | ◎◎ | ○○ | ○○ | △△ | △△ | ||
산/염기acid/base | ○○ | ○○ | ○○ | XX | △△ | |||
표면 광택도surface gloss | ◎◎ | ◎◎ | ○○ | △△ | △△ |
◎: 매우 양호, ○: 양호, △: 보통, X: 불량◎: Very good, ○: Good, △: Normal, X: Poor
실시예1Example 1 | 실시예 2Example 2 | 실시예 3Example 3 | 비교예 1Comparative Example 1 | 비교예 2Comparative Example 2 | 비교예 3Comparative Example 3 | 비교예 4Comparative Example 4 | |
건조속도(분)Drying speed (min) | 173173 | 207207 | 235235 | 291291 |
도막 형성 불가film formation impossible |
359359 |
도막 형성 불가film formation impossible |
접착력(MPa)Adhesion (MPa) | 7.57.5 | 7.67.6 | 7.37.3 | 5.65.6 | 5.35.3 | ||
내굴곡성(mm)Flexibility (mm) | 6.96.9 | 6.76.7 | 6.76.7 | 5.85.8 | 6.36.3 | ||
표면광택도surface gloss | 30.930.9 | 31.131.1 | 28.928.9 | 20.520.5 | 19.819.8 |
상기 표 1 및 2에 나타낸 바와 같이, 상기 비교예 2 및 4는 용제 또는 희석제 없이는 높은 점도에 의하여 도막을 형성되지 않음을 확인하였다. 비교예 1의 에폭시 수지의 경우 용제의 혼합 없이도 도막이 형성되었으나, 용제를 혼합한 비교예 3의 도막에 비하여 건조속도를 제외하고는 내굴곡성, 내충격성, 내산/염기성 등 전반적인 물성이 불량하였다. As shown in Tables 1 and 2, in Comparative Examples 2 and 4, it was confirmed that a coating film was not formed due to high viscosity without a solvent or diluent. In the case of the epoxy resin of Comparative Example 1, a coating film was formed without mixing of a solvent, but compared to the coating film of Comparative Example 3 in which a solvent was mixed, overall physical properties such as bending resistance, impact resistance, acid/base resistance, etc. were poor except for the drying speed.
한편, 실시예 1 내지 3의 에폭시 수지는 용제 혼합 없이도 도막 형성이 가능하여, 무용제형 도료로 사용될 수 있음을 확인하였으며, 접착력, 내굴곡성, 내충격성, 내화학성, 표면 광택도 등 전반적인 물성이 비교예 1의 수지는 물론 용제형 비스페놀-A형 에폭시 수지를 사용한 도막에 비해서도 우수하였으며, 건조속도 역시 크게 단축된 효과를 확인할 수 있었다.
On the other hand, it was confirmed that the epoxy resins of Examples 1 to 3 can form a coating film without solvent mixing and can be used as a solvent-free paint, and overall physical properties such as adhesion, bending resistance, impact resistance, chemical resistance, and surface gloss are compared. It was superior to the coating film using the solvent-type bisphenol-A type epoxy resin as well as the resin of Example 1, and it was confirmed that the drying rate was also greatly shortened.
따라서, 본 발명에 따른 에폭시 수지는 낮은 점도를 바탕으로 용제 및/또는 희석제의 배합 없이 도료로 사용될 수 있으며, 상기 에폭시 수지를 포함하는 에폭시 도료 조성물을 이용한 제막에서 기존 도막과 비교하여 건조 속도가 현저히 개선되며, 전반적인 물성이 동등 이상 수준을 갖는 도막을 제조할 수 있다. Therefore, the epoxy resin according to the present invention can be used as a paint without mixing a solvent and/or a diluent based on a low viscosity, and the drying rate is significantly higher than that of the existing coating film in film forming using the epoxy paint composition containing the epoxy resin. It is improved, and it is possible to manufacture a coating film having an equivalent or higher level of overall physical properties.
전술한 실시예 및 비교예는 본 발명을 설명하기 위한 예시로서, 본 발명이 이에 한정되는 것은 아니다. 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 이로부터 다양하게 변형하여 본 발명을 실시하는 것이 가능할 것이므로, 본 발명의 기술적 보호범위는 첨부된 특허청구범위에 의해 정해져야 할 것이다.The above-described Examples and Comparative Examples are examples for explaining the present invention, but the present invention is not limited thereto. Those of ordinary skill in the art to which the present invention pertains will be able to practice the present invention with various modifications therefrom, so the technical protection scope of the present invention should be defined by the appended claims.
Claims (15)
- 하기 화학식 1로 표시되고, Represented by the following formula (1),하기 화학식 1에서 n=0인 화합물, n=1인 화합물 및 n=2인 화합물의 혼합물을 포함하는 에폭시 수지:An epoxy resin comprising a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1):[화학식 1][Formula 1]상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
- 제2항에 있어서, 3. The method of claim 2,상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 것인 에폭시 수지.The epoxy resin is an epoxy resin comprising 50 mol% or more of the compound of n = 0 in Formula 1 above.
- 제1항 또는 제2항에 있어서, 3. The method of claim 1 or 2,상기 에폭시 수지는 상기 화학식 1에서 n=0 내지 1인 화합물을 90 몰% 이상 포함하는 것인 에폭시 수지.The epoxy resin is an epoxy resin comprising 90 mol% or more of the compound of n = 0 to 1 in Formula 1 above.
- 제1항 또는 제2항에 있어서, 3. The method of claim 1 or 2,상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 내지 90 몰%,The epoxy resin is 50 to 90 mol% of the compound of n = 0 in Formula 1,n=1인 화합물을 5 내지 40 몰% 및5 to 40 mol% of a compound with n=1 andn=2 이상인 화합물을 1 내지 11 몰% 포함하는 것인 에폭시 수지.An epoxy resin comprising 1 to 11 mol% of a compound of n = 2 or more.
- 제1항 또는 제2항에 있어서, 3. The method of claim 1 or 2,상기 에폭시 수지의 점도는 25 ℃에서 점도는 2000 cps 이하이고, 에폭시 당량이 120 내지 185 g/eq인 에폭시 수지.The viscosity of the epoxy resin is 2000 cps or less at 25 ℃, the epoxy equivalent of the epoxy resin of 120 to 185 g / eq.
- 하기 화학식 1로 표시되는 에폭시 수지를 포함하고, Including an epoxy resin represented by the following formula (1),상기 에폭시 수지는 하기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 것인 에폭시 도료 조성물:The epoxy resin is an epoxy paint composition comprising 50 mol% or more of a compound having n = 0 in the following formula (1):[화학식 1][Formula 1]상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
- 하기 화학식 1로 표시되는 에폭시 수지를 포함하고,Including an epoxy resin represented by the following formula (1),상기 에폭시 수지는 하기 화학식 1에서 n=0인 화합물, n=1인 화합물 및 n=2인 화합물의 혼합물을 포함하는 것인 에폭시 도료 조성물:The epoxy resin is an epoxy paint composition comprising a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1):[화학식 1][Formula 1]상기 화학식 1에서 n은 0 내지 4의 정수이다.In Formula 1, n is an integer of 0 to 4.
- 제8항에 있어서,9. The method of claim 8,상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 몰% 이상 포함하는 것인 에폭시 도료 조성물.The epoxy resin is an epoxy paint composition comprising 50 mol% or more of the compound of n = 0 in Formula 1 above.
- 제7항 또는 제8항에 있어서,9. The method of claim 7 or 8,상기 에폭시 수지는 상기 화학식 1에서 n=0 내지 1인 화합물을 90 몰% 이상 포함하는 것인 에폭시 도료 조성물.The epoxy resin is an epoxy paint composition comprising 90 mol% or more of the compound having n = 0 to 1 in Formula 1 above.
- 제7항 또는 제8항에 있어서,9. The method of claim 7 or 8,상기 에폭시 수지는 상기 화학식 1에서 n=0인 화합물을 50 내지 90 몰%,The epoxy resin is 50 to 90 mol% of the compound of n = 0 in Formula 1,n=1인 화합물을 5 내지 40 몰% 및5 to 40 mol% of a compound with n=1 andn=2 이상인 화합물을 1 내지 11 몰% 포함하는 것인 에폭시 도료 조성물.An epoxy paint composition comprising 1 to 11 mol% of a compound of n=2 or more.
- 제7항 또는 제8항에 있어서,9. The method of claim 7 or 8,상기 에폭시 수지의 점도는 25 ℃에서 점도는 2000 cps 이하이고, 에폭시 당량이 120 내지 185 g/eq인 에폭시 도료 조성물.The viscosity of the epoxy resin is 2000 at 25 ° C. cps or less and an epoxy equivalent of 120 to 185 g/eq.
- 제7항 또는 제8항에 있어서,9. The method of claim 7 or 8,상기 에폭시 도료 조성물은 상기 에폭시 수지를 포함하는 주제부 및 경화제부를 포함하고,The epoxy paint composition includes a main part and a curing agent part containing the epoxy resin,상기 주제부는 상기 주제부 100 중량부를 기준으로 상기 에폭시 수지를 5 내지 50 중량부 및 안료 50 내지 95 중량부 포함하는 에폭시 도료 조성물.The main part is an epoxy paint composition comprising 5 to 50 parts by weight of the epoxy resin and 50 to 95 parts by weight of the pigment based on 100 parts by weight of the main part.
- 제7항 또는 제8항에 따른 에폭시 도료 조성물로 형성된 도막.A coating film formed of the epoxy paint composition according to claim 7 or 8.
- 제14항에 따른 도막과 기재를 포함하는 도막 부착 기재.A substrate with a coating film comprising the coating film according to claim 14 and the substrate.
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