WO2020175766A1 - Powder coating composition - Google Patents

Powder coating composition Download PDF

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Publication number
WO2020175766A1
WO2020175766A1 PCT/KR2019/015957 KR2019015957W WO2020175766A1 WO 2020175766 A1 WO2020175766 A1 WO 2020175766A1 KR 2019015957 W KR2019015957 W KR 2019015957W WO 2020175766 A1 WO2020175766 A1 WO 2020175766A1
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WIPO (PCT)
Prior art keywords
epoxy resin
powder coating
coating composition
weight
urethane
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PCT/KR2019/015957
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French (fr)
Korean (ko)
Inventor
이기성
이진석
왕현웅
Original Assignee
주식회사 케이씨씨
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Publication of WO2020175766A1 publication Critical patent/WO2020175766A1/en

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Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • 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

Definitions

  • the present invention relates to a powder coating composition excellent in heat resistance and boiling water resistance.
  • Epoxy resin powder coating has a high glass transition temperature, so it has excellent thermal properties, as well as excellent adhesive strength, chemical resistance, mechanical strength, and electrical insulation, preventing corrosion and improving durability of steel pipes or pipelines buried underground or under the sea. It is being used for the purpose of. However, as the environment in which the pipe is buried becomes harsher, the conventional epoxy resin powder coating having a glass transition temperature of about 100° C. cannot obtain a sufficient effect to protect the pipe from corrosion. Accordingly, there is a demand for improvement in thermal, chemical, and physical properties of the epoxy coating film, and studies on paints that satisfy these physical properties are also ongoing.
  • U.S. Patent No. 9,617,413 discloses a powder coating composition using a divinylarene dioxide resin and a dicyandiamide curing agent.
  • Japanese Patent No. 6,342,696 discloses a powder coating composition comprising a trifunctional or higher epoxy resin and at least one curing agent of a guanidine compound and an imidazole compound.
  • the powder coating composition even in the case of the powder coating composition, there is a problem that the boiling water resistance and adhesion required in a high temperature environment are insufficient.
  • the present invention provides a powder coating composition excellent in heat resistance and boiling water resistance.
  • the present invention provides a powder coating composition
  • a powder coating composition comprising at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin, a curing agent and an extender pigment.
  • the powder coating composition according to the present invention has excellent heat resistance, boiling water resistance, and negative electrode peeling resistance, and decreases the generation rate of bubbles, thereby improving adhesion and appearance characteristics decrease due to bubbles generated during coating film formation.
  • the powder coating composition of the present invention is excellent in impact resistance and bending resistance, while securing constant workability and a glass transition temperature of 120° C. or higher, and can effectively protect it when applied to a steel pipe.
  • the powder coating composition according to the present invention includes at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin, a curing agent and an extender pigment.
  • the powder coating composition according to the present invention may further include additives commonly used in the field of colored pigments, catalysts and powder coatings, if necessary.
  • looking at the composition of the powder coating composition of the present invention is as follows.
  • the epoxy resin includes at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin as the main resin.
  • Non-limiting examples of usable urethane-modified epoxy resins include urethane-modified novolac epoxy resins, urethane-modified bisphenol epoxy resins, urethane-modified cresol epoxy resins, or a mixture thereof.
  • the urethane-modified epoxy resin may include a urethane-modified novolac epoxy resin.
  • the urethane-modified epoxy resin may be an epoxy resin obtained from a reaction of a urethane prepolymer and an epoxy resin.
  • the urethane prepolymer may be prepared by reacting a polyol and an isocyanate compound.
  • the type of the polyol is not particularly limited, for example, one selected from the group consisting of polyester polyol, polyoxypropylene glycol, polybutadiene, bisphenol A, diethylene glycol, dipropylene glycol, polycaprolactone, and polycaprolactam. You can use the above.
  • the kind of the isocyanate compound is not particularly limited, but, for example, 2,4-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, and 4 At least one selected from the group consisting of ,4-biphenyl diisocyanate may be used.
  • the isocyanate modification rate of the urethane-modified epoxy resin is not particularly limited, but may be, for example, 10% to 40%, and another example, 15% to 30%.
  • the epoxy equivalent (EEW) and softening point of the urethane-modified epoxy resin are not particularly limited, but the epoxy equivalent (EEW) may be 250 to 700 g/eq, for example, 400 to 650 g/eq, and the softening point is 100°C to It may be 130 °C, for example 105 °C to 120 °C.
  • the urethane-modified epoxy resin has an epoxy equivalent and a softening point in the above-described range, the dispersibility of the coating film may be excellent.
  • the viscosity and glass transition temperature of the urethane-modified epoxy resin are not particularly limited, but the viscosity (175° C., ICI viscometer) may be 1,000 to 3,500 cps, for example, 1,500 to 3,000 cps, and the glass transition temperature is 50 to 65° C. , For example, it may be 52 to 60 °C.
  • the urethane-modified epoxy resin has a viscosity and a glass transition temperature in the above-described range, chemical resistance may be excellent.
  • Bisphenol A-type epoxy resin is an epoxy resin obtained from the reaction of bisphenol A (BPA) and epichlorohydrin.
  • BPA bisphenol A
  • epichlorohydrin a conventional epoxy resin known in the art may be used without particular limitation.
  • the epoxy equivalent (EEW) and softening point of the bisphenol A-type epoxy resin are not particularly limited, but the epoxy equivalent may be 700 to 1,500 g/eq, for example, 1,000 to 1,300 g/eq, and the softening point may be 100 to 130°C. have.
  • the bisphenol A-type epoxy resin has an epoxy equivalent weight and a softening point in the above-described range, storage stability may be excellent.
  • the viscosity and glass transition temperature of the bisphenol A-type epoxy resin are not particularly limited, but the viscosity (200° C., ICI viscometer) may be 1,000 to 5,000 cps, for example, 1,500 to 4,500 cps, and the glass transition temperature is 50 to 80° C. , For example, it may be 60 to 70 °C.
  • the bisphenol A-type epoxy resin has a viscosity and a glass transition temperature in the above-described ranges, appearance characteristics and flexibility of the coating film are improved, thereby minimizing the occurrence of cracks in the coating film.
  • the powder coating composition of the present invention may include the urethane-modified epoxy resin and bisphenol A-type epoxy resin as an epoxy resin.
  • the mixing ratio of the urethane-modified epoxy resin and the bisphenol A-type epoxy resin is not particularly limited, but may be a weight ratio of 1 to 5: 1, for example, 1 to 3: 1.
  • heat resistance and boiling water resistance of the powder coating composition may be improved.
  • the epoxy resin may be 45 to 90% by weight, for example, 60 to 80% by weight, and another example, 65 to 75% by weight based on the total weight of the powder coating composition.
  • content of the epoxy resin is less than 45% by weight, a heat resistance problem may occur due to a decrease in the glass transition temperature of the coating film, and when it exceeds 90% by weight, mechanical properties may be poor.
  • the powder coating composition of the present invention may contain one or more of an amine-based curing agent and a phenol-based curing agent as a curing agent.
  • the amine-based curing agent is not particularly limited as long as it is an amine-based curing agent capable of curing reaction with an epoxy resin.
  • an aliphatic amine-based curing agent there are an aliphatic amine-based curing agent, an alicyclic amine-based curing agent, and an aromatic amine-based curing agent, and these may be used alone or in combination of two or more.
  • the amine value of the amine-based curing agent is not particularly limited, and may be, for example, 15 to 30 mgKOH/g. When the amine value of the amine-based curing agent satisfies the above range, excellent corrosion resistance can be secured.
  • phenolic curing agent those conventionally used in the powder coating field may be used without limitation.
  • Non-limiting examples of the phenolic curing agent that can be used include resol-type phenolic resins, novolac-type phenolic resins, and polyhydroxystyrene resins.
  • the resol-type phenolic resin include aniline-modified resol resin and melamine-modified resol resin.
  • the novolak-type phenolic resin include phenol novolac resin, cresol novolak resin, tert-butylphenol novolac resin, nonylphenol novolac resin, naphthol novolac resin, dicyclopentadiene-modified phenol resin, terpene-modified phenol.
  • Type resin triphenol-methane type resin, naphthol aralkyl resin, and the like.
  • the polyhydroxystyrene resin include poly(p-hydroxystyrene).
  • the hydroxyl group equivalent of the phenolic curing agent is not particularly limited, and may be, for example, 200 to 300 g/eq.
  • the curing agent may be included in an amount of 0.1 to 5% by weight, for example, 0.1 to 3% by weight, based on the total weight of the powder coating composition.
  • content of the curing agent is within the above-described range, the degree of curing of the coating film is high, and physical properties of the coating film may be improved.
  • the powder coating composition of the present invention may further include an extender pigment commonly used in the powder coating field within a range that does not impair the intrinsic properties of the composition.
  • the extender pigment can further improve the high temperature/high pressure chemical resistance of the paint.
  • Non-limiting examples of extender pigments that can be used include calcium carbonate, barium sulfate, feldspar, kaolin, alumina hydroxide, magnesium hydroxide, titanium dioxide, magnesium carbonate, alumina, mica, montmorillonite, olastonite, talc, aluminum nitride, silicon nitride, There are boron nitride, aluminum oxide, aluminum nitride, and the like, and these may be used alone or in combination of two or more.
  • the extender pigment may include one or more extender pigments selected from the group of inorganic pigments including calcium carbonate, barium sulfate, feldspar, and kaolin.
  • the extender pigment may include barium sulfate and feldspar.
  • the blending ratio of barium sulfate and feldspar is not particularly limited, but may be 1: 0.5 to 5, for example, 1: 0.8 to 2.5 weight ratio.
  • the extender pigment includes barium sulfate and feldspar in the above-described blending ratio, it is possible to secure excellent corrosion resistance by improving the boiling water resistance and long-term negative electrode peeling resistance of the coating film.
  • the shape of the extender pigment may be spherical or amorphous, and is not particularly limited thereto.
  • the average particle diameter of the extender pigment is not particularly limited, and may be, for example, 1 to 20 ⁇ m.
  • the extender pigment may be 5 to 45% by weight based on the total weight of the powder coating composition, in another example 15 to 40% by weight.
  • content of the extender pigment is in the above-described range, mechanical properties, impact resistance, and adhesion of the coating film may be improved.
  • the powder coating composition of the present invention may further include a colored pigment commonly used in the powder coating field within a range that does not impair the inherent properties of the composition.
  • the colored pigment may be mixed with an epoxy resin to express a desired color (color) in the powder coating or used to increase the strength or gloss of the coating film.
  • colored pigments organic pigments, inorganic pigments, metallic pigments, aluminum-paste, pearl, etc., which are commonly used in powder coatings, can be used without limitation, and these can be used alone or in two or more types.
  • Non-limiting examples of the color pigments that can be used include azo-based, phthalocyanine-based, iron oxide-based, cobalt-based, carbonate-based, sulfate-based, silicate-based, chromate-based pigments, and the like, such as titanium dioxide, zinc oxide, bismuth vanadium. Date, cyanine green, carbon black, iron oxide, sulfur iron oxide, navy blue, cyanine blue, and mixtures of two or more thereof.
  • the content of the colored pigment is not particularly limited, and may be, for example, 0.1 to 15% by weight, for example 0.1 to 10% by weight, based on the total weight of the powder coating composition.
  • the content of the colored pigment is within the above-described range, the color expression of the coating film to which the powder coating composition of the present invention is applied is excellent, and the hiding property and mechanical properties of the coating film can be improved.
  • the powder coating composition of the present invention may further include a catalyst commonly used in the powder coating field within a range that does not harm the inherent properties of the composition.
  • the catalyst is a material that accelerates the reaction between the epoxy resin and the curing agent, which is the main resin, and includes, for example, an imidazole catalyst, a phosphonium catalyst, an amine catalyst, and a metal catalyst. Can be used by mixing.
  • Non-limiting examples of the imidazole-based catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-hectylimidazole, 2-isopropylimida Sol, 2-undecylimidazole, 2-heptanedecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl -2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-
  • Non-limiting examples of the phosphonium-based catalyst include benzyltriphenyl phosphonium chloride, butyltriphenyl phosphonium chloride, butyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium acetate, ethyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium Phonium iodide, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride or tetraphenyl phosphonium iodide.
  • Non-limiting examples of the amine-based catalyst include triethylamine, triethylenediamine, tetramethyl-1,3-butanediamine, ethylmorpholine, diazabicycloundecene, and diazabicyclononene.
  • the metal catalyst may include organic metal complexes or organic metal salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complex examples include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • Organic zinc complexes organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese complexes such as manganese (II) acetylacetonate, etc. It is not limited.
  • organic metal salt include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.
  • the content of the catalyst may be adjusted according to the reactivity of the epoxy resin and the curing agent.
  • the content of the catalyst may be 0.01 to 2% by weight, in another example 0.01 to 1% by weight, based on the total weight of the powder coating composition.
  • the content of the catalyst is out of the above-described range, mechanical properties of the coating film may be deteriorated.
  • the powder coating composition of the present invention may further include additives commonly used in the powder coating field within a range that does not harm the inherent properties of the composition.
  • Non-limiting examples of additives that can be used in the present invention include leveling agents, pinhole inhibitors, dispersants, adhesion promoters, flow additives, flow improvers, low stress agents, cratering inhibitors, coupling agents, gloss modifiers, flame retardants, matting agents. , An auxiliary curing agent and a light absorbing agent, and these may be used alone or in combination of two or more.
  • the leveling agent is intended to improve the appearance characteristics of the coating film while improving adhesion in the composition by leveling the coating composition to be coated smoothly and smoothly.
  • the pinhole inhibitor allows volatile substances to be released from the coating film during the curing process, thereby preventing the occurrence of pinholes in the coating film and improving appearance characteristics.
  • pinhole inhibitors include amide-based (eg, ceraflour 960 (BYK)), polypropylene-based, stearic acid-based pinhole inhibitors, and the like.
  • the pinhole inhibitor may be benzoin or a mixture of benzoin and an amide pinhole inhibitor.
  • dispersant conventional ones known in the art may be used without limitation, and as an example, a polyacrylic dispersant may be used that is adsorbed on the surface of a colored pigment to maximize a degassing effect.
  • the adhesion promoter is a substance for enhancing the adhesion of the coating film, and a silane adhesion promoter or the like may be used.
  • Non-limiting examples of the adhesion promoter include mercaptoalkylakoxysilane, gammaglydoxypropyltrimethoxysilane, and the like, and as an example, the adhesion promoter is a mercaptoalkylalkoxysilane having a molecular weight of 150 to 300 g/mol.
  • the fluid additive is used to maximize the fluidity effect, and can secure long-term fluidity while improving the adhesion of the paint.
  • waxes, silica, and the like may be used as the flowable additive.
  • Non-limiting examples of flowable additives that can be used include paraffin wax, natural wax (e.g., carnauba wax, etc.), synthetic wax (e.g., polyethylene wax, etc.), silica, etc., which are used alone or in combination of two or more. Can be used.
  • waxes may be mixed with silica and used.
  • the flowable additive may be used as an additive component after adding it after making a chip.
  • the flow improving agent is used to lower the surface tension of the coating film and realize a flexible appearance, and a conventional one known in the art may be used.
  • Non-limiting examples include acrylic or silicone flow enhancers.
  • Such additives may be added within a range known in the art, for example, 0.01 to 15% by weight based on the total weight of the powder coating composition, and in another example, 0.1 to 5% by weight. When the content of the additive is within the above-described range, the appearance and hardness of the coating film may be improved.
  • the powder coating composition according to the present invention may be prepared by a method known in the art, and for example, may be prepared through processes such as basis weight of raw materials, dry premixing, dispersion and coarse pulverization, pulverization and classification.
  • a raw material mixture containing an epoxy resin, a curing agent, an extender pigment, a colored pigment, a catalyst, and optionally an additive is added to a container mixer to be uniformly mixed, and the mixed composition is melt-mixed and then pulverized.
  • a container mixer for example, by melting and dispersing the raw material mixture at 85 to 120°C by a melt-kneading device such as a kneader or an extruder to prepare chips with a predetermined thickness (eg, 1 to 5 mm). Thereafter, the prepared chips may be pulverized in a range of 30 to 100 ⁇ m using a pulverizing device such as a high-speed mixer, and then classified to prepare a powder coating composition.
  • the classification process is not particularly limited, and may be filtered by, for example, 80 to 120 mesh. Accordingly, a powder coating having an average particle size in the range of 30 to 100 ⁇ m can be obtained.
  • the average particle diameter of the powder is not particularly limited, but when the above-described range is satisfied, coating workability and appearance characteristics of the coating film may be improved.
  • the surface of the powder coating particles according to the present invention may be coated with a fine powder such as silica.
  • a pulverization mixing method in which fine powder is added and mixed during pulverization, a dry mixing method using a Henschel mixer or the like can be used.
  • a powder coating composition of Comparative Example 1-3 was prepared in the same manner as in Example, except for the composition of Table 3 below.
  • the units used in Table 3 below are weight percent.
  • Epoxy resin 1 Urethane modified epoxy resin (epoxy equivalent 465 g/eq, softening point 115 °C, viscosity (175 °C, ICI viscometer) 2,250 cps, glass transition temperature 57 °C, isocyanate modification rate 25%)
  • Epoxy resin 2 Urethane modified epoxy resin (epoxy equivalent 400 g/eq, softening point 105°C, viscosity (175°C, ICI viscometer) 1,500 cps, glass transition temperature 52°C, isocyanate modification rate 15%)
  • Epoxy resin 3 urethane modified epoxy resin (epoxy equivalent 600 g/eq, softening point 120 °C, viscosity (175 °C, ICI viscometer) 3,000 cps, glass transition temperature 60 °C, isocyanate modification rate 30%)
  • Epoxy resin 4 Urethane modified epoxy resin (epoxy equivalent 900 g/eq, softening point 90 °C, viscosity (175 °C, ICI viscometer) 1,000 cps, glass transition temperature 45 °C)
  • Epoxy resin 5 Bisphenol A-type epoxy resin (epoxy equivalent 1,150 g/eq, softening point 120 °C, viscosity (200 °C, ICI viscometer) 2,300 cps, glass transition temperature 65 °C)
  • Epoxy resin 6 Bisphenol A-type epoxy resin (epoxy equivalent 1,000 g/eq, softening point 115 °C, viscosity (200 °C, ICI viscometer) 1,500 cps, glass transition temperature 60 °C)
  • Epoxy resin 7 Bisphenol A-type epoxy resin (epoxy equivalent 1,300 g/eq, softening point 125 °C, viscosity (200 °C, ICI viscometer) 4,500 cps, glass transition temperature 70 °C)
  • Epoxy resin 8 Bisphenol A-type epoxy resin (epoxy equivalent 650 g/eq, softening point 130 °C, viscosity (200 °C, ICI viscometer) 3,000 cps, glass transition temperature 45 °C)
  • Extender pigment 1 barium sulfate
  • Imidazole-based catalyst (Curesol, Shikoku Corporation)
  • Additive 1 Acrylic polymer (Resiflow P-67, Estron Chemical, leveling agent)
  • the powder coating compositions prepared according to Examples 1-12 and 1-3 were electrostatically spray-painted on specimens preheated at 230° C. for 1 hour to have a thickness of 400 ⁇ m. Thereafter, heat was applied at 230° C. for 5 minutes, and then immersion-cooled with water to prepare a coating specimen, and the physical properties were measured as follows, and the results are shown in Tables 4 to 6 below.
  • the coagulation time was measured through a geltime tester at a temperature of 204 °C.
  • the angle and temperature of the specimen are set to 3° (5 °C), 3.75 ° (10 °C), and 5.5 ° (25 °C). It was measured for cracks.
  • the temperature of the specimen was set to 25°C, and after applying an impact of 4 J/g, it was checked whether damage caused by the impact was performed through a holiday tester.
  • the specimen was immersed in a constant temperature water bath at 75° C. and taken out after 28 days to evaluate adhesion.
  • adhesion After cooling the removed specimen at room temperature for 1 hour, scrape a rectangular shape of 15 mm in width and 30 mm in length with a knife until the material is exposed, and push the knife between the coating film and the material around the exposed part of the material. After measuring the adhesion by the principle of, the peeling area was evaluated.
  • the evaluation criteria are as follows.
  • salt water of 3% concentration was applied to the surface of the coating film to make it abut, and a container was used to prevent evaporation, and a voltage of 1.5 V was applied to the substrate at 65° C. for 30 days.
  • the peeling distance of was measured twice. If the peeling distance was less than 20 mm, it was evaluated as pass, and if it exceeded 20 mm, it was evaluated as failing.
  • the coating film formed of the powder coating composition of Examples 1-12 according to the present invention was generally superior to the coating film formed of the powder coating composition of Comparative Example 1-3.
  • the coating film formed of the powder coating composition of Examples 1-12 had excellent boiling water resistance and negative electrode peeling resistance, and improved the bubble generation rate to secure excellent adhesion.
  • the powder coating composition according to the present invention has excellent heat resistance, boiling water resistance, and negative electrode peeling resistance, and decreases the generation rate of bubbles, thereby improving adhesion and appearance characteristics decrease due to bubbles generated during coating film formation.
  • the powder coating composition of the present invention is excellent in impact resistance and bending resistance, while securing constant workability and a glass transition temperature of 120° C. or higher, and can effectively protect it when applied to a steel pipe.

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a powder coating composition comprising at least one of urethane-modified epoxy resin and bisphenol A-type epoxy resin, a curing agent, and two or more kinds of extender pigment.

Description

분체도료 조성물Powder coating composition
본 발명은 내열성 및 내비등수성이 우수한 분체도료 조성물에 관한 것이다.The present invention relates to a powder coating composition excellent in heat resistance and boiling water resistance.
에폭시 수지 분체도료는 높은 유리전이온도를 가짐으로써 열적 특성이 우수할 뿐만 아니라 접착 강도, 내화학성, 기계적 강도 및 전기 절연성 또한 우수하여, 지하 또는 해저에 매설되는 강관 또는 파이프 라인의 부식 방지 및 내구력 향상을 위한 목적으로 사용되고 있다. 그러나 파이프의 매설 환경이 점차 가혹해짐에 따라, 100 ℃ 내외 수준의 유리전이온도를 갖는 종래의 에폭시 수지 분체도료로는 파이프를 부식으로부터 보호하기 위한 충분한 효과를 얻을 수 없다. 이에 에폭시 도막에 대한 열적, 화학적, 물리적 특성의 개선이 요구되고 있으며, 이러한 물성을 만족하는 도료에 대한 연구도 지속되고 있다.Epoxy resin powder coating has a high glass transition temperature, so it has excellent thermal properties, as well as excellent adhesive strength, chemical resistance, mechanical strength, and electrical insulation, preventing corrosion and improving durability of steel pipes or pipelines buried underground or under the sea. It is being used for the purpose of. However, as the environment in which the pipe is buried becomes harsher, the conventional epoxy resin powder coating having a glass transition temperature of about 100° C. cannot obtain a sufficient effect to protect the pipe from corrosion. Accordingly, there is a demand for improvement in thermal, chemical, and physical properties of the epoxy coating film, and studies on paints that satisfy these physical properties are also ongoing.
일례로, 미국특허 제9,617,413호는 이산화디비닐아렌 수지와 디시안디아마이드 경화제를 이용한 분체도료 조성물을 기술하고 있다. 또한 일본특허 제6,342,696호는 3관능 이상의 에폭시 수지와 구아니딘 화합물 및 이미다졸 화합물 중 1종 이상의 경화제를 포함하는 분체도료 조성물을 기술하고 있다. 그러나 상기 분체도료 조성물의 경우에도 고온 환경에서 요구되는 내비등수성 및 부착성이 충분하지 못하다는 문제가 있다.For example, U.S. Patent No. 9,617,413 discloses a powder coating composition using a divinylarene dioxide resin and a dicyandiamide curing agent. In addition, Japanese Patent No. 6,342,696 discloses a powder coating composition comprising a trifunctional or higher epoxy resin and at least one curing agent of a guanidine compound and an imidazole compound. However, even in the case of the powder coating composition, there is a problem that the boiling water resistance and adhesion required in a high temperature environment are insufficient.
본 발명은 내열성 및 내비등수성이 우수한 분체도료 조성물을 제공한다.The present invention provides a powder coating composition excellent in heat resistance and boiling water resistance.
본 발명은 우레탄 변성 에폭시 수지 및 비스페놀 에이형 에폭시 수지 중 1종 이상, 경화제 및 체질 안료를 포함하는 분체도료 조성물을 제공한다.The present invention provides a powder coating composition comprising at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin, a curing agent and an extender pigment.
본 발명에 따른 분체도료 조성물은 내열성, 내비등수성 및 내음극박리성이 우수하고, 기포 발생율을 저하시켜 도막 형성 시 발생하는 기포로 인한 부착성 저하 및 외관 특성 저하를 개선할 수 있다. 또한, 본 발명의 분체도료 조성물은 충격성 및 내굴곡성이 우수하면서도 일정한 작업성과 120 ℃ 이상의 유리전이온도를 확보하여, 강관에 적용 시 이를 효과적으로 보호할 수 있다.The powder coating composition according to the present invention has excellent heat resistance, boiling water resistance, and negative electrode peeling resistance, and decreases the generation rate of bubbles, thereby improving adhesion and appearance characteristics decrease due to bubbles generated during coating film formation. In addition, the powder coating composition of the present invention is excellent in impact resistance and bending resistance, while securing constant workability and a glass transition temperature of 120° C. or higher, and can effectively protect it when applied to a steel pipe.
이하, 본 발명에 대하여 설명한다. 그러나, 하기 내용에 의해서만 한정되는 것은 아니며, 필요에 따라 각 구성요소가 다양하게 변형되거나 선택적으로 혼용될 수 있다. 따라서, 본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Hereinafter, the present invention will be described. However, it is not limited only by the following contents, and each component may be variously modified or selectively used as necessary. Therefore, it is to be understood as including all changes, equivalents, and substitutes included in the spirit and scope of the present invention.
본 발명에 따른 분체도료 조성물은 우레탄 변성 에폭시 수지 및 비스페놀 에이형 에폭시 수지 중 1종 이상, 경화제 및 체질 안료를 포함한다. 본 발명에 따른 분체도료 조성물은 필요에 따라 유색 안료, 촉매 및 분체도료 분야에서 통상적으로 사용되는 첨가제를 더 포함할 수 있다. 이하, 본 발명의 분체도료 조성물의 조성을 살펴보면 다음과 같다.The powder coating composition according to the present invention includes at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin, a curing agent and an extender pigment. The powder coating composition according to the present invention may further include additives commonly used in the field of colored pigments, catalysts and powder coatings, if necessary. Hereinafter, looking at the composition of the powder coating composition of the present invention is as follows.
에폭시 수지Epoxy resin
본 발명에 따른 분체도료 조성물에서, 에폭시 수지는 주(主) 수지로서 우레탄 변성 에폭시 수지 및 비스페놀 에이형 에폭시 수지 중 1종 이상을 포함한다.In the powder coating composition according to the present invention, the epoxy resin includes at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin as the main resin.
사용 가능한 우레탄 변성 에폭시 수지의 비제한적인 예로는, 우레탄 변성 노볼락 에폭시 수지, 우레탄 변성 비스페놀 에폭시 수지, 우레탄 변성 크레졸 에폭시 수지 또는 이들의 혼합형태 등이 있다. 일례로, 상기 우레탄 변성 에폭시 수지는 우레탄 변성 노볼락 에폭시 수지를 포함하는 것일 수 있다.Non-limiting examples of usable urethane-modified epoxy resins include urethane-modified novolac epoxy resins, urethane-modified bisphenol epoxy resins, urethane-modified cresol epoxy resins, or a mixture thereof. For example, the urethane-modified epoxy resin may include a urethane-modified novolac epoxy resin.
우레탄 변성 에폭시 수지는 우레탄 프리폴리머와 에폭시 수지의 반응으로부터 얻어지는 에폭시 수지일 수 있다. 상기 우레탄 프리폴리머는 폴리올과 이소시아네이트 화합물을 반응시켜 제조할 수 있다. The urethane-modified epoxy resin may be an epoxy resin obtained from a reaction of a urethane prepolymer and an epoxy resin. The urethane prepolymer may be prepared by reacting a polyol and an isocyanate compound.
상기 폴리올의 종류는 특별히 한정되지 않으나, 예를 들어 폴리에스테르 폴리올, 폴리옥시프로필렌글리콜, 폴리부타디엔, 비스페놀 에이, 디에틸렌글리콜, 디프로필렌글리콜, 폴리카프로락톤 및 폴리카프로락탐으로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다. 상기 이소시아네이트 화합물의 종류는 특별히 한정되지 않으나, 예를 들어 2,4-톨루엔 디이소시아네이트, 4,4-디페닐메탄 디이소시아네이트, 1,6-헥사메틸렌 디이소시아네이트, 1,5-나프탈렌 디이소시아네이트 및 4,4-바이페닐 디이소시아네이트로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.The type of the polyol is not particularly limited, for example, one selected from the group consisting of polyester polyol, polyoxypropylene glycol, polybutadiene, bisphenol A, diethylene glycol, dipropylene glycol, polycaprolactone, and polycaprolactam. You can use the above. The kind of the isocyanate compound is not particularly limited, but, for example, 2,4-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, and 4 At least one selected from the group consisting of ,4-biphenyl diisocyanate may be used.
상기 우레탄 변성 에폭시 수지의 이소시아네이트 변성률은 특별히 한정되지 않으나, 예를 들어 10% 내지 40%, 또 다른 예로는 15% 내지 30%일 수 있다.The isocyanate modification rate of the urethane-modified epoxy resin is not particularly limited, but may be, for example, 10% to 40%, and another example, 15% to 30%.
상기 우레탄 변성 에폭시 수지의 에폭시 당량(EEW) 및 연화점은 특별히 한정되지 않으나, 에폭시 당량(EEW)은 250 내지 700 g/eq, 예를 들어 400 내지 650 g/eq일 수 있고, 연화점은 100 ℃ 내지 130 ℃, 예를 들어 105 ℃ 내지 120 ℃일 수 있다. 상기 우레탄 변성 에폭시 수지가 전술한 범위의 에폭시 당량 및 연화점을 가질 때, 도막의 분산성이 우수해질 수 있다.The epoxy equivalent (EEW) and softening point of the urethane-modified epoxy resin are not particularly limited, but the epoxy equivalent (EEW) may be 250 to 700 g/eq, for example, 400 to 650 g/eq, and the softening point is 100°C to It may be 130 ℃, for example 105 ℃ to 120 ℃. When the urethane-modified epoxy resin has an epoxy equivalent and a softening point in the above-described range, the dispersibility of the coating film may be excellent.
상기 우레탄 변성 에폭시 수지의 점도 및 유리전이온도는 특별히 한정되지 않으나, 점도(175 ℃, ICI 점도계)는 1,000 내지 3,500 cps, 예를 들어 1,500 내지 3,000 cps일 수 있고, 유리전이온도는 50 내지 65 ℃, 예를 들어 52 내지 60 ℃일 수 있다. 상기 우레탄 변성 에폭시 수지가 전술한 범위의 점도 및 유리전이온도를 가질 때, 내화학성이 우수해 질 수 있다.The viscosity and glass transition temperature of the urethane-modified epoxy resin are not particularly limited, but the viscosity (175° C., ICI viscometer) may be 1,000 to 3,500 cps, for example, 1,500 to 3,000 cps, and the glass transition temperature is 50 to 65° C. , For example, it may be 52 to 60 ℃. When the urethane-modified epoxy resin has a viscosity and a glass transition temperature in the above-described range, chemical resistance may be excellent.
비스페놀 에이형 에폭시 수지는 비스페놀 A(BPA)와 에피클로로히드린(epichlorohydrin)의 반응으로부터 얻어지는 에폭시 수지이다. 상기 비스페놀 에이형 에폭시 수지로는 당 분야에 알려진 통상적인 에폭시 수지를 특별한 제한없이 사용할 수 있다.Bisphenol A-type epoxy resin is an epoxy resin obtained from the reaction of bisphenol A (BPA) and epichlorohydrin. As the bisphenol A-type epoxy resin, a conventional epoxy resin known in the art may be used without particular limitation.
상기 비스페놀 에이형 에폭시 수지의 에폭시 당량(EEW) 및 연화점은 특별히 한정되지 않으나, 에폭시 당량은 700 내지 1,500 g/eq, 예를 들어 1,000 내지 1,300 g/eq일 수 있고, 연화점은 100 내지 130 ℃일 수 있다. 상기 비스페놀 에이형 에폭시 수지가 전술한 범위의 에폭시 당량 및 연화점을 가질 때, 저장 안정성이 우수해 질 수 있다.The epoxy equivalent (EEW) and softening point of the bisphenol A-type epoxy resin are not particularly limited, but the epoxy equivalent may be 700 to 1,500 g/eq, for example, 1,000 to 1,300 g/eq, and the softening point may be 100 to 130°C. have. When the bisphenol A-type epoxy resin has an epoxy equivalent weight and a softening point in the above-described range, storage stability may be excellent.
상기 비스페놀 에이형 에폭시 수지의 점도 및 유리전이온도는 특별히 한정되지 않으나, 점도(200 ℃, ICI 점도계)는 1,000 내지 5,000 cps, 예를 들어 1,500 내지 4,500 cps일 수 있고, 유리전이온도는 50 내지 80 ℃, 예를 들어 60 내지 70 ℃일 수 있다. 상기 비스페놀 에이형 에폭시 수지가 전술한 범위의 점도 및 유리전이온도를 가질 때, 도막의 외관 특성 및 굴곡성이 향상되어 도막의 크랙(crack) 발생을 최소화시킬 수 있다.The viscosity and glass transition temperature of the bisphenol A-type epoxy resin are not particularly limited, but the viscosity (200° C., ICI viscometer) may be 1,000 to 5,000 cps, for example, 1,500 to 4,500 cps, and the glass transition temperature is 50 to 80° C. , For example, it may be 60 to 70 ℃. When the bisphenol A-type epoxy resin has a viscosity and a glass transition temperature in the above-described ranges, appearance characteristics and flexibility of the coating film are improved, thereby minimizing the occurrence of cracks in the coating film.
본 발명의 분체도료 조성물은 에폭시 수지로 상기 우레탄 변성 에폭시 수지 및 비스페놀 에이형 에폭시 수지를 포함할 수 있다. 상기 우레탄 변성 에폭시 수지와 비스페놀 에이형 에폭시 수지의 배합비는 특별히 한정되는 것은 아니나, 1 내지 5 : 1, 예를 들어 1 내지 3 : 1의 중량비일 수 있다. 상기 2종의 에폭시 수지를 전술한 범위로 배합하여 사용하는 경우, 분체도료 조성물의 내열성 및 내비등수성을 향상시킬 수 있다.The powder coating composition of the present invention may include the urethane-modified epoxy resin and bisphenol A-type epoxy resin as an epoxy resin. The mixing ratio of the urethane-modified epoxy resin and the bisphenol A-type epoxy resin is not particularly limited, but may be a weight ratio of 1 to 5: 1, for example, 1 to 3: 1. When the two types of epoxy resins are blended and used in the above range, heat resistance and boiling water resistance of the powder coating composition may be improved.
상기 에폭시 수지는 분체도료 조성물 총 중량을 기준으로 45 내지 90 중량%, 예를 들어 60 내지 80 중량%, 또 다른 예로는 65 내지 75 중량%일 수 있다. 상기 에폭시 수지 함량이 45 중량% 미만인 경우 도막의 유리전이온도의 저하에 따른 내열성 문제가 발생할 수 있고, 90 중량%를 초과하는 경우 기계적 물성이 불량해질 수 있다.The epoxy resin may be 45 to 90% by weight, for example, 60 to 80% by weight, and another example, 65 to 75% by weight based on the total weight of the powder coating composition. When the content of the epoxy resin is less than 45% by weight, a heat resistance problem may occur due to a decrease in the glass transition temperature of the coating film, and when it exceeds 90% by weight, mechanical properties may be poor.
경화제Hardener
본 발명의 분체도료 조성물은 경화제로서 아민계 경화제 및 페놀계 경화제 중 1종 이상을 포함할 수 있다.The powder coating composition of the present invention may contain one or more of an amine-based curing agent and a phenol-based curing agent as a curing agent.
상기 아민계 경화제는 에폭시 수지와 경화 반응이 가능한 아민계 경화제라면 특별히 한정되지 않는다. 예컨대, 지방족 아민계 경화제, 지환족 아민계 경화제, 방향족 아민계 경화제 등이 있는데, 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다.The amine-based curing agent is not particularly limited as long as it is an amine-based curing agent capable of curing reaction with an epoxy resin. For example, there are an aliphatic amine-based curing agent, an alicyclic amine-based curing agent, and an aromatic amine-based curing agent, and these may be used alone or in combination of two or more.
상기 아민계 경화제의 아민가는 특히 한정되지 않으며, 예를 들어 15 내지 30 mgKOH/g일 수 있다. 상기 아민계 경화제의 아민가가 전술한 범위를 만족하는 경우, 우수한 내식성을 확보할 수 있다.The amine value of the amine-based curing agent is not particularly limited, and may be, for example, 15 to 30 mgKOH/g. When the amine value of the amine-based curing agent satisfies the above range, excellent corrosion resistance can be secured.
페놀계 경화제로는 분체도료 분야에서 통상적으로 사용되는 것을 제한없이 사용할 수 있다. 사용 가능한 페놀계 경화제의 비제한적인 예로는 레졸형 페놀계 수지, 노볼락형 페놀계 수지, 폴리히드록시스티렌 수지 등이 있다. 상기 레졸형 페놀계 수지의 예에는 아닐린 변성 레졸 수지, 멜라민 변성 레졸 수지 등이 있다. 상기 노볼락형 페놀계 수지의 예에는 페놀 노볼락 수지, 크레졸 노볼락 수지, tert-부틸페놀 노볼락 수지, 노닐페놀 노볼락 수지, 나프톨 노볼락 수지, 디시클로펜타디엔 변성 페놀 수지, 테르펜 변성 페놀계 수지, 트리페놀-메탄형 수지, 나프톨 아르알킬 수지 등이 있다. 상기 폴리히드록시스티렌 수지의 예에는 폴리(p-히드록시스티렌) 등이 있다.As the phenolic curing agent, those conventionally used in the powder coating field may be used without limitation. Non-limiting examples of the phenolic curing agent that can be used include resol-type phenolic resins, novolac-type phenolic resins, and polyhydroxystyrene resins. Examples of the resol-type phenolic resin include aniline-modified resol resin and melamine-modified resol resin. Examples of the novolak-type phenolic resin include phenol novolac resin, cresol novolak resin, tert-butylphenol novolac resin, nonylphenol novolac resin, naphthol novolac resin, dicyclopentadiene-modified phenol resin, terpene-modified phenol. Type resin, triphenol-methane type resin, naphthol aralkyl resin, and the like. Examples of the polyhydroxystyrene resin include poly(p-hydroxystyrene).
상기 페놀계 경화제의 수산기 당량은 특히 한정되지 않으며, 예를 들어 200 내지 300 g/eq일 수 있다.The hydroxyl group equivalent of the phenolic curing agent is not particularly limited, and may be, for example, 200 to 300 g/eq.
상기 경화제는 분체도료 조성물 총 중량을 기준으로 0.1 내지 5 중량%, 예를 들어 0.1 내지 3 중량%로 포함될 수 있다. 경화제의 함량이 전술한 범위일 경우, 도막의 경화도가 높아 도막의 물성이 향상될 수 있다.The curing agent may be included in an amount of 0.1 to 5% by weight, for example, 0.1 to 3% by weight, based on the total weight of the powder coating composition. When the content of the curing agent is within the above-described range, the degree of curing of the coating film is high, and physical properties of the coating film may be improved.
체질 안료Extender pigment
본 발명의 분체도료 조성물은 상기 조성물의 고유 특성을 해하지 않는 범위 내에서, 분체도료 분야에 통상적으로 사용되는 체질 안료를 더 포함할 수 있다. 체질 안료는 도료의 고온/고압 내화학성을 더욱 향상시킬 수 있다.The powder coating composition of the present invention may further include an extender pigment commonly used in the powder coating field within a range that does not impair the intrinsic properties of the composition. The extender pigment can further improve the high temperature/high pressure chemical resistance of the paint.
사용 가능한 체질 안료의 비제한적인 예로는, 탄산칼슘, 황산바륨, 장석, 카오린, 수산화알루미나, 수산화마그네슘, 티타늄다이옥사이드, 탄산마그네슘, 알루미나, 운모, 몬모릴로나이트, 올라스토나이트, 탈크, 질화알루미늄, 질화규소, 질화붕소, 산화알루미늄, 질화알루미늄 등이 있는데, 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of extender pigments that can be used include calcium carbonate, barium sulfate, feldspar, kaolin, alumina hydroxide, magnesium hydroxide, titanium dioxide, magnesium carbonate, alumina, mica, montmorillonite, olastonite, talc, aluminum nitride, silicon nitride, There are boron nitride, aluminum oxide, aluminum nitride, and the like, and these may be used alone or in combination of two or more.
상기 체질 안료는 탄산칼슘, 황산바륨, 장석 및 카오린을 포함하는 무기 안료 군에서 선택되는 1종 이상의 체질 안료를 포함할 수 있다.The extender pigment may include one or more extender pigments selected from the group of inorganic pigments including calcium carbonate, barium sulfate, feldspar, and kaolin.
일례로, 상기 체질 안료는 황산바륨 및 장석을 포함하는 것일 수 있다. 상기 황산바륨 및 장석의 배합비는 특별히 한정되지 않으나, 1 : 0.5 내지 5, 예를 들어 1 : 0.8 내지 2.5 중량비일 수 있다. 체질 안료가 황산바륨 및 장석을 전술한 배합비 범위로 포함하는 경우, 도막의 내비등수성 및 장기 내음극박리성을 향상시켜 우수한 내식성을 확보할 수 있다.For example, the extender pigment may include barium sulfate and feldspar. The blending ratio of barium sulfate and feldspar is not particularly limited, but may be 1: 0.5 to 5, for example, 1: 0.8 to 2.5 weight ratio. When the extender pigment includes barium sulfate and feldspar in the above-described blending ratio, it is possible to secure excellent corrosion resistance by improving the boiling water resistance and long-term negative electrode peeling resistance of the coating film.
상기 체질 안료의 형상은 구형 또는 무정형일 수 있으며, 이에 특별히 한정되지 않는다. 또한, 상기 체질 안료의 평균 입경은 특별히 제한되지 않으며, 예컨대 1 내지 20 ㎛일 수 있다.The shape of the extender pigment may be spherical or amorphous, and is not particularly limited thereto. In addition, the average particle diameter of the extender pigment is not particularly limited, and may be, for example, 1 to 20 μm.
상기 체질 안료는 분체도료 조성물 총 중량을 기준으로 5 내지 45 중량%, 다른 예로 15 내지 40 중량%일 수 있다. 체질 안료의 함량이 전술한 범위일 경우, 도막의 기계적 물성, 내충격성, 부착성 등이 향상될 수 있다.The extender pigment may be 5 to 45% by weight based on the total weight of the powder coating composition, in another example 15 to 40% by weight. When the content of the extender pigment is in the above-described range, mechanical properties, impact resistance, and adhesion of the coating film may be improved.
유색 안료Colored pigments
본 발명의 분체도료 조성물은 상기 조성물의 고유 특성을 해하지 않는 범위 내에서, 분체도료 분야에 통상적으로 사용되는 유색 안료를 더 포함할 수 있다.The powder coating composition of the present invention may further include a colored pigment commonly used in the powder coating field within a range that does not impair the inherent properties of the composition.
유색 안료는 에폭시 수지와 혼합하여 분체도료에 원하는 색상(유색)을 발현하거나 도막의 강도나 광택을 증가시키기 위해 사용될 수 있다. 이러한 유색 안료로는 분체도료에 통상적으로 사용되는 유기 안료, 무기 안료, 메탈릭 안료, 알루미늄-페이스트(Al-paste), 펄(pearl) 등을 제한 없이 사용할 수 있으며, 이들을 단독으로 사용하거나 2종 이상을 혼용할 수 있다. 사용 가능한 유색 안료의 비제한적인 예로는, 아조계, 프탈로시아닌계, 산화철계, 코발트계, 탄산염계, 황산염계, 규산염계, 크롬산염계 안료 등이 있으며, 예컨대, 티타늄 디옥사이드, 징크 옥사이드, 비스무스 바나데이트, 시아닌 그린, 카본 블랙, 산화철적, 산화철황, 네이비 블루, 시아닌 블루 및 이들의 2종 이상의 혼합물 등이 있다. The colored pigment may be mixed with an epoxy resin to express a desired color (color) in the powder coating or used to increase the strength or gloss of the coating film. As such colored pigments, organic pigments, inorganic pigments, metallic pigments, aluminum-paste, pearl, etc., which are commonly used in powder coatings, can be used without limitation, and these can be used alone or in two or more types. Can be mixed. Non-limiting examples of the color pigments that can be used include azo-based, phthalocyanine-based, iron oxide-based, cobalt-based, carbonate-based, sulfate-based, silicate-based, chromate-based pigments, and the like, such as titanium dioxide, zinc oxide, bismuth vanadium. Date, cyanine green, carbon black, iron oxide, sulfur iron oxide, navy blue, cyanine blue, and mixtures of two or more thereof.
본 발명에서, 유색 안료의 함량은 특별히 한정되지 않으며, 예컨대 분체도료 조성물의 총 중량을 기준으로 0.1 내지 15 중량%, 다른 예로 0.1 내지 10 중량%일 수 있다. 유색 안료의 함량이 전술한 범위일 경우, 본 발명의 분체도료 조성물을 적용한 도막의 색상 발현이 우수하고, 도막의 은폐성 및 기계적 물성이 향상될 수 있다.In the present invention, the content of the colored pigment is not particularly limited, and may be, for example, 0.1 to 15% by weight, for example 0.1 to 10% by weight, based on the total weight of the powder coating composition. When the content of the colored pigment is within the above-described range, the color expression of the coating film to which the powder coating composition of the present invention is applied is excellent, and the hiding property and mechanical properties of the coating film can be improved.
촉매catalyst
본 발명의 분체도료 조성물은 상기 조성물의 고유 특성을 해하지 않는 범위 내에서, 분체도료 분야에 통상적으로 사용되는 촉매를 더 포함할 수 있다.The powder coating composition of the present invention may further include a catalyst commonly used in the powder coating field within a range that does not harm the inherent properties of the composition.
상기 촉매는 주(主) 수지인 에폭시 수지와 경화제 간의 반응을 촉진하는 물질로서, 예컨대 이미다졸계 촉매, 포스포늄계 촉매, 아민계 촉매, 금속계 촉매 등이 있는데, 이들을 단독으로 사용하거나 2종 이상을 혼합하여 사용할 수 있다. The catalyst is a material that accelerates the reaction between the epoxy resin and the curing agent, which is the main resin, and includes, for example, an imidazole catalyst, a phosphonium catalyst, an amine catalyst, and a metal catalyst. Can be used by mixing.
상기 이미다졸계 촉매의 비제한적인 예를 들면, 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-데실이미다졸, 2-헥틸이미다졸, 2-이소프로필이미다졸, 2-운데실이미다졸, 2-헵탄데실이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 1-벤질-2-메틸이미다졸, 1-벤질-2-페닐이미다졸, 1-시아노에틸-2-메틸이미다졸, 1-시아노에틸-2-에틸-4-메틸이미다졸, 1-시아노에틸-2-운데실이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-시아노에틸-2-운데실-이미다졸 트리멜리테이트, 1-시아노에틸-2-페닐이미다졸 트리멜리테이트, 2,4-디아미노-6-(2'-메틸이미다졸-(1')-에틸-s-트리아진, 2-페실-4,5-디하이드록시메틸이미다졸, 2-페실-4-메틸-5-하이드록시메틸이미다졸, 2-페실-4-벤질-5-하이드록시메틸이미다졸, 4,4'-메틸렌-비스-(2-에틸-5-메틸이미다졸), 2-아미노에틸-2-메틸 이미다졸, 1-시아노에틸-2-페닐-4,5-디(시아노에톡시메틸)이미다졸, 1-도데실-2-메틸-3-벤질이미다졸리늄클로라이드, 이미다졸 함유 폴리아미드 등이 있다.Non-limiting examples of the imidazole-based catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-hectylimidazole, 2-isopropylimida Sol, 2-undecylimidazole, 2-heptanedecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl -2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-cyanoethyl-2 -Phenylimidazole trimellitate, 2,4-diamino-6-(2'-methylimidazole-(1')-ethyl-s-triazine, 2-fesyl-4,5-dihydroxy Methylimidazole, 2-fesyl-4-methyl-5-hydroxymethylimidazole, 2-fesyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-(2 -Ethyl-5-methylimidazole), 2-aminoethyl-2-methyl imidazole, 1-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dode Sil-2-methyl-3-benzylimidazolinium chloride, imidazole-containing polyamide, and the like.
상기 포스포늄계 촉매의 비제한적인 예로는 벤질트리페닐 포스포늄 클로라이드, 부틸트리페닐 포스포늄 클로라이드, 부틸트리페닐 포스포늄 브로마이드, 에틸트리페닐 포스포늄 아세테이트, 에틸트리페닐 포스포늄 브로마이드, 에틸트리페닐 포스포늄 아이오다이드, 테트라페닐 포스포늄 브로마이드, 테트라페닐 포스포늄 클로라이드 또는 테트라페닐 포스포늄 아이오다이드 등이 있다.Non-limiting examples of the phosphonium-based catalyst include benzyltriphenyl phosphonium chloride, butyltriphenyl phosphonium chloride, butyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium acetate, ethyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium Phonium iodide, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride or tetraphenyl phosphonium iodide.
상기 아민계 촉매의 비제한적인 예로는, 트리에틸아민, 트리에틸렌디아민, 테트라메틸-1,3-부탄디아민, 에틸모르폴린, 디아자비시클로운데센, 디아자비시클로노넨 등이 있다.Non-limiting examples of the amine-based catalyst include triethylamine, triethylenediamine, tetramethyl-1,3-butanediamine, ethylmorpholine, diazabicycloundecene, and diazabicyclononene.
상기 금속계 촉매로는 코발트, 구리, 아연, 철, 니켈, 망간, 주석 등의 유기 금속 착체 또는 유기 금속염을 들 수 있다. 상기 유기 금속 착체의 예로는, 코발트(II) 아세틸아세토네이트, 코발트(III) 아세틸아세토네이트 등의 유기 코발트 착체, 구리(II) 아세틸아세토네이트 등의 유기 구리 착체, 아연(II) 아세틸아세토네이트 등의 유기 아연 착체, 철(III) 아세틸아세토네이트 등의 유기 철 착체, 니켈(II) 아세틸아세토네이트 등의 유기 니켈 착체, 망간(II) 아세틸아세토네이트 등의 유기 망간 착체 등을 들 수 있는데, 이에 한정되지는 않는다. 상기 유기 금속염의 예로는, 옥틸산 아연, 옥틸산 주석, 나프텐산 아연, 나프텐산 코발트, 스테아르산 주석, 스테아르산 아연 등을 들 수 있는데, 이에 한정되지는 않는다. Examples of the metal catalyst may include organic metal complexes or organic metal salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese complexes such as manganese (II) acetylacetonate, etc. It is not limited. Examples of the organic metal salt include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.
본 발명에서, 상기 촉매의 함량은 에폭시 수지와 경화제의 반응성에 따라 조절될 수 있다. 예컨대, 상기 촉매의 함량은 분체도료 조성물의 총 중량을 기준으로 0.01 내지 2 중량%, 다른 예로 0.01 내지 1 중량%일 수 있다. 상기 촉매의 함량이 전술한 범위를 벗어날 경우, 도막의 기계적 물성이 저하될 수 있다.In the present invention, the content of the catalyst may be adjusted according to the reactivity of the epoxy resin and the curing agent. For example, the content of the catalyst may be 0.01 to 2% by weight, in another example 0.01 to 1% by weight, based on the total weight of the powder coating composition. When the content of the catalyst is out of the above-described range, mechanical properties of the coating film may be deteriorated.
첨가제additive
본 발명의 분체도료 조성물은 상기 조성물의 고유 특성을 해하지 않는 범위 내에서, 분체도료 분야에 통상적으로 사용되는 첨가제를 더 포함할 수 있다.The powder coating composition of the present invention may further include additives commonly used in the powder coating field within a range that does not harm the inherent properties of the composition.
본 발명에서 사용 가능한 첨가제의 비제한적인 예를 들면, 레벨링제, 핀홀 방지제, 분산제, 부착 증진제, 유동성 첨가제, 흐름성 향상제, 저응력화제, 크래터링 방지제, 커플링제, 광택조절제, 난연제, 소광제, 보조 경화제 및 광 흡수제 등이 있는데, 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of additives that can be used in the present invention include leveling agents, pinhole inhibitors, dispersants, adhesion promoters, flow additives, flow improvers, low stress agents, cratering inhibitors, coupling agents, gloss modifiers, flame retardants, matting agents. , An auxiliary curing agent and a light absorbing agent, and these may be used alone or in combination of two or more.
레벨링제는 도료 조성물이 평탄하고 매끄럽게 코팅되도록 레벨링함으로써, 조성물 내의 접착력을 증진시키면서 도막의 외관 특성을 향상시키기 위한 것이다. 예를 들면, 아크릴계, 실리콘계, 폴리에스테르계, 아민계 레벨링제 등이 있는데, 이에 특별히 한정되지 않는다.The leveling agent is intended to improve the appearance characteristics of the coating film while improving adhesion in the composition by leveling the coating composition to be coated smoothly and smoothly. For example, there are acrylic, silicone, polyester, and amine leveling agents, but are not particularly limited thereto.
핀홀 방지제는 경화 공정 시 도막으로부터 휘발성 물질이 방출되도록 하여, 도막 내 핀홀 발생을 방지하고 외관 특성을 높여줄 수 있다. 핀홀 방지제의 비제한적인 예로는 아마이드계[예, ceraflour 960(BYK社)], 폴리프로필렌계, 스테아릭산계 핀홀 방지제 등이 있다. 일례로, 핀홀 방지제는 벤조인(benzoin) 또는 벤조인과 아마이드계 핀홀 방지제의 혼합물일 수 있다.The pinhole inhibitor allows volatile substances to be released from the coating film during the curing process, thereby preventing the occurrence of pinholes in the coating film and improving appearance characteristics. Non-limiting examples of pinhole inhibitors include amide-based (eg, ceraflour 960 (BYK)), polypropylene-based, stearic acid-based pinhole inhibitors, and the like. For example, the pinhole inhibitor may be benzoin or a mixture of benzoin and an amide pinhole inhibitor.
상기 분산제로는 당 분야에 알려진 통상적인 것을 제한 없이 사용할 수 있으며, 일례로 유색 안료 표면에 흡착되어 탈기(degassing) 효과를 극대화시키는 폴리아크릴계 분산제를 사용할 수 있다.As the dispersant, conventional ones known in the art may be used without limitation, and as an example, a polyacrylic dispersant may be used that is adsorbed on the surface of a colored pigment to maximize a degassing effect.
부착 증진제는 도막의 부착성을 증진시키기 위한 물질로서, 실란계 부착 증진제 등을 사용할 수 있다. 상기 부착 증진제의 비제한적인 예로는 머캅토알킬알콕시실란(mercaptoalkylakoxysilane), 감마글리독시프로필트리메톡시실란 등이 있고, 일례로, 부착 증진제는 분자량이 150 내지 300 g/mol인 머캅토알킬알콕시실란일 수 있다.The adhesion promoter is a substance for enhancing the adhesion of the coating film, and a silane adhesion promoter or the like may be used. Non-limiting examples of the adhesion promoter include mercaptoalkylakoxysilane, gammaglydoxypropyltrimethoxysilane, and the like, and as an example, the adhesion promoter is a mercaptoalkylalkoxysilane having a molecular weight of 150 to 300 g/mol. Can be
유동성 첨가제는 유동성 효과를 극대화하기 위해 사용 되는 것으로, 도료의 부착성 향상과 함께 장기 유동성을 확보할 수 있다. 상기 유동성 첨가제로는 왁스류, 실리카 등을 사용할 수 있다. 사용 가능한 유동성 첨가제의 비제한적인 예로는 파라핀 왁스, 천연 왁스(예, 카르나우바 왁스 등), 합성 왁스(예, 폴리에틸렌 왁스 등), 실리카 등이 있는데, 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다. 또한, 왁스류는 실리카와 혼합되어 사용될 수 있다. 상기 유동성 첨가제는 칩을 만든 후 첨가하는 후(後) 첨가 성분으로 사용될 수 있다.The fluid additive is used to maximize the fluidity effect, and can secure long-term fluidity while improving the adhesion of the paint. As the flowable additive, waxes, silica, and the like may be used. Non-limiting examples of flowable additives that can be used include paraffin wax, natural wax (e.g., carnauba wax, etc.), synthetic wax (e.g., polyethylene wax, etc.), silica, etc., which are used alone or in combination of two or more. Can be used. In addition, waxes may be mixed with silica and used. The flowable additive may be used as an additive component after adding it after making a chip.
흐름성 향상제는 도막의 표면장력을 낮추고 유연한 외관을 구현하기 위해 사용하는 것으로서, 당 분야에 알려진 통상적인 것을 사용할 수 있다. 비제한적인 예로는 아크릴계 또는 실리콘계 흐름성 향상제 등이 있다.The flow improving agent is used to lower the surface tension of the coating film and realize a flexible appearance, and a conventional one known in the art may be used. Non-limiting examples include acrylic or silicone flow enhancers.
이와 같은 첨가제는 당 기술분야에 공지된 함량 범위 내에서 첨가될 수 있으며, 예컨대 분체도료 조성물 총 중량에 대하여 0.01 내지 15 중량%, 다른 예로 0.1 내지 5 중량%일 수 있다. 상기 첨가제의 함량이 전술한 범위일 경우, 도막의 외관 및 경도가 향상될 수 있다.Such additives may be added within a range known in the art, for example, 0.01 to 15% by weight based on the total weight of the powder coating composition, and in another example, 0.1 to 5% by weight. When the content of the additive is within the above-described range, the appearance and hardness of the coating film may be improved.
본 발명에 따른 분체도료 조성물은 당 분야에 알려진 방법에 의해 제조될 수 있으며, 일례로 원료 평량, 건식 예비 혼합, 분산 및 조분쇄, 분쇄 및 분급 등의 공정을 통해 제조될 수 있다.The powder coating composition according to the present invention may be prepared by a method known in the art, and for example, may be prepared through processes such as basis weight of raw materials, dry premixing, dispersion and coarse pulverization, pulverization and classification.
예를 들어, 에폭시 수지, 경화제, 체질 안료, 유색 안료, 촉매 및 선택적으로 첨가제 등을 함유하는 원재료 혼합물을 컨테이너 믹서에 투입하여 균일하게 혼합하고, 상기 혼합된 조성물을 용융 혼합시킨 후 이를 분쇄하여 제조될 수 있다. 일례로, 상기 원재료 혼합물을 니이더(kneader) 또는 익스트루더(extruder) 등의 용융 혼련 장치에 의해 85 내지 120 ℃로 용융 분산시켜 소정의 두께(예, 1 내지 5 mm)로 칩을 제조한 후, 제조된 칩을 고속믹서 등의 분쇄 장치를 이용하여 30 내지 100 ㎛ 범위로 분쇄한 후 분급하여 분체도료 조성물을 제조할 수 있다.For example, a raw material mixture containing an epoxy resin, a curing agent, an extender pigment, a colored pigment, a catalyst, and optionally an additive is added to a container mixer to be uniformly mixed, and the mixed composition is melt-mixed and then pulverized. Can be. For example, by melting and dispersing the raw material mixture at 85 to 120°C by a melt-kneading device such as a kneader or an extruder to prepare chips with a predetermined thickness (eg, 1 to 5 mm). Thereafter, the prepared chips may be pulverized in a range of 30 to 100 μm using a pulverizing device such as a high-speed mixer, and then classified to prepare a powder coating composition.
상기 분급 공정은 특별히 한정되지 않으며, 예컨대 80 내지 120 메쉬로 필터링할 수 있다. 이에 따라, 평균입자의 크기가 30 내지 100 ㎛ 범위인 분체도료를 얻을 수 있다. 분체의 평균 입경은 특별히 제한되지 않으나, 전술한 범위를 만족할 경우 도장 작업성 및 도막의 외관 특성이 증진될 수 있다.The classification process is not particularly limited, and may be filtered by, for example, 80 to 120 mesh. Accordingly, a powder coating having an average particle size in the range of 30 to 100 μm can be obtained. The average particle diameter of the powder is not particularly limited, but when the above-described range is satisfied, coating workability and appearance characteristics of the coating film may be improved.
분체도료의 유동성 향상을 위해 실리카 등의 미분말로 본 발명에 따른 분체도료 입자의 표면을 피복할 수도 있다. 이러한 처리를 하는 방법으로서는 분쇄 시에 미분말을 첨가하면서 혼합하는 분쇄 혼합법이나 헨셸 믹서 등에 의한 건식 혼합법을 이용할 수 있다.In order to improve the flowability of the powder coating, the surface of the powder coating particles according to the present invention may be coated with a fine powder such as silica. As a method of performing such treatment, a pulverization mixing method in which fine powder is added and mixed during pulverization, a dry mixing method using a Henschel mixer or the like can be used.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나, 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.
[실시예 1-12][Example 1-12]
하기 표 1 및 표 2에 나타난 조성에 따라 각 성분을 배합한 후, 컨테이너 믹서(씨엠식스)를 이용하여 균일하게 혼합하였다. 균일하게 혼합된 조성물을 니이더(피엘케이-46, 부스社)를 통하여 85 내지 120 ℃에서 용융혼합시킨 다음, 분쇄기를 이용하여 분쇄한 후 평균 입도 30 내지 100 마이크론으로 분급하여 실시예 1-12의 분체도료 조성물을 제조하였다. 하기 표 1 및 표 2의 사용량 단위는 중량%이다.After mixing each component according to the composition shown in Table 1 and Table 2, it was uniformly mixed using a container mixer (CMS). The uniformly mixed composition was melt-mixed at 85 to 120°C through a kneader (PLK-46, Bus company), pulverized using a grinder, and classified into an average particle size of 30 to 100 microns, and Examples 1-12 A powder coating composition was prepared. The units used in Tables 1 and 2 are weight percent.
[비교예 1-3][Comparative Example 1-3]
하기 표 3의 조성에 따른 것을 제외하고, 실시예와 동일한 방법으로 비교예 1-3의 분체도료 조성물을 제조하였다. 하기 표 3의 사용량 단위는 중량%이다.A powder coating composition of Comparative Example 1-3 was prepared in the same manner as in Example, except for the composition of Table 3 below. The units used in Table 3 below are weight percent.
Figure PCTKR2019015957-appb-T000001
Figure PCTKR2019015957-appb-T000001
Figure PCTKR2019015957-appb-T000002
Figure PCTKR2019015957-appb-T000002
Figure PCTKR2019015957-appb-T000003
Figure PCTKR2019015957-appb-T000003
에폭시 수지 1: 우레탄 변성 에폭시 수지(에폭시 당량 465 g/eq, 연화점 115 ℃, 점도(175 ℃, ICI 점도계) 2,250 cps, 유리전이온도 57 ℃, 이소시아네이트 변성률 25%)Epoxy resin 1: Urethane modified epoxy resin (epoxy equivalent 465 g/eq, softening point 115 ℃, viscosity (175 ℃, ICI viscometer) 2,250 cps, glass transition temperature 57 ℃, isocyanate modification rate 25%)
에폭시 수지 2: 우레탄 변성 에폭시 수지(에폭시 당량 400 g/eq, 연화점 105 ℃, 점도(175 ℃, ICI 점도계) 1,500 cps, 유리전이온도 52 ℃, 이소시아네이트 변성률 15%)Epoxy resin 2: Urethane modified epoxy resin (epoxy equivalent 400 g/eq, softening point 105°C, viscosity (175°C, ICI viscometer) 1,500 cps, glass transition temperature 52°C, isocyanate modification rate 15%)
에폭시 수지 3: 우레탄 변성 에폭시 수지(에폭시 당량 600 g/eq, 연화점 120 ℃, 점도(175 ℃, ICI 점도계) 3,000 cps, 유리전이온도 60 ℃, 이소시아네이트 변성률 30%)Epoxy resin 3: urethane modified epoxy resin (epoxy equivalent 600 g/eq, softening point 120 ℃, viscosity (175 ℃, ICI viscometer) 3,000 cps, glass transition temperature 60 ℃, isocyanate modification rate 30%)
에폭시 수지 4: 우레탄 변성 에폭시 수지(에폭시 당량 900 g/eq, 연화점 90 ℃, 점도(175 ℃, ICI 점도계) 1,000 cps, 유리전이온도 45 ℃)Epoxy resin 4: Urethane modified epoxy resin (epoxy equivalent 900 g/eq, softening point 90 ℃, viscosity (175 ℃, ICI viscometer) 1,000 cps, glass transition temperature 45 ℃)
에폭시 수지 5: 비스페놀 에이형 에폭시 수지(에폭시 당량 1,150 g/eq, 연화점 120 ℃, 점도(200 ℃, ICI 점도계) 2,300 cps, 유리전이온도 65 ℃)Epoxy resin 5: Bisphenol A-type epoxy resin (epoxy equivalent 1,150 g/eq, softening point 120 ℃, viscosity (200 ℃, ICI viscometer) 2,300 cps, glass transition temperature 65 ℃)
에폭시 수지 6: 비스페놀 에이형 에폭시 수지(에폭시 당량 1,000 g/eq, 연화점 115 ℃, 점도(200 ℃, ICI 점도계) 1,500 cps, 유리전이온도 60 ℃)Epoxy resin 6: Bisphenol A-type epoxy resin (epoxy equivalent 1,000 g/eq, softening point 115 ℃, viscosity (200 ℃, ICI viscometer) 1,500 cps, glass transition temperature 60 ℃)
에폭시 수지 7: 비스페놀 에이형 에폭시 수지(에폭시 당량 1,300 g/eq, 연화점 125 ℃, 점도(200 ℃, ICI 점도계) 4,500 cps, 유리전이온도 70 ℃)Epoxy resin 7: Bisphenol A-type epoxy resin (epoxy equivalent 1,300 g/eq, softening point 125 ℃, viscosity (200 ℃, ICI viscometer) 4,500 cps, glass transition temperature 70 ℃)
에폭시 수지 8: 비스페놀 에이형 에폭시 수지(에폭시 당량 650 g/eq, 연화점 130 ℃, 점도(200 ℃, ICI 점도계) 3,000 cps, 유리전이온도 45 ℃)Epoxy resin 8: Bisphenol A-type epoxy resin (epoxy equivalent 650 g/eq, softening point 130 ℃, viscosity (200 ℃, ICI viscometer) 3,000 cps, glass transition temperature 45 ℃)
경화제: 디시안디아미드(디시아넥스1400에프, 에어프로덕트社, 아민가 21 mgKOH/g)Hardener: Dicyandiamide (Dicianex 1400F, Air Products, amine value 21 mgKOH/g)
체질 안료 1: 황산바륨Extender pigment 1: barium sulfate
체질 안료 2: 장석Extender Pigment 2: Feldspar
유색 안료: 산화철Colored pigment: iron oxide
촉매: 이미다졸계 촉매(큐어졸, 시코쿠社)Catalyst: Imidazole-based catalyst (Curesol, Shikoku Corporation)
첨가제 1: 아크릴폴리머(레시플로우 피-67, 에스트론케미칼社, 레벨링제)Additive 1: Acrylic polymer (Resiflow P-67, Estron Chemical, leveling agent)
첨가제 2: 트리스아미노(부착 증진제)Additive 2: Trisamino (adhesion enhancer)
첨가제 3: 아마이드(보조 경화제)Additive 3: Amide (auxiliary hardener)
첨가제 4: 액상 실란(부착 증진제)Additive 4: Liquid silane (adhesion enhancer)
[실험예 - 물성 평가][Experimental Example-Evaluation of Physical Properties]
시편 제조Specimen preparation
실시예 1-12 및 비교예 1-3에 따라 제조된 분체도료 조성물을 230 ℃에서 1시간동안 예열시킨 시편에 정전 스프레이 도장하여 400 ㎛ 두께로 도장하였다. 이후 230 ℃에서 5분동안 열을 가한 다음, 물로 침적 냉각하여 도막 시편을 제조하여 물성을 하기와 같이 측정하였으며, 이의 결과를 하기 표 4 내지 표 6에 나타내었다.The powder coating compositions prepared according to Examples 1-12 and 1-3 were electrostatically spray-painted on specimens preheated at 230° C. for 1 hour to have a thickness of 400 μm. Thereafter, heat was applied at 230° C. for 5 minutes, and then immersion-cooled with water to prepare a coating specimen, and the physical properties were measured as follows, and the results are shown in Tables 4 to 6 below.
응고시간Coagulation time
204 ℃의 온도에서 응고시간 측정기기(Geltime tester)를 통해 응고되는 시간을 측정하였다.The coagulation time was measured through a geltime tester at a temperature of 204 °C.
유리전이온도Glass transition temperature
시차 주사 열량 측정기(Differential Scanning Calorimeter)를 이용하여 측정하였다.It was measured using a Differential Scanning Calorimeter.
굴곡성Flexibility
CSA Z245.20 규격에 따라, 시편의 각도 및 온도를 3°(5 ℃), 3.75°(10 ℃), 5.5°(25 ℃)로 설정한 다음 맨드럴을 이용하여 시편을 꺾었을 때 도막의 깨짐 여부를 측정하였다.According to CSA Z245.20 standard, the angle and temperature of the specimen are set to 3° (5 °C), 3.75 ° (10 °C), and 5.5 ° (25 °C). It was measured for cracks.
충격성Impact
CSA Z245.20 규격에 따라, 시편의 온도를 25 ℃가 되도록 한 후, 4 J/g의 충격을 가한 후 holiday tester기를 통하여 충격에 의한 손상 여부를 확인하였다.According to the CSA Z245.20 standard, the temperature of the specimen was set to 25°C, and after applying an impact of 4 J/g, it was checked whether damage caused by the impact was performed through a holiday tester.
기포 발생율Bubble generation rate
CSA Z245.20 규격에 따라, 시편에서 피도물과 도막을 강제로 분리한 후 접착 부분을 실체현미경(SZX16)으로 관찰하였다.According to the CSA Z245.20 standard, after forcibly separating the coated object and the coating film from the specimen, the bonded portion was observed with a stereoscopic microscope (SZX16).
내비등수성Boiling water resistance
시편을 75 ℃의 항온수조에 침적하고 28일 후 꺼내어 부착력을 평가하였다. 부착력은 꺼내어진 시편을 1시간 동안 상온으로 식힌 후, 가로 15 ㎜, 세로 30 ㎜의 직사각형 모양을 칼로 소지가 노출될 때까지 긁고, 소지 노출 부위를 중심으로 도막과 소지 사이에 칼을 밀어 넣어 지레의 원리로 부착성을 측정한 후, 박리면적을 평가하였다. 평가 기준은 하기와 같다.The specimen was immersed in a constant temperature water bath at 75° C. and taken out after 28 days to evaluate adhesion. For adhesion, after cooling the removed specimen at room temperature for 1 hour, scrape a rectangular shape of 15 mm in width and 30 mm in length with a knife until the material is exposed, and push the knife between the coating film and the material around the exposed part of the material. After measuring the adhesion by the principle of, the peeling area was evaluated. The evaluation criteria are as follows.
1등급 : 도막이 벗겨지지 않음Grade 1: The coating film does not come off
2등급 : 50% 박리Grade 2: 50% peeling
3등급 : 75% 박리Grade 3: 75% peeling
4등급 : 100% 박리Grade 4: 100% peeling
5등급 : 도막부착을 유지 못함Grade 5: Can't maintain coating film adhesion
내음극박리성Cathodic peeling resistance
시편 중앙에 직경 3 ㎜의 구멍을 뚫은 후, 3% 농도의 소금물을 도막 표면에 가하여 맞닿게 하고, 용기를 이용하여 증발을 막은 후, 소지에 1.5 V 전압을 65 ℃에서 30일간 가하여 상기 구멍으로부터의 박리 거리를 2회 측정하였다. 박리 거리가 20 mm 이하면 합격, 20 mm을 초과하면 불합격으로 평가하였다.After drilling a hole with a diameter of 3 mm in the center of the specimen, salt water of 3% concentration was applied to the surface of the coating film to make it abut, and a container was used to prevent evaporation, and a voltage of 1.5 V was applied to the substrate at 65° C. for 30 days. The peeling distance of was measured twice. If the peeling distance was less than 20 mm, it was evaluated as pass, and if it exceeded 20 mm, it was evaluated as failing.
Figure PCTKR2019015957-appb-T000004
Figure PCTKR2019015957-appb-T000004
Figure PCTKR2019015957-appb-T000005
Figure PCTKR2019015957-appb-T000005
Figure PCTKR2019015957-appb-T000006
Figure PCTKR2019015957-appb-T000006
상기 표 4 내지 6에 나타난 바와 같이, 본 발명에 따른 실시예 1-12의 분체도료 조성물로 형성된 도막은 비교예 1-3의 분체도료 조성물로 형성된 도막에 비해 전반적으로 물성이 우수하였다. 특히 실시예 1-12의 분체도료 조성물로 형성된 도막은 내비등수성 및 내음극박리성이 우수하고, 기포 발생율을 개선하여 우수한 부착성을 확보할 수 있음을 확인할 수 있었다.As shown in Tables 4 to 6, the coating film formed of the powder coating composition of Examples 1-12 according to the present invention was generally superior to the coating film formed of the powder coating composition of Comparative Example 1-3. In particular, it was confirmed that the coating film formed of the powder coating composition of Examples 1-12 had excellent boiling water resistance and negative electrode peeling resistance, and improved the bubble generation rate to secure excellent adhesion.
본 발명에 따른 분체도료 조성물은 내열성, 내비등수성 및 내음극박리성이 우수하고, 기포 발생율을 저하시켜 도막 형성 시 발생하는 기포로 인한 부착성 저하 및 외관 특성 저하를 개선할 수 있다. 또한, 본 발명의 분체도료 조성물은 충격성 및 내굴곡성이 우수하면서도 일정한 작업성과 120 ℃ 이상의 유리전이온도를 확보하여, 강관에 적용 시 이를 효과적으로 보호할 수 있다.The powder coating composition according to the present invention has excellent heat resistance, boiling water resistance, and negative electrode peeling resistance, and decreases the generation rate of bubbles, thereby improving adhesion and appearance characteristics decrease due to bubbles generated during coating film formation. In addition, the powder coating composition of the present invention is excellent in impact resistance and bending resistance, while securing constant workability and a glass transition temperature of 120° C. or higher, and can effectively protect it when applied to a steel pipe.

Claims (7)

  1. 우레탄 변성 에폭시 수지 및 비스페놀 에이형 에폭시 수지 중 1종 이상, 경화제 및 2종 이상의 체질 안료를 포함하는 분체도료 조성물.Powder coating composition comprising at least one of a urethane-modified epoxy resin and a bisphenol A-type epoxy resin, a curing agent and at least two extender pigments.
  2. 제1항에 있어서, 상기 우레탄 변성 에폭시 수지의 에폭시 당량은 250 내지 700 g/eq이고, 연화점은 100 내지 130 ℃이고, 점도(175 ℃, ICI 점도계)는 1,000 내지 3,500 cps이고, 유리전이온도는 50 내지 65 ℃인 분체도료 조성물.The method of claim 1, wherein the urethane-modified epoxy resin has an epoxy equivalent of 250 to 700 g/eq, a softening point of 100 to 130°C, a viscosity (175°C, ICI viscometer) of 1,000 to 3,500 cps, and a glass transition temperature Powder coating composition of 50 to 65 ℃.
  3. 제1항에 있어서, 상기 비스페놀 에이형 에폭시 수지의 에폭시 당량은 700 내지 1,500 g/eq이고, 연화점은 100 내지 130 ℃이고, 점도(200 ℃, ICI 점도계)는 1,000 내지 5,000 cps이고, 유리전이온도는 50 내지 80 ℃인 분체도료 조성물.The method of claim 1, wherein the bisphenol A-type epoxy resin has an epoxy equivalent of 700 to 1,500 g/eq, a softening point of 100 to 130 °C, a viscosity (200 °C, ICI viscometer) of 1,000 to 5,000 cps, and a glass transition temperature Powder coating composition of 50 to 80 ℃.
  4. 제1항에 있어서, 상기 우레탄 변성 에폭시 수지 및 비스페놀 에이형 에폭시 수지의 배합비는 1 내지 5 : 1 중량비인 분체도료 조성물.The powder coating composition according to claim 1, wherein the urethane-modified epoxy resin and the bisphenol A-type epoxy resin are mixed in a ratio of 1 to 5: 1 by weight.
  5. 제1항에 있어서, 상기 체질 안료는 탄산칼슘, 황산바륨, 장석 및 카오린으로 이루어진 군에서 선택되는 1종 이상을 포함하는 분체도료 조성물.The powder coating composition according to claim 1, wherein the extender pigment comprises at least one selected from the group consisting of calcium carbonate, barium sulfate, feldspar, and kaolin.
  6. 제1항에 있어서, 상기 체질 안료는 황산바륨 및 장석을 포함하고, 상기 황산 바륨 및 장석의 배합비는 1 : 0.5 내지 5 중량비인 분체도료 조성물.The powder coating composition according to claim 1, wherein the extender pigment comprises barium sulfate and feldspar, and the blending ratio of barium sulfate and feldspar is 1: 0.5 to 5 weight ratio.
  7. 제1항에 있어서, 분체도료 조성물 총 중량을 기준으로 우레탄 변성 에폭시 및 비스페놀 에이형 에폭시 수지 중 1종 이상 45 내지 90 중량%, 경화제 0.1 내지 5 중량% 및 체질 안료 5 내지 45 중량%를 포함하는 분체도료 조성물.The powder of claim 1, comprising 45 to 90% by weight of at least one of urethane-modified epoxy and bisphenol A-type epoxy resins, 0.1 to 5% by weight of a curing agent, and 5 to 45% by weight of an extender pigment based on the total weight of the powder coating composition. Paint composition.
PCT/KR2019/015957 2019-02-26 2019-11-20 Powder coating composition WO2020175766A1 (en)

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