WO2021010787A2 - Solventless epoxy paint composition, and marine structure and ship tank which comprise coating formed therefrom - Google Patents

Solventless epoxy paint composition, and marine structure and ship tank which comprise coating formed therefrom Download PDF

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Publication number
WO2021010787A2
WO2021010787A2 PCT/KR2020/009438 KR2020009438W WO2021010787A2 WO 2021010787 A2 WO2021010787 A2 WO 2021010787A2 KR 2020009438 W KR2020009438 W KR 2020009438W WO 2021010787 A2 WO2021010787 A2 WO 2021010787A2
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Prior art keywords
weight
parts
solvent
content
coating composition
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PCT/KR2020/009438
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French (fr)
Korean (ko)
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WO2021010787A3 (en
Inventor
황경섭
신상문
소용신
추승곤
우범철
사공성
김태희
이도형
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주식회사 케이씨씨
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Priority to CN202080051063.3A priority Critical patent/CN114207060A/en
Publication of WO2021010787A2 publication Critical patent/WO2021010787A2/en
Publication of WO2021010787A3 publication Critical patent/WO2021010787A3/en

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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
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • 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
    • C08G59/68—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 catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the present invention relates to a tank of a marine structure and a ship including a solvent-free epoxy coating composition and a coating film formed therefrom.
  • Such a solvent-free epoxy coating composition is generally an extender pigment and includes at least one selected from silica, barite (natural barium sulfate), blanc fixe (synthetic barium sulfate), talc, and calcium carbonate.
  • these extender pigments are applied to solvent-free epoxy paints, their oil absorption is high, causing high viscosity and agglomeration under low temperature conditions of 10 °C or less, resulting in poor patterns or poor flowability during airless spraying. There is a problem in that airless spray coating workability is inferior in low temperature conditions such as that.
  • the present invention was created to solve the problems of the prior art as described above, and an object of the present invention is to provide a solvent-free epoxy coating composition having excellent workability while maintaining excellent rust and corrosion resistance when applied to a ship paint. .
  • a solvent-free epoxy coating composition includes an epoxy resin containing two or more epoxy groups in a molecule, a reactive diluent containing an epoxy group, a first non-reactive diluent containing a hydroxy group, and a subject including feldspar, and It is characterized by comprising a curing agent comprising an aliphatic amine, an alicyclic amine, a second non-reactive diluent containing a hydroxy group, and a curing accelerator.
  • the curing agent based on 100 parts by weight of the curing agent, the content of the aliphatic amine is 40 parts by weight or more and 60 parts by weight or less, and the content of the alicyclic amine may be 15 parts by weight or more and 35 parts by weight or less. It is not limited.
  • the content of the feldspar may be 20 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the subject, but is not limited thereto.
  • the content of the epoxy resin may be 30 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the subject, but is not limited thereto.
  • the content of the reactive diluent may be 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the subject matter, but is not limited thereto.
  • the content of the first non-reactive diluent may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the subject, but is not limited thereto.
  • the content of the second non-reactive diluent may be 10 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the curing agent, but is not limited thereto.
  • the content of the curing accelerator may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the curing agent, but is not limited thereto.
  • the weight ratio of the subject and the curing agent may be 75:25 to 85:15.
  • the marine structure according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
  • a tank of a ship according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
  • the solvent-free epoxy coating composition according to the present invention can implement a coating film having excellent rust prevention and corrosion resistance.
  • the solvent-free epoxy coating composition according to the present invention can improve the patterning workability of airless spray coating under low temperature conditions of 10° C. or less.
  • the solvent-free epoxy coating composition according to the present invention can improve pot life in a high temperature condition of 35° C. or higher.
  • the unit "part by weight” may mean a ratio of weight between each component.
  • the present inventors When using feldspar as an extender pigment included in the solvent-free epoxy paint composition, the present inventors have high hardness while maintaining the general net function of the extender pigment, thereby improving the hardness of the paint, thereby having excellent abrasion resistance and low oil absorption at 10 °C. It was found that a coating composition having excellent airless spray coating workability can be prepared under the following low temperature conditions. In addition, it was found that the airless spray coating workability and coating properties of the coating composition can be improved by controlling the content of the aliphatic amine and the alicyclic amine contained in the curing agent. Accordingly, the following solvent-free epoxy coating composition was developed.
  • the epoxy resin according to an embodiment of the present invention may include a solvent-free epoxy resin having a solid content volume ratio of 95% or more with little content of a volatile solvent.
  • a coating composition containing an epoxy resin having a solid content volume ratio of 95% or more can implement a coating film having excellent physical properties such as corrosion resistance and seawater resistance.
  • the epoxy equivalent (EEW) of the epoxy resin is not limited thereto, but may be, for example, 160 g/eq or more and 220 g/eq or less. Specifically, the epoxy equivalent of the epoxy resin may be 170 g/eq or more and 200 g/eq or less, or 175 g/eq or more and 190 g/eq or less.
  • the epoxy resin is not limited thereto, but may include, for example, at least one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin having two or more epoxy groups in a molecule.
  • the epoxy resin may include at least one of bisphenol-A diglycidyl ether (DGEBA) and bisphenol-F (BPF) diglycidyl ether.
  • the content of the epoxy resin is not limited thereto, for example, 30 parts by weight or more and 50 parts by weight or less, specifically 35 parts by weight or more and 45 parts by weight or less, 30 parts by weight or more and 42.5 parts by weight, based on 100 parts by weight of the subject. It may be less than or equal to 40 parts by weight or more and 50 parts by weight or less.
  • the viscosity of the coating composition increases as the pigment content increases, so that the workability and the appearance of the coating film can be suppressed from becoming inferior, and the coating film properties such as rust prevention property and seawater resistance decrease. Can be suppressed.
  • the pot life of the solvent-free epoxy coating composition can be improved, and mechanical properties such as coating film hardness can be suppressed from being deteriorated, but the effect of the present invention is limited thereto. It does not become.
  • the solvent-free epoxy coating composition according to an embodiment of the present invention includes a diluent in each of the main material and the curing agent, thereby overcoming the limitations of pigment application due to the high viscosity of the epoxy resin, and maintaining the viscosity at which airless spray painting work is possible. I can.
  • the solvent-free epoxy coating composition according to an embodiment of the present invention may include a reactive diluent and a non-reactive diluent in the main material, and may include a non-reactive diluent in the curing agent.
  • the non-reactive diluent included in the subject matter in the present specification is referred to as a first non-reactive diluent
  • the non-reactive diluent included in the curing agent is used as the second non-reactive diluent.
  • the reactive diluent included in the subject contains an epoxy group, and thus participates in the reaction with the curing agent to form a part of the cured coating film. Meanwhile, the first non-reactive diluent included in the subject and the second non-reactive diluent included in the curing agent do not participate in the curing reaction, but remain in the coating film and may affect the physical properties of the coating film.
  • the content of the reactive diluent according to an embodiment of the present invention may be 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the subject. Specifically, based on 100 parts by weight of the subject, the content of the reactive diluent may be 7 parts by weight or more and 18 parts by weight or less, or 10 parts by weight or more and 15 parts by weight or less.
  • the content of the reactive diluent is within the above-described range, it is possible to suppress a phenomenon in which mechanical properties are deteriorated and inferior airless spray coating workability as the amount of usable pigment decreases.
  • the content of the reactive diluent in the above-described range it is possible to improve coating film properties such as coating film hardness and rust prevention property, and shorten the drying time of the coating film, but the effect of the present invention is not limited thereto.
  • the epoxy equivalent of the reactive diluent is not limited thereto, but may be, for example, 150 g/eq or more and 300 g/eq or less.
  • the reactive diluent may include an alkyl glycidyl ether having the above-described epoxy equivalent.
  • the reactive diluent may include a monoepoxy type compound containing one epoxy group.
  • a reactive diluent containing a monoepoxy type compound By using a reactive diluent containing a monoepoxy type compound, the viscosity of the solvent-free epoxy coating composition can be appropriately adjusted.
  • the content of the first non-reactive diluent according to an embodiment of the present invention is 1 part by weight or more and 10 parts by weight or less, specifically 3 parts by weight or more and 8 parts by weight or less, or 4.5 parts by weight or more, based on 100 parts by weight of the subject matter. It may be less than or equal to 6.5 parts by weight.
  • the first non-reactive diluent contains a hydroxy group and may include, for example, at least one of benzyl alcohol, dodecyl phenol, and a phenol modified liquid hydrocarbon resin.
  • Feldspar included in the solvent-free epoxy coating composition according to an embodiment of the present invention has high hardness while maintaining the general net function of the extender pigment, increasing the hardness of the coating material, thereby implementing a coating film having excellent wear resistance.
  • feldspar has low oil absorption and improves the atomization degree of airless spray under low temperature conditions of 10°C or less, so that the spray patterning is good, and due to the thixotropy, the flowability is good, and the workability of airless spray painting under low temperature conditions is improved. Paint composition can be provided.
  • the content of the feldspar is not limited thereto, but may be, for example, 20 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the subject. Specifically, based on 100 parts by weight of the subject, the content of feldspar is 25 parts by weight or more and 37.5 parts by weight or less, 27 parts by weight or more and 35 parts by weight or less, 20 parts by weight or more and 32.5 parts by weight or less, or 30 parts by weight or more and 40 parts by weight. It can be below.
  • the average particle size of the feldspar is not limited thereto, but may be, for example, 1 ⁇ m or more and 75 ⁇ m or less.
  • the average particle size of the feldspar may be measured according to a method of, for example, PSA (Particle Size Analysis).
  • the solvent-free epoxy coating composition according to an embodiment of the present invention further includes an anti-settling agent, thereby solving the problem of feldspar, which is inferior in paint storage stability.
  • the anti-settling agent may be used without limitation, a conventional one known in the art, but for example, a clay type, a wax type, a urethane polymer type may be used, and preferably, a clay type anti-settling agent It may further include.
  • a clay-type anti-settling agent can improve the workability and properties of the coating film while compensating for the disadvantages of feldspar, which is inferior in coating storage stability, but the effect of the present invention is not limited thereto.
  • the content of the anti-settling agent is not limited thereto, for example, 0.5 parts by weight or more and 5 parts by weight or less, specifically 1.5 parts by weight or more and 4.5 parts by weight or less, or 2 parts by weight or more and 3.5 parts by weight, based on 100 parts by weight of the main body. It may be less than or equal to part.
  • the content of the anti-settling agent is within the above-described range, coating properties, storage stability, and workability of the solvent-free epoxy coating composition can be simultaneously secured. Specifically, by adjusting the content of the anti-settling agent in the above-described range, the workability of the paint (flowability during vertical surface coating) is prevented from deteriorating, and a coating film having excellent leveling can be implemented. In addition, it is possible to suppress a decrease in coating properties such as poor workability and water resistance due to an increase in the viscosity of the coating material, but the effect of the present invention is not limited thereto.
  • the feldspar and the anti-settling agent may be included in a weight ratio of 5:1 to 20:1 or 8:1 to 15:1, and when the weight ratio of the feldspar and the anti-settling agent is less than 5:1, the viscosity of the paint is increased As a result, workability and appearance defects may occur, and if it exceeds 20:1, the flowability during vertical surface painting may decrease, but the effect of the present invention is not limited thereto.
  • the subject matter according to an embodiment of the present invention may further include an additive including at least one of a dispersant, a defoaming agent, and a functional additive.
  • the dispersant may play a role of preventing re-aggregation of the pigments by adsorbing on the pigment surface and maintaining a constant gap between the pigment and the pigment due to electric repulsion or steric hindrance effect.
  • the dispersant used in the art may be used without limitation, and examples thereof include a silicone-based dispersant or a non-silicone-based dispersant (eg, a polycarboxylic acid polyester type dispersant).
  • the antifoaming agent is for preventing defects in the coating film such as generation of bubbles in the coating film, and when such bubbles remain in the coating film, it may cause poor adhesion to the substrate or deterioration in physical properties.
  • the antifoaming agent used in the art may be used without limitation, and examples thereof include mineral oil-based, silicone-based, non-silicone-based, and the like.
  • a silicone-based antifoaming agent is used in terms of maximizing the defoaming force. I can.
  • silicone additives such as polyethersiloxane and polyester siloxane are used as additives for preventing deterioration of defoaming, preventing occurrence of cratering, preventing color separation, removing air bubbles on the surface of the coating film, and providing smoothness of the coating film. And it may be desirable to select a type that has both leveling performance and defoaming performance.
  • the total content of the additive is not limited thereto, but may be, for example, 0.5 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the subject matter.
  • the subject according to an embodiment of the present invention may further include a colored pigment.
  • Colored pigments are used to express color on a coating film of a solvent-free epoxy coating composition, and colored pigments used in the art may be used without limitation.
  • TiO 2 etc. can be used as a white pigment
  • carbon black etc. can be used as a black pigment.
  • the content of the colored pigment is not limited thereto, but may be, for example, 7.5 parts by weight or more and 12.5 parts by weight or less based on 100 parts by weight of the subject.
  • two-component epoxy resin coatings that require rust prevention and seawater resistance are used as a curing agent along with a subject such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and the like.
  • the curing agent according to an embodiment of the present invention includes an aliphatic amine and an alicyclic amine, and amines containing active hydrogen such as ketimines prepared by condensation reaction of amines and ketones, or polyamine amides and polyamidos using these amines It may further include a modified resin such as amine, phenol-modified amine, epoxy addition-type amine.
  • the aliphatic amine may include at least one of diethylenetriamine, triethylenetetraamine, and polyoxypropylenediamine, but the type of the aliphatic amine is not limited.
  • the alicyclic amine may include at least one alicyclic group among cyclohexyl, cycloheptyl, and cyclopentyl, but the type of the alicyclic group is not limited.
  • the content of the aliphatic amine is not limited thereto, but may be, for example, 40 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the aliphatic amine is 42.5 parts by weight or more and 55 parts by weight or less, 45 parts by weight or more and 50 parts by weight or less, 40 parts by weight or more and 52.5 parts by weight or less, or 47.5 parts by weight or more and 57.5 parts by weight. It may be less than or equal to part.
  • the content of the alicyclic amine is not limited thereto, but may be, for example, 15 parts by weight or more and 35 parts by weight or less based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the alicyclic amine is 17.5 parts by weight or more and 30 parts by weight or less, 20 parts by weight or more and 28.5 parts by weight or less, 15 parts by weight or more and 27.5 parts by weight or less, or 25 parts by weight or more and 32.5 parts by weight. It may be less than or equal to parts by weight.
  • the solvent-free epoxy coating composition of the present invention can improve coating workability and coating properties by including the aliphatic amine and alicyclic amine in a weight ratio of 1:0.1 to 1.5, or 1:0.2 to 1:1.
  • the effect of the present invention is not limited thereto.
  • the second non-reactive diluent according to an embodiment of the present invention may be the same as or different from the first non-reactive diluent.
  • the content of the second non-reactive diluent is not limited thereto, but, for example, based on 100 parts by weight of the curing agent, 10 parts by weight or more and 30 parts by weight or less, specifically 15 parts by weight or more and 28 parts by weight or less, or 20 parts by weight It may be more than 25 parts by weight or less.
  • the content of the curing accelerator according to an embodiment of the present invention may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the curing accelerator may be 1.5 parts by weight or more and 8 parts by weight or less, or 2.5 parts by weight or more and 5 parts by weight or less.
  • the curing rate can be appropriately controlled. Through this, it is possible to suppress the problem that the coating film properties such as coating film hardness and brushing decrease due to an increase in the curing speed, the problem that the curing speed is increased and the pot life is reduced, and the flowability is inferior, but the effect of the present invention is limited thereto. no.
  • the curing accelerator is not limited thereto, but may include, for example, at least one of tridimethyl amino methyl phenol, triphenyl phosphite, and amino ethyl piperazine.
  • the weight ratio of the subject and the curing agent may be 75:25 to 85:15, 77.5:22.5 to 82.5:17.5, or 80:20 to 85:15. .
  • the marine structure according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
  • the coating film provided on the marine structure according to an embodiment of the present invention may include a cured product of the solvent-free epoxy coating composition.
  • a tank of a ship according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
  • the coating film provided on the tank of the ship according to an embodiment of the present invention may include a cured product of the solvent-free epoxy coating composition.
  • the tank of the ship having the coating film includes a ballast tank and a crude oil tank, and may include other tanks provided on the ship.
  • the solvent-free epoxy coating composition according to an embodiment of the present invention can be applied to severe corrosive environments such as ballast tanks and crude oil tanks of ships, and does not use any solvents harmful to the human body and environment, so construction is not possible. It can be safe.
  • the solvent-free epoxy coating composition has excellent workability due to good spray patterning during airless spray painting under low temperature conditions of 10 °C or lower, unlike conventional solvent-free epoxy paints, and pot life at high temperatures of 35 °C or higher. It is good in more than 30 minutes, so it can have the advantage of easy painting.
  • the solvent-free epoxy coating composition according to an embodiment of the present invention may be used by coating for rust prevention purposes on offshore structures such as crude oil drilling facilities in addition to a tank of a ship.
  • a subject was prepared in the composition (unit: parts by weight) as shown in Table 1 below.
  • reaction solution was prepared by adding a defoaming agent, a clay type anti-settling agent (BYK, GARAMITE 1958), and a first non-reactive diluent and stirring. After slowly adding and stirring an extender pigment to the reaction solution in the amount shown in Table 1 below, a white pigment (TiO 2 ) was slowly added and stirred as a colored pigment. Thereafter, the reaction solution was dispersed using a HSD (High Speed Dissolver) until the average particle size in the solution became 80 ⁇ m or less to prepare a main body.
  • HSD High Speed Dissolver
  • a curing agent mixture 50 parts by weight of an aliphatic amine, 25 parts by weight of an alicyclic amine, 3 parts by weight of a curing accelerator, and 22 parts by weight of a second non-reactive diluent were quantified and introduced into the reactor.
  • the reactor was mixed by low-speed stirring to prepare a curing agent mixture.
  • a solvent-free epoxy coating composition was prepared by mixing the prepared main material and the curing agent in a weight ratio of 80:20.
  • the specific composition is as described in Table 1 below.
  • a solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that a bisphenol-F type epoxy resin (epoxy equivalent 175 g/eq) was used instead of the bisphenol-A type epoxy resin.
  • the specific composition is as described in Table 1 below.
  • a solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that the bisphenol-A type epoxy resin and the bisphenol-F type epoxy resin were mixed in a weight ratio as shown in Table 1 below.
  • compositions of each of the subject and curing agent according to Examples 3 to 11 are as described in Table 1 below.
  • a solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that muscovite ore and kaolin were used instead of feldspar as extender pigments.
  • the muscovite ore and kaolin were mixed and used in a weight ratio of 20:10.
  • a solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that the contents of the bisphenol-A type epoxy resin, the aliphatic amine and the alicyclic amine were adjusted as described in Table 2 below.
  • the content (parts by weight) of the BPA resin, BPF resin, reactive diluent, dispersant, antifoaming agent, anti-settling agent, colored pigment, extender pigment, and first non-reactive diluent is 100 parts by weight It is a standard.
  • the content (parts by weight) of an aliphatic amine, an alicyclic amine, a curing accelerator, and a second non-reactive diluent is based on a total of 100 parts by weight of the curing agent.
  • rust, dust, moisture, oil and other contaminants on the surface of the substrate were completely removed using fresh water or an appropriate solvent, and then blasted to a surface roughness of 25 ⁇ m to 75 ⁇ m. Then, the prepared specimens were coated with a nozzle diameter of 0.019" to 0.025", spraying pressure of 3bar to 5bar, and spraying angle of 50° using an airless spray. Workability was evaluated through airless spray, and the workability results are shown in Tables 4 and 5.
  • the specific test method is as follows.
  • the degree of defect occurrence after 160lb.in impact was evaluated on the front and rear surfaces of the coated specimen by the method of ASTM D2794.
  • the degree of defect occurrence was evaluated after the Conical Mandrel test on the coated specimen by the method of ASTM D522.
  • the nozzle diameter was set to 0.019" to 0.025", spraying pressure 3 bar to 5 bar, spray angle 50°, and then painted, and an airless spray pattern under low temperature (10 °C or less) conditions, The maximum flowability thickness, leveling of thin film dry film (200 ⁇ m or less), and pot life under high temperature (35 °C or more) were measured.
  • Comparative Example 1 using muscovite ore and kaolin as extender pigments, it was confirmed that the spray patterning under the conditions of bending resistance and low temperature was poor.
  • the solvent-free epoxy coating composition of Comparative Example 2 including a curing agent without using an alicyclic amine was found to be poor in spray patterning under low temperature conditions, and it was confirmed that the visibility time under high temperature conditions was also poor.
  • the solvent-free epoxy coating composition of Comparative Example 3 including a curing agent without using an aliphatic amine was found to be poor in spray patterning under low temperature conditions, and it was confirmed that the seawater resistance was significantly inferior.
  • the solvent-free epoxy coating composition according to Comparative Example 4 has poor pot life, It was confirmed that the solvent-free epoxy coating composition according to Comparative Examples 4 and 5 was inferior in seawater resistance.
  • the solvent-free epoxy coating composition according to Comparative Example 6 is spray patterning under low temperature conditions, visibility time under high temperature conditions, and It was confirmed that the bending resistance was poor, and the solvent-free epoxy coating composition according to Comparative Example 7 was inferior in seawater resistance and bending resistance.
  • the solvent-free epoxy coating composition according to an embodiment of the present invention has excellent airless spray coating workability and pot life, and can implement a coating film having excellent physical properties.
  • the present invention is not limited to the above-described embodiments, and may include a combination of the above embodiments or a combination of at least one of the above embodiments and a known technology as another embodiment.

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Abstract

The present invention relates to a solventless epoxy paint composition, and a marine structure and a ship tank which comprise a coating formed therefrom. The solventless epoxy paint composition of the present invention comprises: a base comprising an epoxy resin containing two or more epoxy groups in a molecule, a reactive diluent containing an epoxy group, a first nonreactive diluent containing a hydroxyl group, and feldspar; and a curing agent comprising an aliphatic amine, an alicyclic amine, a second nonreactive diluent containing a hydroxyl group, and a curing accelerator.

Description

무용제형 에폭시 도료 조성물 및 이로부터 형성되는 도막을 포함하는 해양 구조물, 선박의 탱크Offshore structures including solvent-free epoxy coating compositions and coating films formed therefrom, tanks of ships
본 발명은 무용제형 에폭시 도료 조성물 및 이로부터 형성되는 도막을 포함하는 해양 구조물, 선박의 탱크에 관한 것이다.The present invention relates to a tank of a marine structure and a ship including a solvent-free epoxy coating composition and a coating film formed therefrom.
선박의 밸러스트(ballast) 탱크, 원유(crude oil) 탱크 및 해양 구조물의 해수 침지 부위 등의 혹독한 부식 환경에 적용 가능한 무용제 에폭시 도료 조성물에 대한 개발 및 사용이 증대되고 있다.Development and use of solvent-free epoxy coating compositions applicable to severe corrosive environments such as ballast tanks, crude oil tanks, and seawater immersion sites of marine structures are increasing.
이러한 무용제 에폭시 도료 조성물은 일반적으로 체질안료로, 실리카, 바라이트(barite, 천연바륨설페이트), 블랑픽스(blanc fixe, 합성바륨설페이트), 탈크 및 탄산 칼슘 중에서 선택된 1종 이상을 포함한다. 다만, 이러한 체질안료는 무용제 에폭시 도료에 적용 시에 흡유량이 높아 10 ℃ 이하의 저온 조건에서 고점도 및 뭉침 현상이 발생하여 에어리스 스프레이(Airless Spray) 작업 시의 패턴(pattern)이 불량하거나 흐름성이 열세하게 되는 등, 저온 조건에서의 에어리스 스프레이 도장 작업성이 열등한 문제가 있다.Such a solvent-free epoxy coating composition is generally an extender pigment and includes at least one selected from silica, barite (natural barium sulfate), blanc fixe (synthetic barium sulfate), talc, and calcium carbonate. However, when these extender pigments are applied to solvent-free epoxy paints, their oil absorption is high, causing high viscosity and agglomeration under low temperature conditions of 10 ℃ or less, resulting in poor patterns or poor flowability during airless spraying. There is a problem in that airless spray coating workability is inferior in low temperature conditions such as that.
또한, 종래의 무용제 에폭시 도료 조성물 대비, 35 ℃ 이상의 고온 조건에서 가사 시간(pot life)이 우수한 무용제 에폭시 도료 조성물에 대한 수요가 증가하고 있으며, 이에 대한 연구가 진행되고 있다.In addition, compared to the conventional solvent-free epoxy coating composition, there is an increasing demand for a solvent-free epoxy coating composition having excellent pot life at a high temperature of 35° C. or higher, and research on this is being conducted.
본 발명은 상기와 같은 종래기술의 문제점을 해결하고자 창출된 것으로서, 본 발명의 목적은, 선박 도료에 적용 시 우수한 방청성 및 방식성은 유지하면서도, 작업성이 우수한 무용제형 에폭시 도료 조성물을 제공하기 위한 것이다.The present invention was created to solve the problems of the prior art as described above, and an object of the present invention is to provide a solvent-free epoxy coating composition having excellent workability while maintaining excellent rust and corrosion resistance when applied to a ship paint. .
본 발명의 일 측면에 따른 무용제형 에폭시 도료 조성물은, 분자 중에 2개 이상의 에폭시기를 함유하는 에폭시 수지, 에폭시기를 함유하는 반응성 희석제, 히드록시기를 함유하는 제1 비반응성 희석제, 및 장석을 포함하는 주제 및 지방족 아민, 지환족 아민, 히드록시기를 함유하는 제2 비반응성 희석제, 및 경화 촉진제를 포함하는 경화제를 포함하는 것을 특징으로 한다.A solvent-free epoxy coating composition according to an aspect of the present invention includes an epoxy resin containing two or more epoxy groups in a molecule, a reactive diluent containing an epoxy group, a first non-reactive diluent containing a hydroxy group, and a subject including feldspar, and It is characterized by comprising a curing agent comprising an aliphatic amine, an alicyclic amine, a second non-reactive diluent containing a hydroxy group, and a curing accelerator.
구체적으로, 상기 경화제는, 상기 경화제 100 중량부 기준으로, 상기 지방족 아민의 함량은 40 중량부 이상 60 중량부 이하이고, 상기 지환족 아민의 함량은 15 중량부 이상 35 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, the curing agent, based on 100 parts by weight of the curing agent, the content of the aliphatic amine is 40 parts by weight or more and 60 parts by weight or less, and the content of the alicyclic amine may be 15 parts by weight or more and 35 parts by weight or less. It is not limited.
구체적으로, 상기 주제는, 상기 장석의 함량이 상기 주제 100 중량부를 기준으로, 20 중량부 이상 40 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, in the subject matter, the content of the feldspar may be 20 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the subject, but is not limited thereto.
구체적으로, 상기 주제는, 상기 에폭시 수지의 함량이 상기 주제 100 중량부를 기준으로, 30 중량부 이상 50 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, in the subject matter, the content of the epoxy resin may be 30 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the subject, but is not limited thereto.
구체적으로, 상기 주제는, 상기 반응성 희석제의 함량이 상기 주제 100 중량부를 기준으로, 5 중량부 이상 20 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, in the subject matter, the content of the reactive diluent may be 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the subject matter, but is not limited thereto.
구체적으로, 상기 주제는, 상기 제1 비반응성 희석제의 함량이 상기 주제 100 중량부를 기준으로, 1 중량부 이상 10 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, in the subject matter, the content of the first non-reactive diluent may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the subject, but is not limited thereto.
구체적으로, 상기 경화제는, 상기 제2 비반응성 희석제의 함량이 상기 경화제 100 중량부를 기준으로, 10 중량부 이상 30 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, the content of the second non-reactive diluent may be 10 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the curing agent, but is not limited thereto.
구체적으로, 상기 경화제는, 상기 경화 촉진제의 함량이 상기 경화제 100 중량부를 기준으로, 1 중량부 이상 10 중량부 이하일 수 있으나, 이에 제한되는 것은 아니다.Specifically, the content of the curing accelerator may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the curing agent, but is not limited thereto.
구체적으로, 상기 주제와 상기 경화제의 중량비는 75:25 내지 85:15일 수 있다.Specifically, the weight ratio of the subject and the curing agent may be 75:25 to 85:15.
본 발명의 일 측면에 따른 해양 구조물은 상기 무용제형 에폭시 도료 조성물로부터 형성되는 도막을 포함하는 것을 특징으로 한다.The marine structure according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
본 발명의 일 측면에 따른 선박의 탱크는 상기 무용제형 에폭시 도료 조성물로부터 형성되는 도막을 포함하는 것을 특징으로 한다.A tank of a ship according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
본 발명에 따른 무용제형 에폭시 도료 조성물은, 우수한 방청성 및 방식성을 갖는 도막을 구현할 수 있다.The solvent-free epoxy coating composition according to the present invention can implement a coating film having excellent rust prevention and corrosion resistance.
본 발명에 따른 무용제형 에폭시 도료 조성물은, 10 ℃ 이하의 저온 조건에서 에어리스 스프레이 도장의 패터닝 작업성을 향상시킬 수 있다.The solvent-free epoxy coating composition according to the present invention can improve the patterning workability of airless spray coating under low temperature conditions of 10° C. or less.
본 발명에 따른 무용제형 에폭시 도료 조성물은, 35 ℃ 이상의 고온 조건에서의 가사 시간을 개선할 수 있다. The solvent-free epoxy coating composition according to the present invention can improve pot life in a high temperature condition of 35° C. or higher.
본 발명의 효과는 상술한 효과로 한정되는 것은 아니며, 언급되지 아니한 효과들은 본원 명세서로부터 당업자에게 명확히 이해될 수 있을 것이다.The effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification.
본원 명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있음을 의미한다.In the entire specification of the present application, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.
본원 명세서 전체에서, 단위 "중량부"는 각 성분간의 중량의 비율을 의미할 수 있다.Throughout the specification of the present application, the unit "part by weight" may mean a ratio of weight between each component.
본 발명자들은 무용제형 에폭시 도료 조성물에 포함되는 체질안료로서 장석(feldspar)을 사용하는 경우, 체질안료의 일반적인 순기능을 유지하면서도 경도가 높아 도료의 경도를 향상시켜 우수한 내마모성을 가지며, 흡유량이 낮아 10 ℃ 이하의 저온 조건에서 에어리스 스프레이 도장 작업성이 우수한 도료 조성물을 제조할 수 있음을 밝혀 내었다. 또한, 경화제에 포함되는 지방족 아민과 지환족 아민의 함량을 조절하여 도료 조성물의 에어리스 스프레이 도장 작업성 및 도장 물성을 개선할 수 있음을 밝혀 내었다. 이에 따라, 하기와 같은 무용제형 에폭시 도료 조성물을 개발하였다.When using feldspar as an extender pigment included in the solvent-free epoxy paint composition, the present inventors have high hardness while maintaining the general net function of the extender pigment, thereby improving the hardness of the paint, thereby having excellent abrasion resistance and low oil absorption at 10 ℃. It was found that a coating composition having excellent airless spray coating workability can be prepared under the following low temperature conditions. In addition, it was found that the airless spray coating workability and coating properties of the coating composition can be improved by controlling the content of the aliphatic amine and the alicyclic amine contained in the curing agent. Accordingly, the following solvent-free epoxy coating composition was developed.
이하, 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, the present specification will be described in more detail.
본 발명의 일 실시예에 따른 에폭시 수지는 휘발성 용제의 함량이 거의 없는 고형분 용적비가 95 % 이상인 무용제형 에폭시 수지를 포함할 수 있다. 고형분 용적비가 95 % 이상인 에폭시 수지를 포함하는 도료 조성물은 방식성 및 내해수성 등의 물성이 우수한 도막을 구현할 수 있다.The epoxy resin according to an embodiment of the present invention may include a solvent-free epoxy resin having a solid content volume ratio of 95% or more with little content of a volatile solvent. A coating composition containing an epoxy resin having a solid content volume ratio of 95% or more can implement a coating film having excellent physical properties such as corrosion resistance and seawater resistance.
상기 에폭시 수지의 에폭시 당량(EEW)은 이에 제한되는 것은 아니나, 예를 들어 160 g/eq 이상 220 g/eq 이하일 수 있다. 구체적으로, 상기 에폭시 수지의 에폭시 당량은 170 g/eq 이상 200 g/eq 이하, 또는 175 g/eq 이상 190 g/eq 이하일 수 있다. 상기 에폭시 수지의 에폭시 당량을 전술한 범위로 조절함으로써, 무용제형 에폭시 도료 조성물의 점도가 지나치게 증가하는 것을 억제하여, 도료의 분산성 및 에어리스 스프레이 도장 작업성이 저하되는 것을 방지할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.The epoxy equivalent (EEW) of the epoxy resin is not limited thereto, but may be, for example, 160 g/eq or more and 220 g/eq or less. Specifically, the epoxy equivalent of the epoxy resin may be 170 g/eq or more and 200 g/eq or less, or 175 g/eq or more and 190 g/eq or less. By adjusting the epoxy equivalent of the epoxy resin to the above range, the viscosity of the solvent-free epoxy coating composition can be suppressed from excessively increasing, thereby preventing the dispersibility of the paint and the airless spray coating workability from deteriorating. The effect of is not limited thereto.
상기 에폭시 수지는 이에 제한되는 것은 아니나, 예를 들어 분자 중에 2개 이상의 에폭시기를 갖는 비스페놀 A형 에폭시 수지 및 비스페놀 F형 에폭시 수지 중 적어도 하나를 포함할 수 있다. 구체적으로, 상기 에폭시 수지는 비스페놀-A 디글리시딜 에테르(DGEBA) 및 비스페놀-F(BPF) 디글리시딜 에테르 중 적어도 하나를 포함할 수 있다. The epoxy resin is not limited thereto, but may include, for example, at least one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin having two or more epoxy groups in a molecule. Specifically, the epoxy resin may include at least one of bisphenol-A diglycidyl ether (DGEBA) and bisphenol-F (BPF) diglycidyl ether.
상기 에폭시 수지의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 주제 100 중량부를 기준으로, 30 중량부 이상 50 중량부 이하, 구체적으로 35 중량부 이상 45 중량부 이하, 30 중량부 이상 42.5 중량부 이하, 또는 40 중량부 이상 50 중량부 이하일 수 있다. The content of the epoxy resin is not limited thereto, for example, 30 parts by weight or more and 50 parts by weight or less, specifically 35 parts by weight or more and 45 parts by weight or less, 30 parts by weight or more and 42.5 parts by weight, based on 100 parts by weight of the subject. It may be less than or equal to 40 parts by weight or more and 50 parts by weight or less.
상기 에폭시 수지의 함량을 전술한 범위로 조절함으로써, 안료 함량이 증가함에 따라 도료 조성물의 점도가 높아져 작업성 및 도막 외관이 열등해지는 것을 억제할 수 있고, 방청성, 내해수성 등의 도막 물성이 저하되는 것을 억제할 수 있다. 또한, 상기 에폭시 수지의 함량이 전술한 범위 내인 경우, 무용제형 에폭시 도료 조성물의 가사 시간을 개선시킬 수 있고, 도막 경도 등의 기계적 물성이 저하되는 것을 억제할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.By adjusting the content of the epoxy resin within the above-described range, the viscosity of the coating composition increases as the pigment content increases, so that the workability and the appearance of the coating film can be suppressed from becoming inferior, and the coating film properties such as rust prevention property and seawater resistance decrease. Can be suppressed. In addition, when the content of the epoxy resin is within the above-described range, the pot life of the solvent-free epoxy coating composition can be improved, and mechanical properties such as coating film hardness can be suppressed from being deteriorated, but the effect of the present invention is limited thereto. It does not become.
본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은 주제와 경화제 각각에 희석제를 포함함으로써, 에폭시 수지의 고점도로 인한 안료 적용의 제한성을 극복시킬 수 있고, 에어리스 스프레이 도장 작업이 가능한 점도를 유지시킬 수 있다.The solvent-free epoxy coating composition according to an embodiment of the present invention includes a diluent in each of the main material and the curing agent, thereby overcoming the limitations of pigment application due to the high viscosity of the epoxy resin, and maintaining the viscosity at which airless spray painting work is possible. I can.
본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은 주제에 반응성 희석제와 비반응성 희석제를 포함할 수 있으며, 경화제에 비반응성 희석제를 포함할 수 있다. 이하, 본 명세서에서 주제에 포함되는 비반응성 희석제를 제1 비반응성 희석제라 하고, 경화제에 포함되는 비반응성 희석제를 제2 비반응성 희석제로 한다. The solvent-free epoxy coating composition according to an embodiment of the present invention may include a reactive diluent and a non-reactive diluent in the main material, and may include a non-reactive diluent in the curing agent. Hereinafter, the non-reactive diluent included in the subject matter in the present specification is referred to as a first non-reactive diluent, and the non-reactive diluent included in the curing agent is used as the second non-reactive diluent.
상기 주제에 포함되는 반응성 희석제는 에폭시기를 함유하고 있어, 상기 경화제와 함께 반응에 참여하여 경화된 도막의 일부분을 형성할 수 있다. 한편, 상기 주제에 포함되는 제1 비반응성 희석제와 상기 경화제에 포함되는 제2 비반응성 희석제는 경화 반응에는 참여하지 않지만, 도막에 잔존하여 도막의 물성에 영향을 미칠 수 있다.The reactive diluent included in the subject contains an epoxy group, and thus participates in the reaction with the curing agent to form a part of the cured coating film. Meanwhile, the first non-reactive diluent included in the subject and the second non-reactive diluent included in the curing agent do not participate in the curing reaction, but remain in the coating film and may affect the physical properties of the coating film.
본 발명의 일 실시예에 따른 상기 반응성 희석제의 함량은 상기 주제 100 중량부를 기준으로, 5 중량부 이상 20 중량부 이하일 수 있다. 구체적으로 상기 주제 100 중량부를 기준으로, 상기 반응성 희석제의 함량은 7 중량부 이상 18 중량부 이하, 또는 10 중량부 이상 15 중량부 이하일 수 있다. The content of the reactive diluent according to an embodiment of the present invention may be 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the subject. Specifically, based on 100 parts by weight of the subject, the content of the reactive diluent may be 7 parts by weight or more and 18 parts by weight or less, or 10 parts by weight or more and 15 parts by weight or less.
상기 반응성 희석제의 함량이 전술한 범위 내인 경우, 사용 가능한 안료의 함량이 적어짐에 따라 기계적 물성이 저하되는 현상 및 에어리스 스프레이 도장 작업성이 열등해지는 것을 억제할 수 있다. 또한, 상기 반응성 희석제의 함량을 전술한 범위로 조절함으로써, 도막 경도 및 방청성 등의 도막 물성을 개선시킬 수 있고, 도막의 건조 시간을 단축시킬 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.When the content of the reactive diluent is within the above-described range, it is possible to suppress a phenomenon in which mechanical properties are deteriorated and inferior airless spray coating workability as the amount of usable pigment decreases. In addition, by adjusting the content of the reactive diluent in the above-described range, it is possible to improve coating film properties such as coating film hardness and rust prevention property, and shorten the drying time of the coating film, but the effect of the present invention is not limited thereto.
상기 반응성 희석제의 에폭시 당량은 이에 제한되는 것은 아니나, 예를 들어 150 g/eq 이상 300 g/eq 이하일 수 있다. 또한, 상기 반응성 희석제는 전술한 에폭시 당량을 가지는 알킬 글리시딜 에테르(alkyl glycidyl ether)를 포함할 수 있다. 상기와 같은 반응성 희석제를 사용함으로써, 상기 무용제형 에폭시 도료 조성물의 도장 작업성을 개선할 수 있다.The epoxy equivalent of the reactive diluent is not limited thereto, but may be, for example, 150 g/eq or more and 300 g/eq or less. In addition, the reactive diluent may include an alkyl glycidyl ether having the above-described epoxy equivalent. By using the reactive diluent as described above, it is possible to improve the coating workability of the solvent-free epoxy coating composition.
상기 반응성 희석제는 하나의 에폭시기를 함유하는 모노에폭시 타입의 화합물을 포함할 수 있다. 모노에폭시 타입의 화합물을 포함하는 반응성 희석제를 사용함으로써, 무용제형 에폭시 도료 조성물의 점도를 적절하게 조절할 수 있다.The reactive diluent may include a monoepoxy type compound containing one epoxy group. By using a reactive diluent containing a monoepoxy type compound, the viscosity of the solvent-free epoxy coating composition can be appropriately adjusted.
본 발명의 일 실시예에 따른 상기 제1 비반응성 희석제의 함량은 상기 주제 100 중량부를 기준으로, 1 중량부 이상 10 중량부 이하, 구체적으로 3 중량부 이상 8 중량부 이하, 또는 4.5 중량부 이상 6.5 중량부 이하일 수 있다. The content of the first non-reactive diluent according to an embodiment of the present invention is 1 part by weight or more and 10 parts by weight or less, specifically 3 parts by weight or more and 8 parts by weight or less, or 4.5 parts by weight or more, based on 100 parts by weight of the subject matter. It may be less than or equal to 6.5 parts by weight.
상기 제1 비반응성 희석제의 함량을 전술한 범위로 조절함으로써, 에어리스 스프레이 도장 작업성을 향상시킬 수 있고, 도막의 경도 및 방청성 등의 물성이 저하되는 것을 억제할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다. By adjusting the content of the first non-reactive diluent in the above-described range, airless spray coating workability can be improved, and physical properties such as hardness and rust prevention property of the coating film can be suppressed from being deteriorated, but the effect of the present invention is thus It is not limited.
상기 제1 비반응성 희석제는 히드록시기를 함유하고, 그 예로서 벤질 알코올, 도데실 페놀, 및 페놀로 변성된 액상의 탄화수소 수지(phenol modified liquid hydrocarbon resin) 중 적어도 하나를 포함할 수 있다.The first non-reactive diluent contains a hydroxy group and may include, for example, at least one of benzyl alcohol, dodecyl phenol, and a phenol modified liquid hydrocarbon resin.
본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물에 포함되는 장석은, 체질안료의 일반적인 순기능을 유지하면서도 경도가 높아 도료의 경도를 증가시켜 우수한 내마모성을 가지는 도막을 구현할 수 있다. 또한, 장석은 흡유량이 낮아 10℃ 이하의 저온 조건에서 에어리스 스프레이의 무화도를 향상시켜 스프레이 패터닝이 양호하고, 칙소성이 부여됨에 따라 흐름성이 양호하여 저온 조건에서의 에어리스 스프레이 도장 작업성이 개선된 도료 조성물을 제공할 수 있다.Feldspar included in the solvent-free epoxy coating composition according to an embodiment of the present invention has high hardness while maintaining the general net function of the extender pigment, increasing the hardness of the coating material, thereby implementing a coating film having excellent wear resistance. In addition, feldspar has low oil absorption and improves the atomization degree of airless spray under low temperature conditions of 10°C or less, so that the spray patterning is good, and due to the thixotropy, the flowability is good, and the workability of airless spray painting under low temperature conditions is improved. Paint composition can be provided.
상기 장석의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 주제 100 중량부를 기준으로, 20 중량부 이상 40 중량부 이하일 수 있다. 구체적으로 상기 주제 100 중량부를 기준으로, 상기 장석의 함량은 25 중량부 이상 37.5 중량부 이하, 27 중량부 이상 35 중량부 이하, 20 중량부 이상 32.5 중량부 이하, 또는 30 중량부 이상 40 중량부 이하일 수 있다. The content of the feldspar is not limited thereto, but may be, for example, 20 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the subject. Specifically, based on 100 parts by weight of the subject, the content of feldspar is 25 parts by weight or more and 37.5 parts by weight or less, 27 parts by weight or more and 35 parts by weight or less, 20 parts by weight or more and 32.5 parts by weight or less, or 30 parts by weight or more and 40 parts by weight. It can be below.
상기 장석의 함량을 전술한 범위로 조절함으로써, 상기 무용제형 에폭시 도료 조성물의 에어리스 스프레이 도장 작업성을 개선시킬 수 있고, 도막의 기계적 물성이 저하되는 것을 억제할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.By adjusting the content of feldspar in the above-described range, it is possible to improve the airless spray coating workability of the solvent-free epoxy coating composition, and it is possible to suppress deterioration of the mechanical properties of the coating film, but the effect of the present invention is limited thereto. It does not become.
상기 장석의 평균 입자크기는 이에 제한되는 것은 아니나, 예를 들어 1 ㎛ 이상 75 ㎛ 이하일 수 있다.The average particle size of the feldspar is not limited thereto, but may be, for example, 1 µm or more and 75 µm or less.
일 실시예에서, 상기 장석의 평균 입자크기는 예컨대 PSA(Particle Size A nalysis)의 방법에 따라 측정한 것일 수 있다.In one embodiment, the average particle size of the feldspar may be measured according to a method of, for example, PSA (Particle Size Analysis).
본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은 침강방지제를 더 포함함으로써, 도료 저장 안정성이 열등한 장석의 문제를 해소할 수 있다. 침강방지제는 당 분야에 알려진 통상적인 것을 제한 없이 사용할 수 있으나, 예를 들어, 클레이(clay) 타입, 왁스 타입, 우레탄 고분자 타입의 침강방지제 등을 사용할 수 있으며, 바람직하게는, 클레이 타입의 침강방지제를 더 포함시킬 수 있다. 이러한 클레이 타입의 침강방지제는 도료 저장 안정성이 열등한 장석의 단점을 보완하는 동시에, 도료의 작업성 및 도막 물성을 개선시킬 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.The solvent-free epoxy coating composition according to an embodiment of the present invention further includes an anti-settling agent, thereby solving the problem of feldspar, which is inferior in paint storage stability. The anti-settling agent may be used without limitation, a conventional one known in the art, but for example, a clay type, a wax type, a urethane polymer type may be used, and preferably, a clay type anti-settling agent It may further include. Such a clay-type anti-settling agent can improve the workability and properties of the coating film while compensating for the disadvantages of feldspar, which is inferior in coating storage stability, but the effect of the present invention is not limited thereto.
상기 침강방지제의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 주제 100 중량부를 기준으로, 0.5 중량부 이상 5 중량부 이하, 구체적으로 1.5 중량부 이상 4.5 중량부 이하, 또는 2 중량부 이상 3.5 중량부 이하일 수 있다. The content of the anti-settling agent is not limited thereto, for example, 0.5 parts by weight or more and 5 parts by weight or less, specifically 1.5 parts by weight or more and 4.5 parts by weight or less, or 2 parts by weight or more and 3.5 parts by weight, based on 100 parts by weight of the main body. It may be less than or equal to part.
상기 침강방지제의 함량이 전술한 범위 내인 경우, 상기 무용제형 에폭시 도료 조성물의 도막물성 및 저장안정성, 작업성을 동시에 확보할 수 있다. 구체적으로, 상기 침강방지제의 함량을 전술한 범위로 조절함으로써, 도료의 작업성(수직면 도장 시의 흐름성)이 저하되는 것을 방지하며, 레벨링이 우수한 도막을 구현할 수 있다. 또한, 도료의 점도 상승으로 인한 작업성 불량 및 내수성 등의 도막 물성이 저하되는 것을 억제할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.When the content of the anti-settling agent is within the above-described range, coating properties, storage stability, and workability of the solvent-free epoxy coating composition can be simultaneously secured. Specifically, by adjusting the content of the anti-settling agent in the above-described range, the workability of the paint (flowability during vertical surface coating) is prevented from deteriorating, and a coating film having excellent leveling can be implemented. In addition, it is possible to suppress a decrease in coating properties such as poor workability and water resistance due to an increase in the viscosity of the coating material, but the effect of the present invention is not limited thereto.
일 실시예에서, 상기 장석과 상기 침강방지제는 5:1 내지 20:1 또는 8:1 내지 15:1의 중량비로 포함될 수 있으며, 장석과 침강방지제의 중량비가 5:1 미만인 경우 도료의 점도 상승으로 인한 작업성 문제 및 외관 불량 문제가 발생할 수 있고, 20:1이 초과될 경우 수직면 도장 시의 흐름성이 저하되는 문제점이 발생할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.In one embodiment, the feldspar and the anti-settling agent may be included in a weight ratio of 5:1 to 20:1 or 8:1 to 15:1, and when the weight ratio of the feldspar and the anti-settling agent is less than 5:1, the viscosity of the paint is increased As a result, workability and appearance defects may occur, and if it exceeds 20:1, the flowability during vertical surface painting may decrease, but the effect of the present invention is not limited thereto.
본 발명의 일 실시예에 따른 주제는 분산제, 소포제, 및 기능성 첨가제 중 적어도 하나를 포함하는 첨가제를 더 포함할 수 있다.The subject matter according to an embodiment of the present invention may further include an additive including at least one of a dispersant, a defoaming agent, and a functional additive.
상기 분산제는 안료 표면에 흡착하여 전기 반발력이나 입체 장애 효과로 안료와 안료 사이의 간격을 일정하게 유지시켜 안료들이 재응집 되는 것을 방지하는 역할을 수행할 수 있다. 상기 분산제로 당업계에서 사용되는 것을 제한 없이 사용할 수 있고, 예를 들면 실리콘계 분산제 또는 비실리콘계 분산제(예컨대, 폴리카르복실산 폴리에스터 타입 분산제) 등을 들 수 있다. The dispersant may play a role of preventing re-aggregation of the pigments by adsorbing on the pigment surface and maintaining a constant gap between the pigment and the pigment due to electric repulsion or steric hindrance effect. The dispersant used in the art may be used without limitation, and examples thereof include a silicone-based dispersant or a non-silicone-based dispersant (eg, a polycarboxylic acid polyester type dispersant).
상기 소포제는 도막 내의 기포 발생 등 도막 결함을 방지하기 위한 것으로서, 이러한 기포가 도막 내에 잔존할 경우 소지와의 부착 불량 또는 물리적 물성의 저하를 가져올 수 있다. 상기 소포제로 당업계에서 사용되는 것을 제한 없이 사용할 수 있고, 예를 들면 미네랄 오일계, 실리콘계, 비실리콘계 등을 들 수 있는데, 본 발명의 일 실시예에서는 소포력을 극대화하는 측면에서 실리콘계 소포제를 사용할 수 있다. The antifoaming agent is for preventing defects in the coating film such as generation of bubbles in the coating film, and when such bubbles remain in the coating film, it may cause poor adhesion to the substrate or deterioration in physical properties. The antifoaming agent used in the art may be used without limitation, and examples thereof include mineral oil-based, silicone-based, non-silicone-based, and the like. In one embodiment of the present invention, a silicone-based antifoaming agent is used in terms of maximizing the defoaming force. I can.
또한, 상기 기능성 첨가제는 소포성 불량 방지, 크레터링 발생 방지, 색분리 방지 및 도막 표면의 기포를 제거하고, 도막의 평활성을 부여하기 위한 첨가제로서 폴리에테르실록산, 폴리에스테르 실록산 등의 실리콘 첨가제를 사용할 수 있고, 레벨링 성능과 소포 성능을 함께 가진 타입을 선정하는 것이 바람직할 수 있다. In addition, as the functional additive, silicone additives such as polyethersiloxane and polyester siloxane are used as additives for preventing deterioration of defoaming, preventing occurrence of cratering, preventing color separation, removing air bubbles on the surface of the coating film, and providing smoothness of the coating film. And it may be desirable to select a type that has both leveling performance and defoaming performance.
상기 첨가제의 총 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 주제 100 중량부를 기준으로, 0.5 중량부 이상 5 중량부 이하일 수 있다.The total content of the additive is not limited thereto, but may be, for example, 0.5 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the subject matter.
본 발명의 일 실시예에 따른 주제는 유색안료를 더 포함할 수 있다. 유색안료는 무용제형 에폭시 도료 조성물의 도막에 색을 발현하기 위하여 사용되는 것으로서, 당업계에서 사용되는 유색안료를 제한 없이 사용할 수 있다. 예를 들면, 백색 안료로서 TiO2 등을 사용할 수 있고, 흑색 안료로서 카본 블랙 등을 사용할 수 있다.The subject according to an embodiment of the present invention may further include a colored pigment. Colored pigments are used to express color on a coating film of a solvent-free epoxy coating composition, and colored pigments used in the art may be used without limitation. For example, TiO 2 etc. can be used as a white pigment, and carbon black etc. can be used as a black pigment.
상기 유색안료의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 주제 100 중량부에 대하여, 7.5 중량부 이상 12.5 중량부 이하일 수 있다.The content of the colored pigment is not limited thereto, but may be, for example, 7.5 parts by weight or more and 12.5 parts by weight or less based on 100 parts by weight of the subject.
일반적으로 방청성, 내해수성 등이 요구되는 2액형 에폭시 수지 도료에는 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지, 페놀노볼락 에폭시수지, 크레졸노볼락 에폭시수지 등의 주제와 함께 경화제가 사용된다.In general, two-component epoxy resin coatings that require rust prevention and seawater resistance are used as a curing agent along with a subject such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and the like.
본 발명의 일 실시예에 따른 경화제는 지방족 아민과 지환족 아민을 포함하며, 아민과 케톤의 축합반응에 의해 제조되는 케티민류 등과 같은 활성수소를 포함하는 아민류 또는 이들 아민류를 이용한 폴리아민아마이드, 폴리아미도아민, 페놀변성아민, 에폭시부가형아민 등의 변성 수지를 더 포함할 수 있다.The curing agent according to an embodiment of the present invention includes an aliphatic amine and an alicyclic amine, and amines containing active hydrogen such as ketimines prepared by condensation reaction of amines and ketones, or polyamine amides and polyamidos using these amines It may further include a modified resin such as amine, phenol-modified amine, epoxy addition-type amine.
상기 지방족 아민은 디에틸렌트리아민, 트리에틸렌테트라아민, 및 폴리옥시프로필렌디아민 중 적어도 하나를 포함할 수 있으나, 상기 지방족 아민의 종류를 한정하는 것은 아니다. The aliphatic amine may include at least one of diethylenetriamine, triethylenetetraamine, and polyoxypropylenediamine, but the type of the aliphatic amine is not limited.
상기 지환족 아민은 사이클로헥실, 사이클로헵틸, 및 사이클로펜틸 중 적어도 하나의 지환족기를 포함할 수 있으나, 지환족기의 종류를 한정하는 것은 아니다.The alicyclic amine may include at least one alicyclic group among cyclohexyl, cycloheptyl, and cyclopentyl, but the type of the alicyclic group is not limited.
상기 지방족 아민의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 경화제 100 중량부 기준으로, 40 중량부 이상 60 중량부 이하일 수 있다. 구체적으로 상기 경화제 100 중량부 기준으로, 상기 지방족 아민의 함량은 42.5 중량부 이상 55 중량부 이하, 45 중량부 이상 50 중량부 이하, 40 중량부 이상 52.5 중량부 이하, 또는 47.5 중량부 이상 57.5 중량부 이하일 수 있다.The content of the aliphatic amine is not limited thereto, but may be, for example, 40 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the aliphatic amine is 42.5 parts by weight or more and 55 parts by weight or less, 45 parts by weight or more and 50 parts by weight or less, 40 parts by weight or more and 52.5 parts by weight or less, or 47.5 parts by weight or more and 57.5 parts by weight. It may be less than or equal to part.
상기 지환족 아민의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 경화제 100 중량부 기준으로, 15 중량부 이상 35 중량부 이하일 수 있다. 구체적으로 상기 경화제 100 중량부 기준으로, 상기 지환족 아민의 함량은 17.5 중량부 이상 30 중량부 이하, 20 중량부 이상 28.5 중량부 이하, 15 중량부 이상 27.5 중량부 이하, 또는 25 중량부 이상 32.5 중량부 이하일 수 있다.The content of the alicyclic amine is not limited thereto, but may be, for example, 15 parts by weight or more and 35 parts by weight or less based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the alicyclic amine is 17.5 parts by weight or more and 30 parts by weight or less, 20 parts by weight or more and 28.5 parts by weight or less, 15 parts by weight or more and 27.5 parts by weight or less, or 25 parts by weight or more and 32.5 parts by weight. It may be less than or equal to parts by weight.
상기 지방족 아민과 지환족 아민의 함량을 전술한 범위로 조절함으로써, 35℃ 이상의 고온 조건에서 반응이 급격하게 발생하는 것을 억제하여, 가사 시간을 개선시킬 수 있다. 또한, 상기 지방족 아민과 지환족 아민의 함량이 상기 범위 내인 경우, 방청성 등의 도막 물성 및 흐름성이 저하되는 것을 방지할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.By controlling the content of the aliphatic amine and the alicyclic amine within the above-described range, rapid reaction at a high temperature of 35° C. or higher can be suppressed, thereby improving pot life. In addition, when the content of the aliphatic amine and the alicyclic amine is within the above range, it is possible to prevent the coating film properties and flow properties such as rust prevention from deteriorating, but the effect of the present invention is not limited thereto.
또한, 본 발명의 무용제 에폭시 도료 조성물은 상기 지방족 아민 및 지환족 아민을 1:0.1 내지 1.5의 중량비, 또는 1:0.2 내지 1:1의 중량비로 포함함으로써, 도장 작업성 및 도장 물성을 향상시킬 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.In addition, the solvent-free epoxy coating composition of the present invention can improve coating workability and coating properties by including the aliphatic amine and alicyclic amine in a weight ratio of 1:0.1 to 1.5, or 1:0.2 to 1:1. However, the effect of the present invention is not limited thereto.
본 발명의 일 실시예에 따른 제2 비반응성 희석제는 상기 제1 비반응성 희석제와 동일하거나 상이할 수 있다. The second non-reactive diluent according to an embodiment of the present invention may be the same as or different from the first non-reactive diluent.
상기 제2 비반응성 희석제의 함량은 이에 제한되는 것은 아니나, 예를 들어 상기 경화제 100 중량부를 기준으로, 10 중량부 이상 30 중량부 이하, 구체적으로 15 중량부 이상 28 중량부 이하, 또는 20 중량부 이상 25 중량부 이하일 수 있다.The content of the second non-reactive diluent is not limited thereto, but, for example, based on 100 parts by weight of the curing agent, 10 parts by weight or more and 30 parts by weight or less, specifically 15 parts by weight or more and 28 parts by weight or less, or 20 parts by weight It may be more than 25 parts by weight or less.
상기 제2 비반응성 희석제의 함량을 전술한 범위로 조절함으로써, 에어리스 스프레이 도장 작업성을 향상시킬 수 있다. 또한, 제2 비반응성 희석제의 함량이 상기 범위 내인 경우, 도막 건조 시간이 지연되는 것, 도막의 경도 및 방청성 등의 물성이 저하되는 것을 억제할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.By adjusting the content of the second non-reactive diluent in the above-described range, airless spray coating workability may be improved. In addition, when the content of the second non-reactive diluent is within the above range, it is possible to suppress a delay in the drying time of the coating film and deterioration of physical properties such as hardness and rust prevention property of the coating film, but the effect of the present invention is not limited thereto. .
본 발명의 일 실시예에 따른 경화 촉진제의 함량은 상기 경화제 100 중량부를 기준으로, 1 중량부 이상 10 중량부 이하일 수 있다. 구체적으로, 상기 경화제 100 중량부를 기준으로, 상기 경화 촉진제의 함량은 1.5 중량부 이상 8 중량부 이하, 또는 2.5 중량부 이상 5 중량부 이하일 수 있다.The content of the curing accelerator according to an embodiment of the present invention may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the curing accelerator may be 1.5 parts by weight or more and 8 parts by weight or less, or 2.5 parts by weight or more and 5 parts by weight or less.
상기 경화 촉진제의 함량을 전술한 범위로 조절함으로써, 경화 속도를 적절하게 제어할 수 있다. 이를 통해, 경화 속도가 늘어나 도막 경도, 브러싱 등의 도막 물성이 떨어지는 문제, 경화속도가 빨라져 가사 시간이 저하되고, 흐름성이 열등해지는 문제를 억제할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.By adjusting the content of the curing accelerator within the above-described range, the curing rate can be appropriately controlled. Through this, it is possible to suppress the problem that the coating film properties such as coating film hardness and brushing decrease due to an increase in the curing speed, the problem that the curing speed is increased and the pot life is reduced, and the flowability is inferior, but the effect of the present invention is limited thereto. no.
상기 경화 촉진제는 이에 제한되는 것은 아니나, 예를 들어 트리 디메틸 아미노 메틸 페놀, 트리페닐 포스파이트 및 아미노 에틸 피페라진 중 적어도 하나를 포함할 수 있다.The curing accelerator is not limited thereto, but may include, for example, at least one of tridimethyl amino methyl phenol, triphenyl phosphite, and amino ethyl piperazine.
본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은, 상기 주제와 상기 경화제의 중량비가 75:25 내지 85:15, 77.5:22.5 내지 82.5:17.5, 또는 80:20 내지 85:15일 수 있다.In the solvent-free epoxy coating composition according to an embodiment of the present invention, the weight ratio of the subject and the curing agent may be 75:25 to 85:15, 77.5:22.5 to 82.5:17.5, or 80:20 to 85:15. .
상기 주제와 경화제의 중량비를 전술한 범위로 조절함으로써, 에어리스 스프레이 도장 작업성이 좋고, 물성이 우수한 도막을 구현할 수 있는 무용제형 에폭시 도료 조성물을 제공할 수 있으나, 본 발명의 효과가 이에 제한되는 것은 아니다.By adjusting the weight ratio of the subject and the curing agent to the above range, it is possible to provide a solvent-free epoxy coating composition capable of implementing a coating film having good airless spray coating workability and excellent physical properties, but the effect of the present invention is limited thereto. no.
본 발명의 일 측면에 따른 해양 구조물은 상기 무용제형 에폭시 도료 조성물로부터 형성되는 도막을 포함하는 것을 특징으로 한다.The marine structure according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
본 발명의 일 실시예에 따른 해양 구조물에 마련되는 도막은 상기 무용제형 에폭시 도료 조성물의 경화물을 포함하는 것일 수 있다.The coating film provided on the marine structure according to an embodiment of the present invention may include a cured product of the solvent-free epoxy coating composition.
본 발명의 일 측면에 따른 선박의 탱크는 상기 무용제형 에폭시 도료 조성물로부터 형성되는 도막을 포함하는 것을 특징으로 한다.A tank of a ship according to an aspect of the present invention is characterized in that it includes a coating film formed from the solvent-free epoxy coating composition.
본 발명의 일 실시예에 따른 선박의 탱크에 마련되는 도막은 상기 무용제형 에폭시 도료 조성물의 경화물을 포함하는 것일 수 있다.The coating film provided on the tank of the ship according to an embodiment of the present invention may include a cured product of the solvent-free epoxy coating composition.
상기 도막을 갖는 선박의 탱크는 밸러스트(ballast) 탱크, 및 원유(crude oil) 탱크를 포함하며, 선박에 마련되는 다른 탱크들을 포함할 수 있다.The tank of the ship having the coating film includes a ballast tank and a crude oil tank, and may include other tanks provided on the ship.
상기한 바와 같이, 본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은 선박의 밸러스트 탱크, 및 원유 탱크 등의 혹독한 부식 환경에 적용 가능하고, 인체 및 환경에 유해한 용제를 전혀 사용하지 않아 시공이 안전할 수 있다. As described above, the solvent-free epoxy coating composition according to an embodiment of the present invention can be applied to severe corrosive environments such as ballast tanks and crude oil tanks of ships, and does not use any solvents harmful to the human body and environment, so construction is not possible. It can be safe.
또한, 상기 무용제형 에폭시 도료 조성물은 기존의 무용제 에폭시 도료와는 달리 10 ℃ 이하의 저온 조건에서 에어리스 스프레이 도장 작업 시에 스프레이 패터닝이 양호하여 작업성이 우수하고, 35 ℃ 이상의 고온 조건에서 가사 시간이 30분 이상으로 양호하여 도장 시공이 용이한 장점을 가질 수 있다. In addition, the solvent-free epoxy coating composition has excellent workability due to good spray patterning during airless spray painting under low temperature conditions of 10 ℃ or lower, unlike conventional solvent-free epoxy paints, and pot life at high temperatures of 35 ℃ or higher. It is good in more than 30 minutes, so it can have the advantage of easy painting.
본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은 선박의 탱크 외에도 원유시추 설비와 같은 해양 구조물에 방청하도 용도로 코팅시켜 사용될 수 있다.The solvent-free epoxy coating composition according to an embodiment of the present invention may be used by coating for rust prevention purposes on offshore structures such as crude oil drilling facilities in addition to a tank of a ship.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 기술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.
무용제형 에폭시 도료 조성물의 제조Preparation of solvent-free epoxy coating composition
실시예 1Example 1
하기 표 1에 나타낸 바와 같은 조성(단위: 중량부)으로 주제를 제조하였다.A subject was prepared in the composition (unit: parts by weight) as shown in Table 1 below.
구체적으로, 비스페놀-A형 에폭시수지(고형분 100 %, 에폭시 당량 189g/eq), 알킬 글리시딜 에테르의 반응성 희석제(에폭시 당량 280g/eq), 폴리카르복실산 폴리에스터 타입의 분산제, 비실리콘계의 소포제, 클레이 타입의 침강 방지제(BYK, GARAMITE 1958), 제1 비반응성 희석제를 투입하고 교반시켜 반응용액을 제조하였다. 상기 반응용액에 체질안료를 하기 표 1에 기재된 함량으로 천천히 투입하며 교반시킨 후, 유색안료로서 백색안료(TiO2)를 서서히 투입하며 교반시켰다. 이후, 상기 반응용액을 HSD(High Speed Dissolver)를 이용하여 용액 중의 평균 입자크기가 80㎛ 이하가 될 때까지 분산을 시켜 주제를 제조하였다.Specifically, bisphenol-A type epoxy resin (solid content 100%, epoxy equivalent 189 g/eq), reactive diluent of alkyl glycidyl ether (epoxy equivalent 280 g/eq), polycarboxylic acid polyester type dispersant, non-silicone type A reaction solution was prepared by adding a defoaming agent, a clay type anti-settling agent (BYK, GARAMITE 1958), and a first non-reactive diluent and stirring. After slowly adding and stirring an extender pigment to the reaction solution in the amount shown in Table 1 below, a white pigment (TiO 2 ) was slowly added and stirred as a colored pigment. Thereafter, the reaction solution was dispersed using a HSD (High Speed Dissolver) until the average particle size in the solution became 80 μm or less to prepare a main body.
또한, 하기 표 1에 나타낸 바와 같은 조성(단위: 중량부)으로 경화제를 제조하였다.In addition, a curing agent was prepared in the composition (unit: parts by weight) as shown in Table 1 below.
구체적으로, 지방족 아민 50 중량부, 지환족 아민 25 중량부, 경화 촉진제 3 중량부 및 제2 비반응성 희석제 22 중량부로 정량하여 반응기에 투입하였다. 상기 반응기를 저속 교반으로 혼합하여 경화제 혼합액을 제조하였다.Specifically, 50 parts by weight of an aliphatic amine, 25 parts by weight of an alicyclic amine, 3 parts by weight of a curing accelerator, and 22 parts by weight of a second non-reactive diluent were quantified and introduced into the reactor. The reactor was mixed by low-speed stirring to prepare a curing agent mixture.
이후, 상기에서 제조한 주제와 경화제를 80:20의 중량비로 혼합하여 무용제형 에폭시 도료 조성물을 제조하였다. 구체적인 조성은 하기 표 1에 기재된 것과 같다.Then, a solvent-free epoxy coating composition was prepared by mixing the prepared main material and the curing agent in a weight ratio of 80:20. The specific composition is as described in Table 1 below.
실시예 2Example 2
주제 제조 시, 비스페놀-A형 에폭시수지 대신 비스페놀-F형 에폭시 수지(에폭시 당량 175g/eq)를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 무용제형 에폭시 도료 조성물을 제조하였다. 구체적인 조성은 하기 표 1에 기재된 것과 같다.In the preparation of the subject, a solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that a bisphenol-F type epoxy resin (epoxy equivalent 175 g/eq) was used instead of the bisphenol-A type epoxy resin. The specific composition is as described in Table 1 below.
실시예 3 내지 11Examples 3 to 11
비스페놀-A형 에폭시수지 및 비스페놀-F형 에폭시수지를 하기 표 1에 기재된 것과 같은 중량비로 혼합한 것을 제외하고는, 실시예 1과 동일한 방법으로 무용제형 에폭시 도료 조성물을 제조하였다. A solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that the bisphenol-A type epoxy resin and the bisphenol-F type epoxy resin were mixed in a weight ratio as shown in Table 1 below.
실시예 3 내지 11에 따른 주제 및 경화제 각각의 구체적인 조성은 하기 표 1에 기재된 것과 같다.Specific compositions of each of the subject and curing agent according to Examples 3 to 11 are as described in Table 1 below.
비교예 1 Comparative Example 1
주제 제조 시, 체질안료로 장석 대신 백운모 광석과 고령토를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 무용제형 에폭시 도료 조성물을 제조하였다. 백운모 광석과 고령토는 20:10의 중량비로 혼합하여 사용하였다.When preparing the subject, a solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that muscovite ore and kaolin were used instead of feldspar as extender pigments. The muscovite ore and kaolin were mixed and used in a weight ratio of 20:10.
비교예 2 내지 7Comparative Examples 2 to 7
비스페놀-A형 에폭시수지, 지방족 아민와 지환족 아민의 함량을 하기 표 2에 기재된 것과 같이 조절한 것을 제외하고는, 실시예 1과 동일한 방법으로 무용제형 에폭시 도료 조성물을 제조하였다. A solvent-free epoxy coating composition was prepared in the same manner as in Example 1, except that the contents of the bisphenol-A type epoxy resin, the aliphatic amine and the alicyclic amine were adjusted as described in Table 2 below.
비교예 2 내지 7에 따른 주제 및 경화제 각각의 구체적인 조성은 하기 표 2에 기재된 것과 같다.Specific compositions of each of the subject and the curing agent according to Comparative Examples 2 to 7 are as described in Table 2 below.
구분division 실시예Example
1One 22 33 44 55 66 77 88 99 1010 1111
에폭시도료조성물Epoxy paint composition 주제(중량부)Subject (part by weight) BPA 수지(1) BPA Resin (1) 4040 -- 3030 3434 2626 3030 3030 3030 3030 2525 4040
BPF 수지(2) BPF Resin (2) -- 4040 1010 1010 88 1010 1010 1010 1313 1111 77
반응성 희석제(3) Reactive Diluent (3) 1010 1010 1010 1010 1010 1010 1010 1010 1010 1010 1010
분산제Dispersant 1One 1One 1One 1One 1One 1One 1One 1One 1One 1One 1One
소포제Antifoam 1One 1One 1One 1One 1One 1One 1One 1One 1One 1One 1One
침강방지제Anti-settling agent 33 33 33 33 1One 33 33 33 -- 77 1One
유색안료Colored pigment 1010 1010 1010 99 88 1010 1010 1010 1010 1010 1010
체질안료Extender pigment 백운모광석(4) Musk Mica Ore (4) -- -- -- -- -- -- -- -- -- -- --
고령토(5) Kaolin (5) -- -- -- -- -- -- -- -- -- -- --
장석(6) Feldspar (6) 3030 3030 3030 2525 4040 3030 3030 3030 -- -- --
제1 비반응성 희석제(7) First non-reactive diluent (7) 55 55 55 77 55 55 55 55 55 55 55
경화제(중량부)Hardener (parts by weight) 지방족 아민(8) Aliphatic amines (8) 5050 5050 5050 5050 5050 4545 4040 6060 5050 5050 5050
지환족 아민(9) Cycloaliphatic amines (9) 2525 2525 2525 2525 2525 3030 3535 1515 2525 2525 2525
경화촉진제(10) Curing Accelerator (10) 33 33 33 33 33 33 33 33 33 33 33
제2 비반응성 희석제(7) Second non-reactive diluent (7) 2222 2222 2222 2222 2222 2222 2222 2222 2222 2222 2222
구분division 비교예Comparative example
1One 22 33 44 55 66 77
에폭시도료조성물Epoxy paint composition 주제(중량부)Subject (part by weight) BPA 수지(1) BPA Resin (1) 4040 4040 4040 4040 4040 3232 4545
BPF 수지(2) BPF Resin (2) -- -- -- -- -- -- --
반응성 희석제(3) Reactive Diluent (3) 1010 1010 1010 1010 1010 77 1717
분산제Dispersant 1One 1One 1One 1One 1One 1One 22
소포제Antifoam 1One 1One 1One 1One 1One 1One 22
침강방지제Anti-settling agent 33 33 33 33 33 22 44
유색안료Colored pigment 1010 1010 1010 1010 1010 88 1010
체질안료Extender pigment 백운모광석(4) Musk Mica Ore (4) 2020 -- -- -- -- -- --
고령토(5) Kaolin (5) 1010 -- -- -- -- -- --
장석(6) Feldspar (6) -- 3030 3030 3030 3030 4545 1515
제1 비반응성 희석제(7) First non-reactive diluent (7) 55 55 55 55 55 44 55
경화제(중량부)Hardener (parts by weight) 지방족 아민(8) Aliphatic amines (8) 5050 7575 -- 6565 3535 5050 5050
지환족 아민(9) Cycloaliphatic amines (9) 2525 -- 7575 1010 4040 2525 2525
경화촉진제(10) Curing Accelerator (10) 33 33 33 33 33 33 33
제2 비반응성 희석제(7) Second non-reactive diluent (7) 2222 2222 2222 2222 2222 2222 2222
(1) 비스페놀-A형 에폭시수지 (에폭시 당량 189g/eq)(2) 비스페놀-F형 에폭시 수지 (에폭시 당량 175g/eq)(3) 알킬 글리시딜 에테르의 반응성 희석제(에폭시 당량 280g/eq)(4) 5 ~ 20㎛의 평균 입자크기를 갖는 백운모광석(5) 0.1 ~ 10㎛의 평균 입자크기를 갖는 고령토(6) 1 ~ 75㎛의 평균 입자크기를 갖는 장석(Feldspar-group minerals)(7) 벤질 알코올(8) ANCAMINE 2636(EVONIC 社)(9) ANCAMINE 1618(EVONIC 社)(10) ANCAMINE K54(EVONIC 社)(1) Bisphenol-A type epoxy resin (epoxy equivalent 189g/eq) (2) Bisphenol-F type epoxy resin (epoxy equivalent 175g/eq) (3) Reactive diluent of alkyl glycidyl ether (epoxy equivalent 280g/eq) (4) Muscular mica ore with an average particle size of 5 to 20㎛ (5) Kaolin with an average particle size of 0.1 to 10㎛ (6) Feldspar-group minerals with an average particle size of 1 to 75㎛ ( 7) Benzyl alcohol (8) ANCAMINE 2636 (EVONIC) (9) ANCAMINE 1618 (EVONIC) (10) ANCAMINE K54 (EVONIC)
상기 표 1 및 표 2에서, BPA 수지, BPF 수지, 반응성 희석제, 분산제, 소포제, 침강방지제, 유색안료, 체질안료, 및 제1 비반응 성희석제의 함량(중량부)은, 주제 총 100 중량부를 기준한 것이다. In Tables 1 and 2, the content (parts by weight) of the BPA resin, BPF resin, reactive diluent, dispersant, antifoaming agent, anti-settling agent, colored pigment, extender pigment, and first non-reactive diluent is 100 parts by weight It is a standard.
또한, 상기 표 1 및 표 2에서, 지방족 아민, 지환족 아민, 경화촉진제 및 제2 비반응성 희석제의 함량(중량부)은, 경화제 총 100 중량부를 기준한 것이다.In addition, in Tables 1 and 2, the content (parts by weight) of an aliphatic amine, an alicyclic amine, a curing accelerator, and a second non-reactive diluent is based on a total of 100 parts by weight of the curing agent.
무용제형 에폭시 도료 조성물의 물성 평가Evaluation of physical properties of solvent-free epoxy coating composition
상기 실시예 1 내지 11 및 비교예 1 내지 7에서 제조된 무용제형 에폭시 도료 조성물을 다음과 같은 조건으로 도장하였다.The solvent-free epoxy coating compositions prepared in Examples 1 to 11 and Comparative Examples 1 to 7 were coated under the following conditions.
먼저, 소지 표면의 녹, 먼지, 습기, 유분 및 기타 오염물을 청수나 적절한 용제를 사용하여 완전히 제거한 후, 표면조도 25 ㎛ 내지 75 ㎛로 블라스터 연마하였다. 그리고 준비된 시편에 에어리스 스프레이를 사용하여 노즐 구경 0.019" 내지 0.025", 분사압력 3bar 내지 5bar, 분사각도 50°로 설정하여 도장하였다. 에어리스 스프레이를 통해 작업성을 평가하였으며, 작업성 결과는 표 4 및 표 5에 나타내었다. First, rust, dust, moisture, oil and other contaminants on the surface of the substrate were completely removed using fresh water or an appropriate solvent, and then blasted to a surface roughness of 25 µm to 75 µm. Then, the prepared specimens were coated with a nozzle diameter of 0.019" to 0.025", spraying pressure of 3bar to 5bar, and spraying angle of 50° using an airless spray. Workability was evaluated through airless spray, and the workability results are shown in Tables 4 and 5.
물성 시편의 경우에는 수평 조건에서 건조도막 320㎛을 도장하였다. 방청성, 내해수성, 시험용 시편은 텅스텐 펜으로 소지면이 보일 정도로 선을 그어 제작하였으며, 내충격성 시편은 ASTM D2794의 시험 방법에 의거하여 시험 진행하였고, 내굴곡성 시편은 ASTM D522에 따라 Conical Mandrel 시험기기를 사용하여 시편에 굴곡을 주어 시험 진행하였다. 얻어진 도막 물성에 대하여 방청성, 내해수성, 내충격성 및 내굴곡성 등의 도막물성을 평가하여 그 결과를 다음 표 4 및 표 5에 나타내었다.In the case of the physical property specimen, a dry coating film of 320 μm was coated under horizontal conditions. Anti-corrosion, seawater resistance, and test specimens were produced by drawing a line with a tungsten pen so that the substrate could be seen, and the impact-resistant specimen was tested according to the test method of ASTM D2794, and the bending-resistant specimen was subjected to a Conical Mandrel test apparatus according to ASTM D522. The test was carried out by giving a bend to the specimen. The obtained coating properties were evaluated for coating properties such as rust prevention, seawater resistance, impact resistance, and bending resistance, and the results are shown in Tables 4 and 5 below.
구체적인 시험 방법은 아래와 같다.The specific test method is as follows.
방청성Anti-rust
ASTM B117에 의거 SALTFOG기기에서 1500 시간 동안 시험한 시편에 대해 녹발생, 표면 블리스터(Blister)발생 및 도막 박리 거리를 평가하였다.In accordance with ASTM B117, rust generation, surface blister generation, and film peeling distance were evaluated for specimens tested for 1500 hours on a SALTFOG device.
내해수성Seawater resistance
해수가 담겨있는 욕조에 3개월 동안 침적한 시편에 대해 녹발생, 표면 블리스터 발생 및 도막 박리 거리를 평가하였다.For the specimens immersed in a bath containing seawater for 3 months, rust generation, surface blister generation, and film peeling distance were evaluated.
내충격성Impact resistance
도장된 시편 전면, 후면에 ASTM D2794의 방법으로 160lb.in Impact 후 Defect 발생 정도를 평가하였다.The degree of defect occurrence after 160lb.in impact was evaluated on the front and rear surfaces of the coated specimen by the method of ASTM D2794.
내굴곡성Flexibility resistance
도장된 시편에 ASTM D522의 방법으로 Conical Mandrel test 후 Defect 발생 정도를 평가하였다.The degree of defect occurrence was evaluated after the Conical Mandrel test on the coated specimen by the method of ASTM D522.
에어리스 스프레이(Airless Spray) 작업성Airless spray workability
에어리스 스프레이를 사용하여 노즐 구경 0.019" 내지 0.025", 분사압력 3 bar 내지 5 bar, 분사각도 50°로 설정한 후 도장하고, 저온(10 ℃ 이하) 조건에서의 에어리스 스프레이 패턴(Airless Spray Pattern), 최대 흐름성 두께, 박막건조도막(200㎛ 이하) Leveling, 고온(35 ℃ 이상) 조건 가사 시간을 측정하였다.Using an airless spray, the nozzle diameter was set to 0.019" to 0.025", spraying pressure 3 bar to 5 bar, spray angle 50°, and then painted, and an airless spray pattern under low temperature (10 °C or less) conditions, The maximum flowability thickness, leveling of thin film dry film (200㎛ or less), and pot life under high temperature (35 ℃ or more) were measured.
구분division 실시예Example
1One 22 33 44 55 66 77 88 99 1010 1111
방청성Anti-rust Blister(1) Blister (1) No.8MNo.8M No.8FNo.8F No.8FNo.8F No.8FNo.8F No.8FNo.8F No.8FNo.8F No.8FNo.8F No.8FNo.8F No.6FNo.6F No.8FNo.8F No.8MNo.8M
도막박리거리Film peeling distance 1mm1mm 0.5mm0.5mm 0.7mm0.7mm 0.7mm0.7mm 0.6mm0.6mm 0.7mm0.7mm 0.7mm0.7mm 0.7mm0.7mm 0.7mm0.7mm 0.8mm0.8mm 0.8mm0.8mm
내해수성Seawater resistance Blister(1) Blister (1) No.10No.10 No.10No.10 No.10No.10 No.10No.10 No.10No.10 No.10No.10 No.10No.10 No.10No.10 No.8FNo.8F No.8FNo.8F No.8FNo.8F
Cross-cut(2) Cross-cut (2) 4B4B 4B4B 4B4B 4B4B 4B4B 4B4B 4B4B 4B4B 3B3B 3B3B 3B3B
내충격성(3) Impact resistance (3) DirectDirect EE EE EE EE EE EE EE EE EE GG EE
ReverseReverse EE EE EE EE EE EE EE EE EE GG EE
내굴곡성(3) Flexibility (3) EE GG EE EE EE GG GG GG EE FF EE
작업성(4) Workability (4) 저온(10℃)Spray patternLow temperature (10℃) Spray pattern ○○ ◎◎ ○○ ○○ ○○ ○○ ○○ ○○ ○○ △△ ○○
Sagging(㎛)(5) Sagging(㎛) (5) 800800 900900 900900 900900 900900 900900 900900 900900 800800 900900 700700
LevelingLeveling ○○ ◎◎ ○○ ○○ ○○ ○○ ○○ ○○ ○○ △ △ ○○
고온(35℃)가사시간(분)High temperature (35℃) Housekeeping time (min) 3030 3030 3030 3030 3030 3333 3535 3030 3030 1515 3030
(1) Blister Size : No.2 > No.4 > No.6 > No.8 > No.10(No Blister) Blister Frequency : D=Dense, MD=Medium Dense, M=Medium, F=Few(2) Cross-cut : ASTM D 3359 5B(우수) 5B > 4B > 3B > 2B > 1B (열세)(3) Impact & Bending Resistance Performance : E > G > F > P > VPE=Excellent, G=Good, F=Fair, P=Poor, VP=Very Poor(4) Pattern & Leveling 평가 : (우수) ◎ > ○ > △ > X (불량)(5) Sagging : 값이 클수록 우수 (해당 도막 두께 이상에서 흐름 발생)(1) Blister Size: No.2> No.4> No.6> No.8> No.10(No Blister) Blister Frequency: D=Dense, MD=Medium Dense, M=Medium, F=Few(2 ) Cross-cut: ASTM D 3359 5B (Excellent) 5B> 4B> 3B> 2B> 1B (Inferior) (3) Impact & Bending Resistance Performance: E> G> F> P> VPE=Excellent, G=Good, F =Fair, P=Poor, VP=Very Poor(4) Pattern & Leveling evaluation: (excellent) ◎> ○> △> X (poor) (5) Sagging: the larger the value, the better (flow occurs above the applicable film thickness)
구분division 비교예Comparative example
1One 22 33 44 55 66 77
방청성Anti-rust Blister(1) Blister (1) No.8FNo.8F No.6FNo.6F No.6DNo.6D No.6FNo.6F No.6MNo.6M No.8MNo.8M No.4DNo.4D
도막박리거리Film peeling distance 1mm1mm 5mm5mm 6mm6mm 4mm4mm 4mm4mm 1mm1mm 8mm8mm
내해수성Seawater resistance Blister(1) Blister (1) No.10No.10 No.4MNo.4M No.4MNo.4M No.4MNo.4M No.6MNo.6M No.10No.10 No.4DNo.4D
Cross-cut(2) Cross-cut (2) 4B4B 2B2B 1B1B 2B2B 2B2B 4B4B 1B1B
내충격성(3) Impact resistance (3) DirectDirect GG EE EE GG EE EE PP
ReverseReverse GG EE EE GG EE EE PP
내굴곡성(3) Flexibility (3) FF EE GG EE EE VPVP VPVP
작업성(4) Workability (4) 저온(10℃)Spray patternLow temperature (10℃) Spray pattern △△ △△ △△ △△ ○○ △△ ○○
Sagging(㎛)(5) Sagging(㎛) (5) 700700 600600 500500 600600 700700 600600 900900
LevelingLeveling ○○ ○○ ○○ ○○ ○○ ○○ ○○
고온(35℃) 가사시간(분)High temperature (35℃) Pot life (minutes) 3030 77 5050 1515 4040 1515 6060
(1) Blister Size : No.2 > No.4 > No.6 > No.8 > No.10(No Blister) Blister Frequency : D=Dense, MD=Medium Dense, M=Medium, F=Few(2) Cross-cut : ASTM D 3359 5B(우수) 5B > 4B > 3B > 2B > 1B (열세)(3) Impact & Bending Resistance Performance : E > G > F > P > VPE=Excellent, G=Good, F=Fair, P=Poor, VP=Very Poor(4) Pattern & Leveling 평가 : (우수) ◎ > ○ > △ > X (불량)(5) Sagging : 값이 클수록 우수 (해당 도막 두께 이상에서 흐름 발생)(1) Blister Size: No.2> No.4> No.6> No.8> No.10(No Blister) Blister Frequency: D=Dense, MD=Medium Dense, M=Medium, F=Few(2 ) Cross-cut: ASTM D 3359 5B (Excellent) 5B> 4B> 3B> 2B> 1B (Inferior) (3) Impact & Bending Resistance Performance: E> G> F> P> VPE=Excellent, G=Good, F =Fair, P=Poor, VP=Very Poor(4) Pattern & Leveling evaluation: (excellent) ◎> ○> △> X (poor) (5) Sagging: the larger the value, the better (flow occurs above the applicable film thickness)
표 1 내지 표 5를 참고하면, 본 발명의 실시예 1 및 11에 따른 무용제형 에폭시 도료 조성물은 작업성이 우수하고, 무용제형 에폭시 도료 조성물을 사용하여 제조한 도막의 물성이 우수한 것을 확인하였다.Referring to Tables 1 to 5, it was confirmed that the solvent-free epoxy coating composition according to Examples 1 and 11 of the present invention had excellent workability, and the physical properties of the coating film prepared using the solvent-free epoxy coating composition were excellent.
반면, 체질안료로서 백운모 광석 및 고령토를 사용한 비교예 1의 경우, 내굴곡성 및 저온 조건에서의 스프레이 패터닝이 열세한 것을 확인하였다. 지환족 아민을 사용하지 않은 경화제를 포함한 비교예 2의 무용제형 에폭시 도료 조성물은 저온 조건에서 스프레이 패터닝이 열세한 것으로 확인되었으며, 고온 조건에서의 가시 시간도 열세한 것을 확인하였다. 지방족 아민을 사용하지 않은 경화제를 포함한 비교예 3의 무용제형 에폭시 도료 조성물은 저온 조건에서 스프레이 패터닝이 열세한 것으로 확인되었으며, 내해수성이 현저히 열세한 것을 확인하였다. On the other hand, in the case of Comparative Example 1 using muscovite ore and kaolin as extender pigments, it was confirmed that the spray patterning under the conditions of bending resistance and low temperature was poor. The solvent-free epoxy coating composition of Comparative Example 2 including a curing agent without using an alicyclic amine was found to be poor in spray patterning under low temperature conditions, and it was confirmed that the visibility time under high temperature conditions was also poor. The solvent-free epoxy coating composition of Comparative Example 3 including a curing agent without using an aliphatic amine was found to be poor in spray patterning under low temperature conditions, and it was confirmed that the seawater resistance was significantly inferior.
한편, 지방족 아민의 함량과 지환족 아민의 함량이 본 발명의 일 실시예에 따른 함량 범위에서 벗어난 비교예 4 및 5의 경우, 비교예 4에 따른 무용제형 에폭시 도료 조성물은 가사 시간이 열세하고, 비교예 4 및 5에 따른 무용제형 에폭시 도료 조성물은 내해수성이 열등한 것을 확인하였다. On the other hand, in the case of Comparative Examples 4 and 5 in which the content of the aliphatic amine and the content of the alicyclic amine are out of the content range according to an embodiment of the present invention, the solvent-free epoxy coating composition according to Comparative Example 4 has poor pot life, It was confirmed that the solvent-free epoxy coating composition according to Comparative Examples 4 and 5 was inferior in seawater resistance.
또한, 장석의 함량이 본 발명의 일 실시예에 따른 함량 범위에서 벗어난 비교예 6 및 7의 경우, 비교예 6에 따른 무용제형 에폭시 도료 조성물은 저온 조건에서 스프레이 패터닝, 고온 조건에서의 가시 시간 및 내굴곡성이 열세하였으며, 비교예 7에 따른 무용제형 에폭시 도료 조성물은 내해수성 및 내굴곡성이 열등한 것을 확인하였다.In addition, in the case of Comparative Examples 6 and 7 in which the content of feldspar is out of the content range according to an embodiment of the present invention, the solvent-free epoxy coating composition according to Comparative Example 6 is spray patterning under low temperature conditions, visibility time under high temperature conditions, and It was confirmed that the bending resistance was poor, and the solvent-free epoxy coating composition according to Comparative Example 7 was inferior in seawater resistance and bending resistance.
따라서, 본 발명의 일 실시예에 따른 무용제형 에폭시 도료 조성물은 에어리스 스프레이 도장 작업성 및 가사 시간이 우수하고, 뛰어난 물성을 가지는 도막을 구현할 수 있음을 알 수 있다.Accordingly, it can be seen that the solvent-free epoxy coating composition according to an embodiment of the present invention has excellent airless spray coating workability and pot life, and can implement a coating film having excellent physical properties.
본 발명은 상기에서 설명한 실시예로 한정되지 않으며, 상기 실시예들의 조합 또는 상기 실시예 중 적어도 어느 하나와 공지 기술의 조합을 또 다른 실시예로서 포함할 수 있음은 물론이다.It goes without saying that the present invention is not limited to the above-described embodiments, and may include a combination of the above embodiments or a combination of at least one of the above embodiments and a known technology as another embodiment.
이상 본 발명을 구체적인 실시예를 통하여 상세히 설명하였으나, 이는 본 발명을 구체적으로 설명하기 위한 것으로, 본 발명은 이에 한정되지 않으며, 본 발명의 기술적 사상 내에서 당해 분야의 통상의 지식을 가진 자에 의해 그 변형이나 개량이 가능함은 명백하다고 할 것이다.Although the present invention has been described in detail through specific examples, this is for explaining the present invention in detail, and the present invention is not limited thereto, and within the technical scope of the present invention, those of ordinary skill in the art It would be clear that the transformation or improvement is possible.
본 발명의 단순한 변형 내지 변경은 모두 본 발명의 영역에 속하는 것으로 본 발명의 구체적인 보호 범위는 첨부된 청구범위에 의하여 명확해질 것이다.All simple modifications to changes of the present invention belong to the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

Claims (9)

  1. 분자 중에 2개 이상의 에폭시기를 함유하는 에폭시 수지; 에폭시기를 함유하는 반응성 희석제; 히드록시기를 함유하는 제1 비반응성 희석제; 및 장석;을 포함하는 주제 및An epoxy resin containing two or more epoxy groups in the molecule; A reactive diluent containing an epoxy group; A first non-reactive diluent containing a hydroxy group; And feldspar; and
    지방족 아민; 지환족 아민; 히드록시기를 함유하는 제2 비반응성 희석제; 및 경화 촉진제;를 포함하는 경화제를 포함하고,Aliphatic amines; Alicyclic amines; A second non-reactive diluent containing a hydroxy group; And a curing accelerator; containing a curing agent,
    상기 장석의 함량은 주제 100 중량부를 기준으로 20 중량부 이상 40 중량부 이하인 것을 특징으로 하는 무용제형 에폭시 도료 조성물.The content of the feldspar is a solvent-free epoxy coating composition, characterized in that 20 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the subject.
  2. 제 1 항에 있어서, The method of claim 1,
    상기 주제는 침강방지제를 더 포함하는 것을 특징으로 하는 무용제형 에폭시 도료 조성물.The subject is a solvent-free epoxy coating composition, characterized in that it further comprises an anti-settling agent.
  3. 제 2 항에 있어서, The method of claim 2,
    상기 침강방지제의 함량은 주제 100 중량부 기준으로 0.5 내지 5 중량부인 것을 특징으로 하는 무용제형 에폭시 도료 조성물.The content of the anti-settling agent is a solvent-free epoxy coating composition, characterized in that 0.5 to 5 parts by weight based on 100 parts by weight of the subject.
  4. 제 2 항에 있어서, The method of claim 2,
    상기 장석과 침강방지제의 중량비는 5:1 내지 20:1인 것을 특징으로 하는 무용제형 에폭시 도료 조성물.Solvent-free epoxy coating composition, characterized in that the weight ratio of the feldspar and the anti-settling agent is 5:1 to 20:1.
  5. 제 1 항에 있어서, The method of claim 1,
    상기 주제는,The subject above is,
    상기 주제 100 중량부를 기준으로,Based on 100 parts by weight of the subject,
    상기 에폭시 수지의 함량이 30 중량부 이상 50 중량부 이하이고,The content of the epoxy resin is 30 parts by weight or more and 50 parts by weight or less,
    상기 반응성 희석제의 함량이 5 중량부 이상 20 중량부 이하이고,The content of the reactive diluent is 5 parts by weight or more and 20 parts by weight or less,
    상기 제1 비반응성 희석제의 함량이 1 중량부 이상 10 중량부 이하인 것을 특징으로 하는 무용제형 에폭시 도료 조성물.A solvent-free epoxy coating composition, characterized in that the content of the first non-reactive diluent is 1 part by weight or more and 10 parts by weight or less.
  6. 제 1 항에 있어서,The method of claim 1,
    상기 경화제는,The curing agent,
    상기 경화제 100 중량부 기준으로, Based on 100 parts by weight of the curing agent,
    상기 지방족 아민의 함량이 40 중량부 이상 60 중량부 이하이고, The content of the aliphatic amine is 40 parts by weight or more and 60 parts by weight or less,
    상기 지환족 아민의 함량이 15 중량부 이상 35 중량부 이하이고,The content of the alicyclic amine is 15 parts by weight or more and 35 parts by weight or less,
    상기 제2 비반응성 희석제의 함량이 10 중량부 이상 30 중량부 이하이고,The content of the second non-reactive diluent is 10 parts by weight or more and 30 parts by weight or less,
    상기 경화 촉진제의 함량이 1 중량부 이상 10 중량부 이하인 것을 특징으로 하는 무용제형 에폭시 도료 조성물.Solvent-free epoxy coating composition, characterized in that the content of the curing accelerator is 1 part by weight or more and 10 parts by weight or less.
  7. 제 1 항에 있어서, The method of claim 1,
    상기 주제와 상기 경화제의 중량비는 75:25 내지 85:15인 것을 특징으로 하는 무용제형 에폭시 도료 조성물.Solvent-free epoxy coating composition, characterized in that the weight ratio of the main material and the curing agent is 75:25 to 85:15.
  8. 제 1 항 내지 제 7 항 중 어느 한 항에 따른 상기 무용제형 에폭시 도료 조성물로부터 형성된 도막을 포함하는 것을 특징으로 하는 해양 구조물.An offshore structure comprising a coating film formed from the solvent-free epoxy coating composition according to any one of claims 1 to 7.
  9. 제 1 항 내지 제 7 항 중 어느 한 항에 따른 상기 무용제형 에폭시 도료 조성물로부터 형성된 도막을 포함하는 것을 특징으로 하는 선박의 탱크.A vessel tank comprising a coating film formed from the solvent-free epoxy coating composition according to any one of claims 1 to 7.
PCT/KR2020/009438 2019-07-17 2020-07-17 Solventless epoxy paint composition, and marine structure and ship tank which comprise coating formed therefrom WO2021010787A2 (en)

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