WO2020141733A1 - Composition de revêtement transparent - Google Patents

Composition de revêtement transparent Download PDF

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Publication number
WO2020141733A1
WO2020141733A1 PCT/KR2019/016885 KR2019016885W WO2020141733A1 WO 2020141733 A1 WO2020141733 A1 WO 2020141733A1 KR 2019016885 W KR2019016885 W KR 2019016885W WO 2020141733 A1 WO2020141733 A1 WO 2020141733A1
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Prior art keywords
weight
resin
parts
coating composition
mgkoh
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PCT/KR2019/016885
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English (en)
Korean (ko)
Inventor
김맹기
정선화
최명기
형우찬
김창혁
문성희
Original Assignee
주식회사 케이씨씨
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Application filed by 주식회사 케이씨씨 filed Critical 주식회사 케이씨씨
Priority to CN201980086752.5A priority Critical patent/CN113227280B/zh
Priority to SG11202106801WA priority patent/SG11202106801WA/en
Publication of WO2020141733A1 publication Critical patent/WO2020141733A1/fr

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to a clear coating composition.
  • the outer plate of the vehicle body should be free from deterioration and rust of the coating film, and must have durability to maintain the gloss or color of the coating film. Therefore, in the coating process of a vehicle, after the electrodeposition coating of a vehicle body that has been subjected to a pre-treatment process, an intermediate coating is applied to improve adhesion and smoothness, and a base coating is applied to the vehicle body that has been coated in the middle for aesthetic appearance of the vehicle body. Thereafter, it is common to apply a clear coating film to protect the color of the base coating film, improve the appearance, and protect the base coating film from the outside.
  • thermosetting coating composition of a resin containing amino groups and an amino resin has been widely used.
  • parts made of plastic materials such as bumpers and rearview mirrors may deform or distort when the components are cured under high temperature curing conditions, so they must be separated from the vehicle body and separately painted. There was a hassle.
  • Patent Document 1 discloses a clear coating composition comprising two types of acrylic polyol resin, polyester polyol resin, reactive silicone additive and isocyanate curing agent.
  • the conventional low-temperature curing type clear coating composition such as the clear coating composition of Patent Literature 1
  • the present invention is to provide a clear coating composition capable of producing a coating film that is capable of curing at a low temperature of 120° C. or lower, but has excellent mechanical properties.
  • the present invention provides a clear coating composition
  • a clear coating composition comprising a silicone-modified polyester polyol resin, an acrylic polyol resin, a polyester resin and an isocyanate resin.
  • the clear coating composition according to the present invention can be cured at a low temperature of 120° C. or lower, thereby reducing the cost required during the coating process, and is economical.
  • the color can prevent different problems.
  • the coating film prepared from the clear coating composition is excellent in mechanical properties such as hardness, adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance, and thus can be usefully used for painting a body.
  • the clear coating composition according to the present invention includes a silicone-modified polyester polyol resin, an acrylic polyol resin, a polyester resin, and an isocyanate resin.
  • the silicone-modified polyester polyol resin serves to improve the scratch resistance of a coating film prepared from a composition comprising the same.
  • the silicone-modified polyester polyol resin may include a first repeating unit derived from an organic polysiloxane, a second repeating unit derived from a polyfunctional alcohol, and a third repeating unit derived from a polyfunctional carboxylic acid.
  • the silicone-modified polyester polyol resin may be composed of a first repeating unit derived from an organic polysiloxane, a second repeating unit derived from a polyfunctional alcohol, and a third repeating unit derived from a polyfunctional carboxylic acid. That is, the silicone-modified polyester polyol resin may be prepared by reacting an organic polysiloxane, a polyfunctional alcohol monomer, and a polyfunctional carboxylic acid monomer. As another example, the silicone-modified polyester polyol resin may be prepared by condensation reaction of an organic polysiloxane, a polyfunctional alcohol monomer, and a polyfunctional carboxylic acid monomer.
  • the organic polysiloxane may include functional groups and non-functional organic groups.
  • the organic polysiloxane may include at least one functional group selected from the group consisting of silanol and alkoxy groups, and may include at least one non-functional organic group selected from the group consisting of methyl, propyl and phenyl groups.
  • the alkoxy group include methoxy, ethoxy and butoxy groups.
  • the organic polysiloxane may have a number average molecular weight of 100 to 5,000 g/mol.
  • the organic polysiloxane may have a number average molecular weight of 200 to 5,000 g/mol, 300 to 5,000 g/mol, or 500 to 5,000 g/mol.
  • organic polysiloxane Commercially available products of the organic polysiloxane include Dow Corning's DC-3037, DC-3074, RSN-0217, RSN-0220, RSN-0233, RSN-0255 and RSN-6018, Wacker's SILRES series, SY300, IC836, REN168 , SY409, IC232, SY231, IC368, IC678, 601, 603, 604 and the like.
  • the polyfunctional alcohol monomer is, for example, ethylene glycol (EG), propylene glycol (PG), trimethylolpropane (TMP), trimethylolethane (TME), cyclohexanedimethanol, neopentyl glycol (NPG), 2 -Butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane It may be one or more selected from the group consisting of diol, triethylolpropane, glycerin and pentaerythritol.
  • the polyfunctional carboxylic acid monomer is, for example, phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, It may be one or more selected from the group consisting of methyltetrahydrophthalic anhydride, succinic anhydride, isophthalic acid, azlaic acid, maleic anhydride and trimellitic anhydride.
  • PA phthalic anhydride
  • HHPA hexahydrophthalic anhydride
  • methyl hexahydrophthalic anhydride methyl hexahydrophthalic anhydride
  • tetrahydrophthalic anhydride tetrahydrophthalic anhydride
  • the silicone-modified polyester polyol resin may be prepared by reacting 100 parts by weight of an organic polysiloxane, 300 to 800 parts by weight of a polyfunctional alcohol monomer, and 300 to 600 parts by weight of a polyfunctional carboxylic acid monomer.
  • the silicone-modified polyester polyol resin is 100 parts by weight of an organic polysiloxane, 400 to 700 parts by weight, or 500 to 650 parts by weight of a polyfunctional alcohol monomer and 350 to 550 parts by weight, or 400 to 500 parts by weight of polyfunctionality It can be prepared by reacting a carboxylic acid monomer.
  • the silicone-modified polyester polyol resin is prepared using the monomers in the above content range, there is an effect of improving appearance characteristics and scratch resistance of the coating film prepared from the coating composition containing the same.
  • the silicone-modified polyester polyol resin has a hydroxyl value (OHv) of 150 to 350 mgKOH/g, an acid value (Av) of more than 0 mgKOH/g and 30 mgKOH/g or less, a number average molecular weight (Mn) of 100 to 10,000 g/mol, and It may have a glass transition temperature (Tg) of -50 °C to 30 °C.
  • the silicone-modified polyester polyol resin may have a hydroxyl value of 150 to 300 mgKOH/g, or 200 to 300 mgKOH/g, 1 to 30 mgKOH/g, or 1 to 20 mgKOH/g acid value, 100 to 5,000 g/mol, or a number average molecular weight of 100 to 2,000 g/mol, and a glass transition temperature of -30°C to 30°C, or greater than 0°C and 20°C or less.
  • the silicone-modified polyester polyol resin may be included in an amount of 1 to 30 parts by weight based on 1 to 30 parts by weight of acrylic polyol resin.
  • the silicone-modified polyester polyol resin may be included in an amount of 5 to 20 parts by weight, or 5 to 15 parts by weight based on 1 to 30 parts by weight of the acrylic polyol resin.
  • the acrylic polyol resin serves to impart coating properties to the composition.
  • the acrylic polyol resin may include a repeating unit derived from an ethylenically unsaturated monomer and a repeating unit derived from an acrylic monomer containing a hydroxyl group. That is, the acrylic polyol resin may be prepared by reacting an ethylenically unsaturated monomer and an acrylic monomer containing a hydroxyl group. For example, the acrylic polyol resin may be prepared by reacting an ethylenically unsaturated monomer, an acrylic monomer containing a hydroxyl group, and a radical polymerization initiator under a solvent.
  • the acrylic polyol resin may be prepared by reacting an ethylenically unsaturated monomer, an acrylic monomer containing a hydroxyl group, a non-functional acrylic monomer, a radical polymerization initiator, and a molecular weight modifier under a solvent.
  • the ethylenically unsaturated monomer may be at least one selected from the group consisting of styrene and derivatives thereof, butadiene, C 1-12 alkyl (meth)acrylic and C 1-12 alkyl (meth)acrylic acid esters.
  • the acrylic monomer containing the hydroxyl group is hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, kaduraacrylate, kaduramethacrylate, capro Lactone acrylate, caprolactone methacrylate, 2,3-dihydroxypropylacrylic, 2,3-dihydroxypropylmethacrylate, polypropylene modified acrylate, polypropylene modified methacrylate, 4-hydroxymethyl It may be one or more selected from the group consisting of cyclohexyl-methylacrylate, 4-hydroxymethylcyclo-methylmethacrylate and ethylenically unsaturated beta-hydroxy ester.
  • the ethylenically unsaturated beta-hydroxy ester may be prepared by reacting an ethylenically unsaturated acid monomer with an epoxy compound.
  • an ethylenically unsaturated acid monomer monocarboxylic acid, such as (meth)acrylic acid, is mentioned, for example.
  • the epoxy compound is not involved in radical polymerization, and examples thereof include glycidyl ether and glycidyl ester.
  • the non-functional acrylic monomer may be at least one selected from the group consisting of alkyl (meth) acrylate, cycloalkyl (meth) acrylate, and bicycloalkyl (meth) acrylate.
  • the non-functional acrylic monomer is methyl methacrylate, ethyl methacrylate, iso-butyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2- Ethyl hexyl methacrylate, iso-carbonyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, iso-butyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2 It may be one or more selected from the group consisting of -ethylhexyl acrylate, n-
  • the solvent is not particularly limited as long as it is a common solvent used in radical polymerization, and examples include aromatic hydrocarbon-based solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, and ethyl propyl ketone; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate and ethyl ethoxypropionate; And alcohol-based solvents such as n-butanol, propanol and 1-methoxy-2-propanol; and the like.
  • aromatic hydrocarbon-based solvents such as toluene and xylene
  • Ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, and ethyl propyl ketone
  • commercially available products of the aromatic hydrocarbon-based solvent include cocosol #100, cocosol #150, and the like.
  • the radical polymerization initiator is not particularly limited as long as it is a conventional polymerization initiator used in radical polymerization.
  • the molecular weight modifier is not particularly limited as long as it is a common one used in the production of acrylic polyols.
  • mercaptans such as n-dodecyl mercaptan, n-decyl mercaptan, and t-dodecyl mercaptan; And alpha methyl styrene dimers; And the like.
  • the acrylic polyol resin has a hydroxyl value of 80 mgKOH/g to 200 mgKOH/g, an acid value of more than 0 mgKOH/g and 30 mgKOH/g or less, a number average molecular weight of 1,000 to 10,000 g/mol, and a glass transition temperature of 0°C or more and 70°C or less.
  • the acrylic polyol resin has a hydroxyl value of 100 mgKOH/g to 200 mgKOH/g, an acid value of 1 mgKOH/g to 25 mgKOH/g, or an acid value of 5 mgKOH/g to 15 mgKOH/g, 1,500 to 7,000 g/mol, or 2,000 to 5,000 g It may have a number average molecular weight of /mol, and a glass transition temperature of 10°C to 70°C, or 20°C to 60°C.
  • the curability of the composition containing the same may be improved, and when the acid value is within the above range, the reactivity of the composition containing the same may be controlled to adjust the appearance characteristics of the coating film prepared therefrom.
  • the number average molecular weight is within the above range, the appearance properties and physical properties of the prepared coating film are appropriate, and when the glass transition temperature is within the above range, the initial hardness of the prepared coating film may be improved.
  • the acrylic polyol resin may be included in an amount of 1 to 30 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the acrylic polyol resin may be included in an amount of 5 to 20 parts by weight, or 5 to 15 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the polyester resin serves to improve the curing speed of the composition containing it.
  • the polyester resin may be synthesized directly according to a known method, or a commercially available product may be used.
  • the polyester resin can be prepared by reacting a carboxylic acid with a polyol.
  • the carboxylic acid is adipic acid (AA), isophthalic acid (IPA), phthalic anhydride (TMA), hexahydrophthalic anhydride (HHPA), cycloaliphatic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, ah It may be one or more selected from the group consisting of dipic acid, fumaric acid, maleic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, and derivatives thereof.
  • the polyol is methoxypolyethylene glycol, neopentyl glycol (NPG), trimethylol propane (TMP), 1,6-hexanediol (1,6-HD), ethylene glycol, propylene glycol, diethylene glycol, butanediol, It may be one or more selected from the group consisting of 1,4-hexanediol and 3-methylpentanediol.
  • the polyester resin may be in a liquid form having a solids content (NV) of 50 to 90% by weight based on the total weight of the resin.
  • the polyester resin may be in a liquid form having a solids content (NV) of 55 to 80% by weight, or 60 to 75% by weight based on the total weight of the resin.
  • VOC volatile organic compound
  • the polyester resin may have an acid value (Av) of 1 to 30 mgKOH/g, and a hydroxyl value (OHv) of 100 to 400 mgKOH/g.
  • the polyester resin may have an acid value of 10 to 30 mgKOH/g, or 15 to 25 mgKOH/g, and a hydroxyl value of 150 to 350 mgKOH/g, or 200 to 320 mgKOH/g.
  • the polyester resin may have a number average molecular weight (Mn) of 100 to 700 g/mol.
  • Mn number average molecular weight
  • the polyester resin may have a number average molecular weight of 200 to 600 g/mol, or 250 to 500 g/mol. When the number average molecular weight of the polyester resin is within the above range, there is an effect of excellent curing density.
  • the polyester resin may be included in the composition in an amount of 5 to 40 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the polyester resin may be included in the composition in an amount of 10 to 30 parts by weight, or 15 to 25 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the isocyanate resin serves to form a coating film by crosslinking the components in the composition and curing the composition.
  • the isocyanate resin is composed of an isocyanurate group, an uretdione group, a biuret group, a urethane group, an allophanate group, and an iminooxadiazinedione group. It may include one or more functional groups selected from the group. That is, the isocyanate resin is an isocyanurate group, an uretdione group, a biuret group, a urethane group, an allophanate group, and an iminooxadiazinedione It may be an isocyanate containing at least one functional group selected from the group consisting of groups.
  • the isocyanate resin may be prepared from aliphatic or alicyclic isocyanates.
  • the isocyanate resin includes aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; And 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), bis-(4-isocyanatocyclohexyl)-methane, Alicyclic isocyanates such as 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4-hexahydrotoluylene diisocyanate and 2,6-hexahydrotoluylene diisocyanate ; Can be prepared from.
  • the isocyanate resin is 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane and bis-(4-isocy Anatocyclohexyl)-methane.
  • the isocyanate resin may be included in an amount of 10 to 40 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the isocyanate resin may be included in an amount of 15 to 35 parts by weight, or 20 to 30 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the content of the isocyanate resin is within the above range, it is possible to prevent a problem that a composition has insufficient reactivity, resulting in a decrease in curing density, and an unreacted substance in the coating film after curing, resulting in deterioration in properties of the coating film.
  • the coating composition may further include an organic solvent.
  • the organic solvent serves to improve the workability of the composition by adjusting the viscosity of the coating composition.
  • the organic solvent may include one or more selected from the group consisting of aromatic, acetate-based, alcohol-based and propionate-based.
  • the organic solvent is an aromatic solvent such as toluene and xylene; Acetate-based solvents such as 1-methoxy-2-propyl acetate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, dimethyl glutarate, dimethyl succinate and dimethyl adipate; alcohol solvents such as n-butanol, propanol and 1-methoxy-2-propanol; And propionate-based solvents such as ethyl ethoxy propionate.
  • commercially available products of the aromatic solvent include cocosol #100, cocosol #150, and the like.
  • commercially available products of the acetate solvent include Rhodiasolv RPDE from Solvay.
  • the organic solvent may be included in an amount of 5 to 60 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the organic solvent may be included in an amount of 10 to 50 parts by weight, or 10 to 45 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the coating composition containing the same has an effect of having excellent workability during painting.
  • the clear coating composition may further include one or more additives selected from the group consisting of flow control agents, curing catalysts, wetting agents, light stabilizers, ultraviolet absorbers, antifoaming agents, surface conditioners and leveling agents.
  • the additive may be included in an amount of 1 to 40 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the additive may be included in an amount of 1 to 35 parts by weight, or 1 to 30 parts by weight based on 1 to 30 parts by weight of the silicone-modified polyester polyol resin.
  • the flow modifier serves to improve the workability of the composition by regulating the composition's sagging.
  • the flow control agent may be, for example, an acrylic resin having a diurea group.
  • the flow-rate modifier is a needle-shaped diurea group obtained by reacting an alkyl acrylate such as butyl acrylate or an alkyl methacrylate such as butyl methacrylate with 1,6-hexamethylene diisocyanate and benzyl amine. It may be an acrylic polyol resin having a containing structure.
  • the curing catalyst serves to prevent the incomplete curing of the coating composition, thereby improving the mechanical properties of the coating film prepared therefrom.
  • the curing catalyst may be at least one selected from the group consisting of dibutyltin dilaurate, triethyl amine, diethylenetriamine, bismuth carboxylate, and zirconium chelate.
  • wetting agents serve to improve the leveling properties and wettability of a coating film prepared from a composition comprising the same, and are not particularly limited as long as they are commonly used in coating compositions.
  • the wetting agent may be a silicone acrylate-based or acetylene alcohol-based wetting agent.
  • the light stabilizer serves to improve weather resistance.
  • the light stabilizer may be used without particular limitation, as long as it is a conventional one that can be used in the coating composition, for example, hindered amine-based.
  • the hindered amine light stabilizer is 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like. have.
  • the ultraviolet absorber absorbs ultraviolet rays to prevent discoloration of the coating composition, and serves to prevent swelling, delamination, and loss of gloss of the coating film prepared from the coating composition.
  • the ultraviolet absorber may be used without particular limitation as long as it is a common one that can be used in the coating composition, and examples thereof include benzotriazole-based hydroxyphenyl benzotriazole.
  • Tinuvin 384 of BASF is mentioned.
  • the anti-foaming agent serves to suppress the generation of air bubbles generated during the preparation of the coating composition and to suppress or remove phenomena such as pinholes or popping caused when the coating film is formed.
  • the antifoaming agent may be used without particular limitation as long as it is a conventional one that can be used in the coating composition.
  • commercial products of the antifoaming agent include BYK-011, BYK-015, BYK-072 from BYK, DF-21 from Air Product, agitan 281 from Munzing, and Foamster-324 from Sannovko.
  • the surface adjuster serves to control the smoothness of the coating layer by adjusting the surface tension after application of the coating composition, and can be used without particular limitation, as long as it is a common one that can be used in the coating composition.
  • the surface modifier may be a surfactant, for example, a silicone-based surfactant.
  • the leveling agent imparts smoothness to the coating composition, thereby improving the appearance characteristics of the coating film prepared therefrom, thereby suppressing the occurrence of orange peel.
  • the leveling agent can be used without particular limitation as long as it is a conventional one that can be used in the coating composition.
  • the clear coating composition may be a two-component coating composition comprising a main portion and a curing agent portion.
  • the clear coating composition may be used after mixing the main part and the curing agent part before application.
  • the main part includes a silicone-modified polyester polyol resin, an acrylic polyol resin, a polyester resin and an organic solvent
  • the curing agent part includes an isocyanate resin and an organic solvent
  • an additive is included in at least one of the main part or the curing agent. can do.
  • the clear coating composition may have a solid content (NV) of 40% to 70% by weight.
  • the clear coating composition may have a solid content of 40% to 65% by weight, for example, 45% to 61% by weight.
  • the coating workability of the composition may be improved.
  • the clear coating composition can be cured at 60 °C to 120 °C.
  • the clear coating composition may be cured at 70 °C to 110 °C, or 80 °C to 110 °C. Since the clear coating composition is curable within the temperature range, it is economical to reduce the cost required during the painting process, and it is economical, and it is possible to integrally coat the vehicle body and material parts coupled thereto, so that the color of the parts and the vehicle body after painting Different problems can be avoided. In addition, since it is possible to coat both the vehicle body and the parts in one coating process, it is possible to reduce process hassle and cost loss.
  • the clear coating composition may have a viscosity of 10 to 40 seconds based on the number 4 pod cup.
  • the clear coating composition may have a viscosity of 15 to 35 seconds, or 20 to 35 seconds based on the number 4 pod cup.
  • the viscosity of the clear coating composition is less than 10 seconds, problems such as vertical surface flow may occur, and if it is more than 40 seconds, the viscosity of the composition is high, thereby deteriorating the appearance characteristics of the coating film produced therefrom or the load on the sprayer. It can cause a sprayer malfunction.
  • the clear coating composition according to the present invention as described above can be cured at a low temperature of 120° C. or lower, thereby reducing the cost required during the coating process, and is economical. After that, it is possible to prevent the problem of different colors of the parts and the body. In addition, since it is possible to coat both the vehicle body and the parts in one coating process, it is possible to reduce process hassle and cost loss. Furthermore, the coating film prepared from the clear coating composition has excellent mechanical properties such as appearance properties, adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance, and thus can be usefully used for car body coating.
  • functional groups such as'acid value' and'hydroxyl value' of the resin can be measured by methods well known in the art, and for example, may represent a value measured by a titration method.
  • the'number average molecular weight' of the resin may be measured by a method well known in the art, for example, may represent a value measured by a method of gel permeation chromatograph (GPC).
  • GPC gel permeation chromatograph
  • the'glass transition temperature' of the resin may be measured by a method well known in the art, for example, may indicate a value measured by a differential scanning calorimetry (DSC) method.
  • DSC differential scanning calorimetry
  • the obtained silicone-modified polyester polyol resin-1 had a number average molecular weight of 928 g/mol, a hydroxyl value of 250 mgKOH/g, an acid value of 10 mgKOH/g, a glass transition temperature of 10°C, a solid content of 70% by weight, and a Gardner viscosity Y property. Had.
  • the obtained silicone-modified polyester polyol resin-2 had a number average molecular weight of 1,018 g/mol, a hydroxyl value of 133.7 mgKOH/g, an acid value of 35 mgKOH/g, a glass transition temperature of -10°C, a solid content of 70% by weight, and a Gardner viscosity Y. Had physical properties.
  • a four-necked flask equipped with a thermometer, stirring device, condenser and heating equipment 155 parts by weight of Cocosol #100, 15 parts by weight of ethyl ethoxypropionate and 148 parts by weight of glycidyl ester (HEXION, CADURA E10P) were purchased. The temperature was raised to 150°C. Thereafter, when the temperature was stable to isothermal, the monomer mixture was added dropwise for 300 minutes, and then isothermal was maintained for 120 minutes.
  • the monomer mixture was prepared by mixing 208 parts by weight of styrene, 125 parts by weight of hydroxyethyl methacrylate, 54 parts by weight of acrylic acid and 20 parts by weight of tertiary butyl peroxide.
  • reaction product was cooled to 80° C., and 100 parts by weight of butyl acetate and 100 parts by weight of Cocosol #100 were added and diluted to prepare an acrylic polyol resin.
  • the obtained acrylic polyol resin had a physical content of 60% by weight, a Gardner viscosity Z, a hydroxyl value of 150mgKOH/g, an acid value of 10mgKOH/g, a glass transition temperature of 40°C, and a number average molecular weight of 2,030g/mol in the total weight of the acrylic polyol resin.
  • the obtained polyester resin had physical properties of a number average molecular weight of 350 g/mol, a hydroxyl value of 255 mgKOH/g, an acid value of 20 mgKOH/g, a solids content of 75% by weight of the total weight, and a Gardner viscosity Z.
  • each component was stirred and mixed for 20 minutes at 1,500 rpm with a composition as described in Tables 1 and 2 below.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Silicone-modified polyester polyol resin-1 10 10 15 5 25 7 Silicone-modified polyester polyol resin-2 - - - - - - - Acrylic polyol resin 10 10 5 15 8
  • Polyester resin 20 28 23 22 16 35 Isocyanate resin 25 20 27 28 21
  • Curing catalyst 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • Surface modifier 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
  • UV absorber 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1
  • Cocosol #150 12.9 9.9 11.9 12
  • 12 12 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Silicone surfactant (BYK-331)
  • Hindered amine light stabilizer (BAu's Tinuvin 123)
  • Test Example Measurement of physical properties of the coating film prepared from the coating composition
  • the top coat (manufacturer: KCC, product name: WT3090) was applied to the specimen and dried to form a top coat of 15 ⁇ m thickness. Thereafter, the clear coating compositions of Examples and Comparative Examples were coated on the top coat and cured at 100° C. for 25 minutes to form a clear coat having a thickness of 40 ⁇ m.
  • the physical properties of the specimens were measured in the following manner, and the results are shown in Tables 3 and 4.
  • the clear coating film using a handgun spray (nozzle diameter: 1.5mm, air pressure: 4.5kgf / cm2 to maintain a constant), while maintaining a constant distance between the nozzle inlet and the specimen 30cm horizontally 40 ⁇ It was applied while moving at a speed of 50 cm/sec.
  • the hardness of the clear coating film was measured by the pencil hardness method. Specifically, 3B, 2B, B, HB, F, H, 2H and 3H were used to measure the maximum hardness without damaging the clear coating film (3B, 2B, B, HB, F, H, 2H) , 3H: thirteen ⁇ excellent).
  • the Go method 100 squares having a width of 2 mm and a width of 2 mm were made with a knife on the surface of the clear coating film, and then the square was removed using a tape to measure adhesion.
  • the measured adhesiveness is M-1 (very good) when 100 squares are 100% intact, M-2 (excellent) when the remaining square is 70% or more and less than 100%, M- when 50% or more and less than 70% 3 (normal), M-4 (bad) when 30% or more and less than 50%, M-5 (very bad) when less than 30%.
  • the heat treatment was repeated for a total of 3 cycles in one cycle, which was allowed to stand at room temperature for 20 minutes after heat treatment at 150°C for 20 minutes.
  • the specimen was immersed in a constant temperature water bath at 40° C. for 240 hours and left at room temperature for 1 hour, and then a peeling test was performed in the same manner as in the Go method of item (2), and the evaluation criteria were also applied.
  • 0.2 ml of 0.1 N sulfuric acid was added dropwise to the surface of the coated film of the specimen, and then treated in an oven preheated to 30° C. or higher for 150 minutes. At this time, the appearance of etching, staining or swelling of the portion where sulfuric acid was dropped on the specimen was visually observed to determine the highest temperature at which the specimen was not damaged as the acid resistance temperature.
  • the 20° gloss of the specimen was measured (initial gloss measurement), and the surface of the specimen was reciprocated 10 times using a wash resistance tester (manufactured by Amtec Kistler), and then the 20° gloss was measured. Subsequently, the initial gloss and the gloss after the surface treatment were calculated by using the following equation (1).
  • Gloss retention rate gloss after surface treatment / initial gloss ⁇ 100
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Solid content in total weight (% by weight) 52.6 50.4 56
  • Hardness F HB F
  • Water resistance M-1 M-1 M-1 M-1 M-1 M-2
  • Acid resistance 45°C 41°C 44°C 43°C 43°C 40°C Scratch resistance (gloss retention rate) 65% 60% 64% 63% 61%
  • Solvent resistance 10 minutes 9 minutes 10 minutes 10 minutes 10 minutes 10 minutes 8 minutes
  • Initial gloss 89% 84% 88% 89% 84% 85%
  • the coating films prepared from the clear coating compositions of Examples 1 to 9 were all excellent in hardness, adhesion, water resistance, acid resistance, scratch resistance, solvent resistance, and initial gloss.
  • the coating film prepared from the composition of Comparative Example 1 which does not contain a silicone-modified polyester polyol resin and Comparative Example 3 that does not contain a polyester resin lacks hardness and solvent resistance. Further, the coating film prepared from the clear coating composition of Comparative Example 2, which did not contain an acrylic polyol resin, had very poor adhesion and poor solvent resistance.
  • the clear coating composition according to the present invention can be cured at a low temperature of 120° C. or lower, thereby reducing the cost required during the painting process, and is economical. It is possible to prevent the problem of different colors of the parts and the body after.
  • the coating film prepared from the clear coating composition has excellent mechanical properties such as hardness, adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance, and thus can be usefully used for coating the body.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne une composition de revêtement transparent comprenant une résine de polyol de polyester modifiée par silicone, une résine de polyol acrylique, une résine de polyester et une résine d'isocyanate.
PCT/KR2019/016885 2018-12-31 2019-12-03 Composition de revêtement transparent WO2020141733A1 (fr)

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CN201980086752.5A CN113227280B (zh) 2018-12-31 2019-12-03 清漆组合物
SG11202106801WA SG11202106801WA (en) 2018-12-31 2019-12-03 Clear coating composition

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KR1020180173813A KR102242958B1 (ko) 2018-12-31 2018-12-31 클리어 도료 조성물
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KR102567438B1 (ko) * 2021-04-01 2023-08-16 주식회사 케이씨씨 저온 경화형 클리어 코트 조성물
KR102567354B1 (ko) * 2021-04-07 2023-08-16 주식회사 케이씨씨 클리어 코트 조성물
KR102583105B1 (ko) * 2021-05-03 2023-09-27 주식회사 케이씨씨 클리어 코트 조성물
KR102583106B1 (ko) * 2021-05-11 2023-09-27 주식회사 케이씨씨 클리어 코트 조성물

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JPH10101996A (ja) * 1996-10-01 1998-04-21 Toyota Motor Corp 一液低温硬化型着色エナメル塗料
JP2002114941A (ja) * 2000-07-31 2002-04-16 Nippon Paint Co Ltd 撥水性塗料用硬化性樹脂組成物及び塗装物
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CN113227280A (zh) 2021-08-06
KR102242958B1 (ko) 2021-04-21
KR20200082837A (ko) 2020-07-08
CN113227280B (zh) 2022-07-26
SG11202106801WA (en) 2021-07-29

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